12 Evaporation

If the temperature difference in a particular express the relationships for calculating the spe-
stage is insufficient to provide a natural, ther- cific heating steam consumption from the en-
mosiphon circulation, then the liquid circulation thalpies fixed by the job specification:
in the evaporators can be forced by installing
VH ∆hD hF −h∗F ∆hD hF −h∗F
pumps. This forced circulation leads to consider- = · = · (35)
able improvement in heat transfer with increas- D ∆hH h+F −hF
∗ ∆hH hF −hC
ing liquid velocity, and thus reduction in heat or
transfer surface. The optimal circulation veloc-
ity is that resulting in minimum total cost. VH ∆hD hC −h∗F
= · (36)
In the case of vapor recompression with an D ∆hH hF −hC
electrically driven compressor, the necessary en- Equation (37) fixes the enthalpy h+ F to which
ergy for compression increases with increas- the fresh feed can be warmed in the evaporated
ing difference in temperature between the con- vapor condenser:
densing heating vapors and the boiling solution,
ϑ = t H − t C . At the same time, however, the evap- h+ ∗
F =hF +hF −hC (37)
orator heating surface decreases. Consequently,
there is an optimal temperature difference at The ratio of inlet steam consumption to evapo-
which a minimal value in the total cost results. rated vapor produced is substantially higher than
The local conditions and specific energy costs that for a single-stage calandria heated evapora-
at the erected location of an evaporation system tor. The reason is that the evaporated vapor D
may materially influence the results of optimiza- raised in the flash separator drum at relatively
tion studies. For example, the cost of cooling high feed liquid preheat, even above the boiling
water in itself may be a decisive factor. temperature itself, makes up only a fraction of
the available liquid flow. Equation (38) gives this
ratio:
2.5. Evaporation Using Pressure +
Reduction D hF −hC hF −h∗F
= = (38)
F ∆hD ∆hD
Figure 9 A shows a flash vaporizer system con- The concentration ratio
sisting of a liquid heater, a separator drum for the
flash vapors formed on expansion, and a vapor ξF hF −hC
= 1− (39)
condenser. Frequently, this type of evaporation ξC ∆hD
scheme is employed for solutions inclined to-
is comparatively unfavorable. Its best value is set
ward forming deposits on or otherwise scaling or
by the maximum attainable feed liquid enthalpy
corroding the heat transfer surfaces. The nomen-
hF . Also, the feed liquid pressure upstream of
clature and units for the following discussion
the throttle valve depends on hF .
of the single-stage flash vaporizer in Figure 9 A
To improve the concentration ratio for a
generally follows previous usage.
single-stage flash vaporizer, an arrangement like
The enthalpy of fresh feed at hF ∗ increases to
in Figure 9 B is used. A pump is installed to re-
h+F in the vapor condenser and to hF in the steam- cycle a partial flow of flashed liquid to mix with
heated liquid preheater. The throttle valve main-
the fresh solution preheated in the vapor con-
tains the required pressure difference between
denser. Thus, liquid flow through the preheater
the liquid preheater outlet and the flash sepa-
increases by the factor f :
rator drum, (pF – p). The vapors D produced in
the flash separator drum condense in the vapor F +U
f= (40)
condenser. If the temperature drop for the con- F
densed vapors or steam in the heat exchangers
By this means the flow of vapor evaporated by
as well as any boiling point rise in the preheater
flashing is greater by the factor f than that with-
is neglected, then only the latent heats ∆hH of
out liquid recycle:
the heating steam in the preheater and that of the
vapors ∆hD in the condenser enter into consid- D hF −hC
= f· (41)
eration. Consequently, Equations (35) and (36) F ∆hD
 Evaporation 13

Also, the fresh feed solution is heated in the va- shows the unmistakably strong dependence of
por condenser to a higher enthalpy: the energy requirement on the number of stages
N, preheat temperature t F , as well as the temper-
h+ ∗
F =hF −f (hF −hC ) (42) ature difference ϑe between a flash vapor con-
Equation (43) also defines the characteristic fac- densing temperature and the outlet feed liquid
tor f , allowing calculation of the recycle flow by temperature of the respective condenser. With
Equation (44) as well as the heating steam con- respect to energy conservation, then, systems
sumption by Equation (45) with a large number of stages and thus higher
seawater preheat are especially suited for eco-
VH ∆hD 1 hC −h∗F nomically producing potable water.
= · · (43)
D ∆hH f hF −hC
U =F (f −1) (44)

VH ∆hD 1 hC −h∗F
= · · (45)
D ∆hH f hF −hC
Corresponding to the greater flow of evaporated
vapor in operation with liquid recycle, the con-
centrated solution has a higher solids concentra-
tion ξ C than that in operation without recycle,
Equation (46), as well as achieving a more fa-
vorable concentration ratio, Equation (47)
ξC
ξC = f −1
(46)
f − ξF /ξC

ξF hF −hC


= 1−f · (47)
ξC ∆hD

The multistage principle may also be applied to

flash vaporization to achieve better heat utiliza-
tion. A series of evaporated vapor condensers
preheats fresh feed solution to progressively
higher temperatures by condensing evaporated
vapors at progressively higher pressures. Inlet
steam completes solution preheating, followed
by successive stages of pressure reduction in
flash separator drums, generating vapors at the
pressures used in preheating. This brings the so-
lution to progressively higher solids concentra-
tion. Recovery of potable water from sea water to
Figure 10. Heat consumption of reduced pressure flash
a large extent makes use of this process of mul- evaporators as a function of number of stages, preheat tem-
tistage flash vaporization. In contrast to multi- perature, and temperature difference
stage calandria evaporators, multistage flash va-
porizers are notable for having no lower limit There are yet a number of other possible in-
with respect to the temperature difference bet- dustrial applications of flash vaporizers. Thus,
ween two neighboring evaporator stages. Thus, vacuum cooling units used in the potash indus-
at otherwise equal conditions, it is possible to try employ this principle of operation. These
build a flash vaporizer system with a substan- serve to cool hot salt solutions by removing heat
tially greater number of stages. through partial autovaporization in a series of
Relationships derived from heat and material vacuum vessels operating at stagewise decreas-
balances also permit engineering energy calcu- ing pressures.
lations for multistage flash vaporizers. Figure 10
14 Evaporation

3. Designing Evaporators for face of a large diameter, externally heated

Fabrication evaporator pipe. The pipe may be tapered.
Sometimes, the units are horizontal;
The decisive factors governing the selection of 11 H) Units with a rotating, externally
an evaporator design are the system capacity heated, conical vaporizing surface, with liq-
and the behavior of the feedstock from an op- uid flowing upward in a thin film, evenly dis-
erational viewpoint. For physically stable so- tributed by centrifugal force, often referred
lutions with little tendency toward scaling and to as molecular stills of the Hickman type;
corrosion, few operational upsets should be ex- 11 I) Units with no heating surface, consist-
pected, and comparatively simple and inexpen- ing of a simple flash separator drum, for flash
sive equipment design would normally be em- vaporization of preheated liquids.
ployed. But for heat-sensitive materials that are While Types 11 A – C employ the same op-
easily decomposed, a relatively expensive unit erating principle wherein the evaporation phe-
having a short product residence time and de- nomenon is coupled with liquid circulation, the
signed to operate at as low vacuum as possible remainder of the units function differently, and
would be necessary. The properties of the sub- there are fundamental differences among them.
stance, which are dependent on the pressure and In Types 11 A – E, the vapor forms in the pres-
temperature, as well as the vaporization behav- ence of a large flow of liquid. In contrast, in
ior, in turn dependent on the concentration of the Types 11 F – H, vaporization occurs from a liq-
solution, determine the equipment design con- uid film or a relatively thin layer. In Type 11 I,
cept. Figure 11 shows some design concepts fre- vaporizing the solvent is achieved by reducing
quently employed: the pressure on a preheated fresh solution.
11 A) Units with vertical evaporator tubes, The indicated differences relative to con-
heated on the outside, and having a central struction and manner of operation lead, in part,
downcomer for natural thermosiphon liquid to diverse operating conditions. Thus, for exam-
circulation, often referred to as calandria; ple, an agitated thin film evaporator, Type 11 G,
11 B) Units with vertical evaporator tubes, must operate with a higher temperature differ-
heated on the outside, contained in an exter- ence between heating medium and boiling liquid
nal heat exchanger, also with external down- to achieve high vaporization capacity. The rea-
comer for natural thermosiphon or forced son is a limitation of this construction in that a
liquid circulation; unit of given total volume can only accomodate
11 C) Units with sloping, or in the limiting a comparatively small heat exchanger surface.
case, horizontal evaporator tubes, heated on Table 1 presents a brief overview of the suit-
the outside, contained in an external heat ex- ability of the various vaporizer operating con-
changer, also with external downcomer for cepts for performing the tasks met in evaporation
natural thermosiphon or forced liquid circu- technology.
lation;
11 D) Units with horizontal, internally
heated evaporator tubes, immersed in the liq- 4. Design
uid, commonly referred to as kettles;
11 E) Units with vertical evaporator tubes,
4.1. Heating Equipment
heated on the outside, for once-through liq- In Types 11 A – E, the energy Q given up by the
uid flow from bottom to top; heating medium is imparted to the solution by
11 F) Units with vertical evaporator tubes, heat transfer through the exchanger tube walls.
heated on the outside, for liquid flow from For this, based on an expression for steady-
top to bottom, in accordance with the falling state transfer of heat through circular walls with
film principle; height H, inner diameter d i , and outer diameter
11 G) Agitated film evaporators, vertical d a , the following relationship applies:
units equipped with rotating wiper blades for
spreading the downward flowing liquid in an πH ϑ
Q= (48)
evenly distributed thin film on the inside sur- 1
αV da
+ 2λ1 ln dda + a 1d
W i L i
 Evaporation 15

Figure 11. Evaporator types

See the text for the description of the various types.
Table 1. Operating characteristics of various types of evaporators

Type of evaporator Viscosity, Evaporative capacity Tendency to salting Holdup time

Pa s and scaling

Natural circulation 0.05 small – large great very long

Forced circulation 1.0 small – large less very long
Climbing film 0.5 small – large great medium
Falling film 0.1 small medium – great short
Thin film 10 – 100 medium – large slight short
Flash 0.01 small – medium slight short – long

where K (W m−2 K−1 ) = overall coefficient of heat

transfer based on the average tube surface
Q (J/s) = heat transferred
sW (m) = tube wall thickness
H (m) = tube length
d i (m)= tube inner diameter For thin-walled heating surface of thick-
d a (m) = tube outer diameter ness sW , the following relationship results from
ϑ (◦ C) = effective overall temperature differ- Equation (48):
ence between heating medium and solu- 1
Q= ·A·ϑ (49)
tion on either side of the tube wall 1
αV
+ λsW + α1
λW (W m−1 K−1 ) = coefficient of thermal W L

conductivity For the case of an exchanger tube bundle with R

αV (W m−2 K−1 ) = film coefficient of heat tubes, Equation (50) gives the total heat transfer
transfer for the tube outer surface surface:
αL (W m−2 K−1 ) = film coefficient of heat di +da
A = R· ·π·H (50)
transfer for the tube inner surface 2
16 Evaporation

Then the expression for the overall heat transfer Frequently, however, the steam condenses on
coefficient K is: the wall in the form of droplets. For example,
this may occur when the steam or the heat-trans-
1
K = (51) fer surface is contaminated with oil or grease.
1
αV
+ λsW + α1 Then, the film heat-transfer coefficients may be
W L

about six to twenty times higher than those with

Equation (51) applies precisely for flat surfaces
pure film condensation. If the assumption that
only. But it may be used for round, thin-walled
the steam is practically static is not admissible,
evaporator tubes with sufficient accuracy for
then Equation (52) gives low numerical values.
equipment design.
According to the Nusselt theory, the equation for
If scaling or severe salting of the tube sur-
the film heat-transfer coefficient αV for flowing
face is expected, a thermal conductivity resis-
condensing saturated steam with the velocity uV
tance in the term sW /λW must be incorporated
then changes in accordance with the relation-
in determining the overall heat transfer coeffi-
ship:
cient K. Scaling or salting of the tube surface 
usually causes severe deterioration in the heat 3 C·∆hV ·K ·V ·λ2K ·u2V ·g
αV =K (53)
transfer. ηK ·ϑV ·H
The sum of the thermal conductivity resis-
Here, the constant is C = 10.5×10−4 .
tances sW /λW and the reciprocals of the film
The saturated steam available in industry is
coefficients 1/αV and 1/αL makes up the to-
usually contaminated with air or inert gases. This
tal thermal resistance 1/K. Tables of values for
air impurity can lead to a severe adverse effect
λW are available for the usual materials used in
on the film heat transfer coefficient for conden-
exchanger fabrication. In general, however, one
sation in heating equipment. Therefore, an im-
must calculate the film coefficients αV and αL ,
portant requirement in fabricating the evaporator
since they are dependent on the mechanical de-
heating element is an absolutely reliable means
sign of the particular unit and on the operating
for venting inert gases from the steam chest.
conditions. For rough estimations, a variety of
The basic types of industrial evaporation
average K values may be used.
equipment represented in Figure 11, in general,
Steam is the medium most often used for
show varied high heat transfer coefficients for
heating evaporators. The physical phenomenon
the boiling liquid. They vary in accordance with
is then a matter of virtually static, saturated
the operating conditions and the principles gov-
steam condensing as a liquid film on a vertical
erning the particular boiling behavior. Without
heating surface with the height H. If this flows
doubt, the nature and conditions for the hy-
continuously as a laminar film on the wall, then
draulic flow regime are determining factors for
one may calculate the film heat-transfer coeffi-
the film heat-transfer coefficient on the liquid
cient αV for the steady state in accordance with
side of the exchanger. Thus, in the case of recir-
the Nusselt film theory:
culating and once-through vaporizers, the pro-
 portion of vapor admixed in the boiling liquid is
4 ∆hV ·2K ·λ3K ·g
αV =K (52) a decisive factor. Then, according to whether nu-
ηK ·ϑH ·H
cleate or convection boiling takes place, distinct
where laws of physics and physical chemistry deter-
mine the film heat-transfer coefficient. The film
∆hv (J/kg) = latent heat of condensation of heat-transfer coefficient αL of the vaporizing so-
steam at the pressure in question lution can be represented as a function of char-
K (kg/m3 ) = density of the condensate film acteristic design parameters of the equipment,
λK (W m−1 K−1 ) = thermal conductivity of the values for the physical properties of the fluids,
condensate film and the operating conditions. These are com-
η K (kg m−1 s−1 ) = dynamic viscosity of the bined into various dimensionless numbers well
condensate film known in the general heat-transfer and fluid-flow
The value of the constant k in the equation is theory.
0.943. For the most part, industry is concerned with
vaporizing flowing or moving liquids. For va-
 Evaporation 17

Figure 12. The film heat-transfer coefficient for boiling water αL as a function of temperature difference ϑL

porizing liquids at rest, the film heat-transfer ter connected between the lower channel of the
coefficient of the boiling liquid αL character- exchanger and the liquid free vapor separation
istically depends on the temperature difference chamber. Empirically, one finds c = 0.24 at an
ϑL between the wall temperature on the liquid apparent level h = 75 % and c = 0.37 at an appar-
side t WL and the boiling temperature t C . Fig- ent level h = 40 %.
ure 12 shows, for example, the behavior for boil- Other nomenclature in Equation (54) is as fol-
ing water at 0.1 MPa. Only occasionally is this lows:
behavior found in vaporizing flowing liquids in σ L (kg/m) = surface tension of the boiling liq-
industrial equipment. uid in contact with its vapor
Representing heat transfer is made more dif- λL (W m−1 K−1 ) = thermal conductivity of the
ficult for vaporization in that one must deal, boiling liquid
in general, with a combined single phase – two cL (J kg−1 K−1 ) = liquid specific heat
phase flow condition. Therefore, predictive cal- ∆h (J/kg) = latent heat of vaporization of the
culation of the film heat-transfer coefficient ac- liquid
cording to the natural laws governing single- L (kg/m3 ) = density of the liquid
phase flow is limited only to special cases. For V (kg/m3 ) = density of the vapor in equilib-
the most part, semi-empirical relationships are rium with the liquid
used. Equation (54) is a dimensionless relation- η L (kg m−1 s−1 ) = dynamic viscosity of the
ship from Kirschbaum, making possible pre- fluid
dictive calculation of the film heat-transfer co-
efficient αL for boiling liquids in natural circu- In predictive calculation of the film heat-transfer
lation vaporizers, as in Figures 11 A and 11 B. It coefficient αL using Equation (54) the selected
agrees well with measured values. temperature difference ϑL should not be smaller

0.5
0.25 than the least temperature difference necessary
αL ·σL ϑL ·cL L ηH20 to stimulate natural circulation. This limiting
=c· (54)
λL ·p ∆h 103 V ηL temperature difference necessary to stimulate
The factor c depends on the apparent liquid level natural circulation may be taken from empiri-
h. The parameter h is the liquid holdup or liq- cally derived limit curves. These curves are also
uid inventory in an exchanger tube, which is de- necessary for design of multistage evaporators
fined as the height of a column of clear liquid, as they identify the relationships that limit the
expressed as a percentage of the tube length mea- number of stages.
sured upward from the lower tube sheet of the Figure 13 reproduces examples of such limit
exchanger, which would appear in a manome- curves. They show the dependence of the appar-
18 Evaporation

ent liquid level h on the temperature difference Table 2. Overall coefficient of heat transfer for some modes of op-
ϑL between the inside tube wall temperature t WL eration
and the boiling temperature t C with t C as a pa-
Overall coefficient of heat transfer k, W m−2 K−1
rameter. These limit curves are typical of those
showing operating points at which natural circu- Natural circulation, viscous solution 350 – 900
Natural circulation, mobile solution 600 – 1800
lation just ceases. At operating conditions lying Forced circulation 900 – 2900
in the area below the curves, natural circulation
will not automatically initiate nor continue if ini-
tiated at other conditions. As compared to evaporators with vertical
tubes, units with inclined tubes have the ad-
vantage that the liquid holdup can be held rela-
tively low in proportion to the evaporator capac-
ity, achieving the desired concentration for the
recycle liquid in short residence times. There-
fore, evaporation of temperature-sensitive solu-
tions or materials inclined to discolor or precip-
itate deposits even at still higher temperatures is
made possible. A further advantage over evapo-
rators with vertical tube arrangements is that the
construction results in a lesser liquid hydrostatic
pressure in the tubes. In turn, a much lower boil-
ing point rise results, which causes a substan-
tially lesser deterioration in the total temperature
difference in the evaporator system. Heat-trans-
Figure 13. Natural circulation limit curves at various boil- fer measurements have been made on operating
ing temperatures evaporators not only with vertical but also in-
clined vaporizer tube arrangements. These show
For evaporating solutions having severely that inclined tube evaporators have substantially
corrosive characteristics, systems using compar- higher heat-transfer coefficients than those with
atively expensive materials of construction for vertical tubes. Figure 14 reproduces these mea-
the heat-exchange surfaces must be designed. surements.
This sets a requirement for designing relatively
small evaporator heat-exchanger elements. In
turn, this may lead to a need for increasing the
velocity of the recirculating, vaporizing liquid.
The Nusselt – Kraussold equation may be
used for calculating the inside film heat trans-
fer coefficient αL for boiling liquid in tubes in
forced circulation evaporators:

0.8
0.37
λL uL ·di L cL ·ηL L
αL = 0.032
di ηi λL

0.054
H
(55) Figure 14. Heat-transfer coefficient in vertical and inclined
di tubes
Equation (55) applies when the liquid-side tem- Figure 11 D shows that kettle-type units, with
perature difference ϑL = (t WL – t L ) ≤ 6 ◦ C and horizontal heat exchanger tubes immersed in
the Reynolds number exceeds 10 000; H denotes the liquid, have an advantage that a still lesser
the tube length and d i its inner diameter. Table 2 level of liquid suffices to envelop the tubes and
contrasts ranges of film heat-transfer coefficients wet them completely. As a result, the vaporiz-
commonly experienced in natural and forced cir- ing liquid is under a low hydrostatic pressure
culation evaporators with one another. and at a boiling temperature only slightly above
 Evaporation 19

the saturated vapor temperature obtaining at the a device that distributes it over the outer surface
pressure in the vapor separation chamber. This of the tube bundle. Here it vaporizes from a thin
type of unit is also able to operate comparatively liquid film. This principle of operation totally
well in vaporizing solutions that foam severely. avoids the disadvantage of any elevation of the
The concept generally permits greater area for boiling point by liquid static pressure. Beyond
vapor – liquid release and allows better separa- that, is the advantage that the liquid inventory
tion of entrained liquid droplets resulting from required for operating the evaporator is compar-
the bubbling and foaming than evaporators with atively small.
vertical tube arrangements. Additionally, related also to a low liquid in-
At small temperature differences, in kettle ventory, the residence time of the feed material
units, free convection is the heat-transfer mech- in the unit can be a deciding factor in the choice
anism on the liquid side. This initiates vaporiza- of evaporator type. Many evaporating solutions
tion at the surface with only slight superheat- incline toward undesirable chemical or physical
ing of the liquid. Therefore, the laws govern- changes if they are exposed too long to temper-
ing heat transfer by free convection apply. At atures too high. To be able to vaporize even such
higher temperature differences, nucleate boiling solutions gently requires evaporators having low
begins. For both boiling regimes, the film heat- residence time for the evaporating material. At
transfer coefficient αL depends on the temper- present, with the normal recirculating evapora-
ature difference ϑL and is characterized by the tors, to achieve the desired concentration the
relationship: liquid undergoes repeated recycling through the
equipment. Moreover, it is exposed to the evap-
αL =C ·ϑn
L (56) orating temperature for a comparatively long
time. Thus, for concentrating thermally unstable
In the free convection regime, n = 0.33. For nu- solutions, a type of evaporator permitting more
cleate boiling, the value of n is in the range gentle treatment of the solution should be in-
2 – 5. The liquid film heat-transfer coefficients stalled: that is, one in which the liquid reaches its
for submerged tube evaporators, however, are specified final concentration after only one pass
not as favorable as, for example, for circulating through the vaporizer tubes. Designs are avail-
vaporizers with vertical tubes. Figure 15 shows able in which the product stream flows not only
this comparison. from bottom to top, Figure 11 E, but also from
top to bottom, Figure 11 F. If the space available
does not permit the required height, then, in any
case, the desired final concentration may be at-
tained by linking several units together in series
each having shorter vaporizing tubes.
For units with upward product flow, if the
superficial velocities (based on the inside cross-
sectional area of a tube of diameter d i ) not only
of the liquid phase, index L, but also of the va-
por phase formed by boiling, index V, are known,
the film heat-transfer coefficient for liquid boil-
Figure 15. Heat-transfer coefficient in recirculating and
ing may be calculated by a relation developed
submerged tube evaporators by Coulson and McNerly:


1.3 + 128di cL ηL L 0.9
In addition to the construction shown in Fig- αL = ·λL ·
di λL
ure 11 D, horizontal heat exchangers having two


tube sheets are also in use. This style of evapora- uV di V 0.34 uL di L 0.23
· ·
tor also finds application as a trickle film vapor- ηV ηL

0.25
izer, for example, for seawater desalting or in the L ηV
· (57)
refrigeration industry. In these, there is a liquid V ηL
sump underneath the tube bundle. A pump re- A principal field for once-through evaporators
moves solution from the sump and conveys it to is the concentration of solutions of alkalis and
20 Evaporation

Figure 16. Heat-transfer coefficient for surface evaporation of refrigerant R11 in a falling film

Figure 17. Heat-transfer coefficient for a falling film evaporator as a function of the feed rate
v = feed evaporated, % and ϑ = temperature difference between the steam and the boiling liquid

salts: NaOH, KOH, Na2 S, and CaCl2 . In these heated, enters the unit above the upper tubesheet.
applications, frequently, two-stages systems are Suitable devices distribute the liquid uniformly
installed with total utilization of the solvent va- among the outside heated evaporator tubes. The
pors. The first stage is a once-through vapor- liquid then flows downward with partial vapor-
izer, preconcentrating the solution from about ization as a thin film on the inner tube walls.
50 – 75 % by weight salts, while the main thick- The momentum of the likewise downward flow-
ening to 99 % solids takes place in a falling film ing evaporated vapors assists in accelerating liq-
evaporator. uid downflow, reducing liquid film thickness.
The evaporating liquid flows downward in This means of operation results in a substan-
a falling film evaporator. Liquid, usually pre- tially lesser liquid residence time even than that
 Evaporation 21

for the once-through vaporizer. In single-stage of the trickling film, taking into account the tem-
systems, the residence time is less than a minute, perature drop ϑL between the tube inner wall and
in comparison to the recirculating evaporators, the surface of the film.
an advantage in evaporating heat-sensitive solu-
tions.
In determining the film heat-transfer coeffi-
cients on the liquid side of falling film evapora-
tors, the physical laws valid for trickling films
are valid if conservative. In so doing, the purely
laminar region, the pseudo laminar or wavy lam-
inar region, the transition region, and, finally,
the turbulent region are differentiated. In these
differing regions, heat-transfer phenomena obey
different laws for the trickling film since the av-
erage film thickness, the film configuration, and
the discharge velocity are different. The mea-
sured results shown in Figure 16 illustrate this.
The data apply to vaporizing a trickling film of
refrigerant R11 on a clean surface with fully de-
veloped flow. Figure 16 shows the dependence
of the film heat-transfer coefficient of the va-
porizing, trickling film αL on the specific liquid
loading l (kg m−1 h−1 ) or l (m3 m−1 h−1 ), the
amount of liquid that flows down 1 m of tube cir-
cumference in 1 h. Since the principal liquid side
heat-transfer resistance itself lies in the trickling
film (for purely laminar flow, the region on the
left of Figure 16) Equation (58) permits deter-
mination of αL : Figure 18. Falling film evaporator with circulating pump

∆h2L  3  An important prerequisite for smooth opera-

αL = s − s3u (58)
3ηL ϑL H 0 tion of a falling film evaporator and for effective
heat transfer is complete wetting of the heating
The film thickness, so at the feed entry posi- surface. This means that, in design, the specific
tion, i.e., the upper end of the tube, for lam- liquid loading l 0 (m3 h−1 m−1 = m2 /h) must be
inar film velocity distribution, is given by the chosen with care so that it is not too small. To
Hagen – Poiseuille law when the quantity of liq- achieve sufficiently high film heat-transfer co-
uid feed L o (kg/h) fed to each evaporator tube efficients, Figure 17 shows that the specific feed
with inside diameter d i is known: quantity at the upper end of the tube l 0 should
  be:
3ηL L0 3 3ηL l0
s0 = 3
= (59)
2L πdi 3600 2 ·3600 l0
> 1.0 − 1.5m3 h−1 m−1 = m2 h−1 (61)

Equation (60) allows calculation of the film In industrial systems, in special cases, deal-
thickness su at the lower end of the tube with ing with evaporative degassing, for example,
length H(m), i.e., at the outlet position: smaller liquid loading values are chosen as well,
as low as l 0 = 0.3. But otherwise, l 0 values fre-

4λL ηL ϑL H quently lie above 2 m3 h−1 m−1 .
su = 4
s4D − (60) Using a recycle pump for recycling liquid to
∆h2L
achieve complete tube surface wetting is com-
In Equations (58) – (60), the liquid-film material mon, for example, for falling film evaporators
properties are taken at the average temperature in the edible oils industry. Figure 18 shows a
scheme for thermally separating free fatty acids
22 Evaporation

from nonvolatile residue. Since such systems op- on the tube circumference l 0 can be maintained
erate at high vacuum, less than 1 kPa, one must high enough that the system can operate with-
take care in design that the vapors developed do out a recycle pump. This design has proven to
not cause an inadmissably high pressure drop. be advantageous as the final stage in fatty acid
By dividing the heat-exchange surface into more evaporation systems.
than one bundle and removing the device for Table 3 lists parametes, including heat-trans-
separated vapor withdrawal from the exchang- fer coefficients, for some falling film evaporators
ers, the vapor hydraulic losses can be held cor- from operating industrial systems.
respondingly low. Relatively small temperature differences bet-
ween heating medium and evaporating liquid, as
little as 4 ◦ C, are possible in operating falling
film evaporators. Moreover, the design excludes
superheating the liquid due to static liquid head.
Thus, at a given operating pressure, the boiling
temperature is lower than in conventional evapo-
rators. At a liquid viscosity of about 1 kg/ms, the
lower limit of pressure is an operating vacuum
of about 4 kPa.

Figure 20. Wiper systems for thin film evaporators

Figure 11 G illustrates a thin film evapora-

tor with rotating internal element. These are
suited for heat-sensitive products requiring low
Figure 19. Falling film evaporator with partial countercur- evaporator operating pressures, down to 0.1 kPa,
rent and partial cocurrent flow of liquid and vapor
and having liquid viscosities far above 1 Pa s.
In principle, it is also possible to design units Mechanical wipers rotate inside an externally
in which vapor and liquid flow partially cocur- heated cylindrical shell, as shown schematically
rently and partially countercurrently to one an- in Figure 20. They produce sufficiently intensive
other, as in Figure 19. By varying the number of agitation to develop thin films even with high
tubes in the respective separate exchanger bun- viscosity liquids. The film thickness varies in
dles or changing the tube diameter along the di- the range 0.5 – 2 mm depending on the design
rection of liquid flow, the specific liquid loading and the speed of rotation. The product residence
 Evaporation 23
Table 3. Coefficient of heat transfer for some industrial applications of falling film evaporators

Falling film evaporator Styrene distillation Fatty acid distillation Fatty acid fractionation
∗
Tube dimensions, mm 38.1×2.64×3000 76.1×2.9×3000 76.1×2.9×3000
Area, m2 214.9 43.6 35
Steam temperature, ◦ C 112.7 251 266
Boiling point, ◦ C 98.0 230 242
Heat-transfer coefficient,
W m−2 K−1 670 400 400
∗
inner diameter (d i ) × wall thickness (sw ) × height (H)

time, depending on the loading conditions, may uw (m/s) = wiper circumferential speed
be even less than that for falling film evaporators. d w (m) = wiper diameter
The liquid to be vaporized enters the unit f w (s−1 ) = wiper frequency
above the heated wall and distributes uniformly H (m) = length of the heated cylinder wall
around the circumference. The wiper system D (kg/h) = evaporator capacity in terms of sol-
provides for developing a thin liquid film which vent evaporated
flows downward along the hot wall under the in- d (kg m−2 h−1 ) = specific evaporator capacity
fluence of gravity while evaporating to a higher
Equation (63) gives the rotor rotational fre-
concentration. Designs using self-aligning, pen-
quency given the wiper circumferential speed:
dulum wiper systems and those using sliding
guide shoes have potential for thickening solu- 60 uw
ηr = · (63)
tions of solids to the point that the end product π dw
leaves the evaporator in powder form.
Recommended values for uw are 8 – 9 m/s for
Inherent in the design concept is that these
fixed and 3.5 – 4 m/s for movable wipers. For
evaporators must operate with a comparatively
thin film evaporators of industrial size, wiper fre-
large temperature difference. Now, since the thin
quencies f w from 15 to 20 have shown favorable
films produced by the rotating wiper systems re-
operating experience. Then, the wiper frequency
sult in residence times less than 1 min for the ma-
results from uw , f w , and the wiper diameter d w .
terial being concentrated, substantially higher
Figure 21 makes it possible to estimate the
temperatures may be used in evaporating solu-
expected heat-transfer coefficients for some uses
tions of temperature-sensitive substances than,
of industrial interest. Equation (64) defines the
for example, with circulating vaporizers.
specific evaporator capacity d. Equation (65)
Equation (62), a result of the experimental in-
shows the relationship between d, the average
vestigations of Dieter, permits calculating ap-
heat transfer coefficient k, and the assigned to-
proximate values of the film heat-transfer coeffi-
tal temperature difference between the heating
cients αL for thin-film evaporators with rotating
medium and the vaporizing liquid ϑ. Given the
internal elements:
solvent latent heat of vaporization ∆h and tem-

3 λL perature difference ϑ sets the specific evaporator
αL =K · di ·nr · 1/3 (62)
ηL capacity d:
The nomenclature for Equations (62) – (64) is D
d= (64)
as follows: di πH
ϑ
K = a constant with the numerical value 500 d = k· (65)
∆h
d i (mm) = internal diameter of the heating
cylinder wall Thin film evaporators with rotating internal
nr (min−1 ) = rotor rotational frequency elements are especially suited for tempera-
λL (W m−1 K−1 ) = thermal conductivity of the ture-sensitive materials that decompose eas-
liquid film ily or change chemically during evaporation
η L (kg m−1 s−1 ) = dynamic viscosity of the in conventional equipment. Condensation and
liquid film polymerization are among possible chemical
24 Evaporation

changes. Applications include concentrating heat-transfer coefficients at the particular posi-

substances whose taste and active ingredients tion considered on the vaporizer rotor at the vary-
are not permitted to degrade. Vaporizing fatty ing cone diameter d k .
acids or softeners, for example, requires low In addition, this principle of operation also
vacuum on the product side and high temper- creates favorable conditions for heat transfer on
ature on the heating medium side. For such the heating medium side of the vaporizer unit. If
cases, the heating medium often is Dowtherm, steam is that heating medium, then it condenses
an azeotropic mixture of diphenyl and diphenyl predominantly in the form of droplets whose size
oxide, or HT-OIL-C. Further fields of applica- decreases with increasing rotational frequency.
tion are concentration of fruit juices, milk, yeast, Now, since centrifugal force flings the conden-
pectin solutions, dyestuff solutions, gelatin so- sate drops off the condensing surface immedi-
lutions, glues, gums, plant extracts, recovery of ately after they are formed, the heat-transfer re-
drug extracts and serums, distilling solutions of sistance is substantially less than in conventional
organic solvents or mixtures of such with water, condensing systems. Consequently, the heat-
and partial separation of multicomponent mix- transer coefficients on the condensing steam side
tures. are about an order of magnitude higher than for
However, based on industrial experience, it pure film condensation of the heating steam.
is known that thin film evaporators with rotat- Operating thin film vaporizers having the de-
ing wipers are not successful in all cases for all sign concept shown in Figure 11 H best fulfills
thermally unstable materials. The reason is that the prerequisites for good heat transfer on both
even product residence times of one minute are sides of the heat-transfer wall of the vaporizer
too long. If product residence times of only one unit. Heat-transfer coefficients k are a factor of
second are required for liquids of high viscos- about two to four times higher, depending on the
ity, 20 kg/ms and more, for example, then con- thermal conductivity resistance of the vaporizer
ventional evaporators are not applicable or ac- wall, than, for example, those for conventional
ceptable only with limitations on product yield falling film vaporizers. This results in less heat-
and quality. A completely different design con- ing surface or even using a comparatively small
cept (Fig. 11 H) enables successful solution of temperature difference between heating medium
even these vaporizing problems. The advantage and product and thus a lesser wall temperature
inherent in this design is extremely mild vapor- on the product side. The high realizable heat
izing behavior. For example, the residence time transfer coefficients result in high specific evap-
in the actual vaporizing zone on the heat-transfer orating capacity and thus comparatively small
surface may even amount to only fractions of a equipment volume.
second. The heat-transfer coefficients vary over a
In this equipment, as in many designs of broad range in accordance with the vaporizer-
molecular distillation apparatus, the vaporizing rotor frequency, the physical property values
surface rotates. Under the influence of high cen- of the feed material at the operating con-
trifugal forces resulting from correspondingly ditions, as well as the state of the heating
high rotational frequency, the liquid spreads out medium, heating surface loading, and capacity.
in an extremely thin film moving at high ve- Numerical values for k range between 500 and
locity. Varying the feed rate and the rotor ro- 10 000 W m−2 K−1 . Total temperature differ-
tational frequency up to 1600 revolutions per ences ϑ may lie between 5 and 80 ◦ C. Whereas
minute permits stepfree adjustment of the film the high heat-transfer coefficients given in Ta-
thickness within defined limits. On the average, ble 4 are more typical of dilute solutions, heat-
under normal operating conditions, even with transfer coefficients calculated for vaporizing
comparatively viscous liquids, the film thick- liquids with high solids concentration would be
ness amounts to only ca. 0.1 mm. With rotational an order of magnitude lower. But even for such
speed adjusted to feed rate conditions and liquid evaporation problems, the figures given in Ta-
viscosity, the film thickness can successfully be ble 5 show the unmistakable advantages of the
held low in such equipment, even at relatively vaporizer with rotating heating surface, attest-
high liquid rates. This leads to comparatively ing convincingly to its far superior heat-transfer
high radial film velocities and to relatively high performance.
 Evaporation 25

Figure 21. Heat-transfer coefficients for thin film evaporators for some applications as a function of the specific evaporator
Table 5. Comparative design parameters for falling film and thin film evaporators for liquids with high solids content

Magnitude Falling-film evaporator Thin-film evaporators

with rotating wipers with rotating heaters

Luwa Rotafilm

A, m2 0.54 0.125 0.2 0.2

p, kPa 2.0 1.3 0.26 0.26 0.53
ϑ, ◦ C 37 31 74 40 40
k, W m−2 K−1 68 57 145 175 530

Table 4. Comparative design parameters for falling film and thin not the least in the foodstuff industry, for small
film evaporators
to medium capacities.
Magnitude Falling film Rotating heater At fixed operating conditions, the transfer-
surfaces rate coefficient k and the difference between the
sW , m 0.002 temperature of the heating medium t H and the
λW , W m−1 K−1 16.3 boiling temperature (t + τ ) set the size of the
tL , ◦ C 99
k, W m−2 K−1 730 2 900
heat-transfer surface A of the evaporator heat-
ϑ, ◦ C 40 10 ing element for the heat-transfer duty Q through
αH , W m−2 K−1 5 800 17 500 the equation:
αL , W m−2 K−1 925 6 100
t WL , ◦ C 130.4 103.8 Q
A= (66)
k {tH − (t+τ )}

Correspondingly, Equation (67) determines the

Installation of a thin film evaporator with size of the required heat-transfer surface for a
rotating heating surface is advantageous in all given evaporator stage of a multistage system,
cases for applications which require, in opera- where Qn is the stage duty. The temperature dif-
tion, the lowest possible wall temperature on the ference {tn−1 − (tn + τn )} refers to the differ-
product side. It is a relatively versatile device ence between the solvent saturation temperature
finding application in the chemical and pharma- corresponding to the pressure in the previous
ceutical industries, the edible oil industry, and stage and the boiling temperature in the stage
under consideration:
26 Evaporation

Qn The orientation of the vapor separation head

An = (67) relative to the evaporator heating element, its
kn {tn−1 − (tn + τn )}
design features, and the way in which the
vapor – liquid mixture is introduced, determine
the degree to which the unit will fulfill the afore-
mentioned requirements. Thus, among the ba-
sic conceptual evaporator designs shown in Fig-
ure 11, there are merely three principal vapor
separation head configuration variations. Fig-
ure 22 illustrates these.
The arrangement in Figure 22 A refers to sub-
merged tube vaporizers called kettles or for sim-
ple evaporator drums heated through the walls.
In these constructions, the vaporizing element
and the vapor separation chamber form a sin-
gle unit. The design in Figure 22 B illustrates
the vapor separation chamber arrangement cor-
responding to the Robert or calandria evaporator,
recirculating evaporators with external liquid
downcomers, as well as to once-through vapor-
izers. In these, the vapor – liquid mixture enters
the vapor separation head from below, directly
under a pool of accumulated liquid. Finally, the
design in Figure 22 C shows the configuration
for all recirculating evaporators with externally
arranged heat exchanger elements, falling film
evaporators with vapor separation chamber be-
low the exchanger, as well as vaporizers flashing
preheated solutions. This last arrangement has
the feature that the vapor – liquid mixture enters
the vapor head above the pool of accumulated
liquid. This allows the level of accumulated liq-
uid to be set comparatively low.
Thin film evaporators with rotating internal
Figure 22. Arrangement of the vapor separation chamber elements, in general, have no vapor separation
in various types of evaporators
chamber in the same sense as the designs shown
in Figures 22 A, B, and C. However, they do pos-
sess special internal devices for removing en-
4.2. The Vapor Separation Chamber trained liquid droplets from the vapor.
The vapor separation head is so dimensioned
The vapor separation chamber, or vapor head, that liquid contained in the separated vapor
has the job of separating the two phase, phase is limited to just the minimum physically
vapor – liquid mixture that flows into it from the attainable. This is in the form of small, entrained
evaporator heater element into its components. liquid particles corresponding in size to equilib-
The separated vapor should be free of entrained rium among the gravity, inertial, surface tension,
liquid particles. This will, insofar as is possible, viscous, and drag forces extant. Installing liq-
prevent fouling the condensing surface of the uid separators as illustrated in Figure 23 achieve
vapor condenser in single-stage systems or of further purification of the exiting vapor from
the vaporizing surface of the succeeding stage residual liquid. Setting the dimensions of the
in mul-tistage systems. For its part, the liquid vapor separation chamber determines the spe-
leaving the vapor separation chamber should be cific vapor volume per hour per cubic meter of
as completely free of vapor as is possible.
 Evaporation 27

chamber volume that a given head can handle the usual in practice. At lower pressure, the equa-
at the least liquid content. Empirical Equations tions give even higher vapor velocities. Then
(68) – (70) serve to calculate this flow of vapor Equation (73) sets the diameter d B of the vapor
v in accord with the three characteristic vapor separation chamber:
separation chamber configurations A, B, and C 
of Figure 22. These apply to a vapor separation 4D
dB = (73)
head pressure of 100 kPa. πuD D ·3600
Equation (68) applies to the case shown in
Figure 22 A where H v (m) is the height of Since the liquid density is practically indepen-
the vapor space measured from the liquid sur- dent of pressure, geometrically similar vapor
face to the demister pad or droplet separator. separation heads are then about equal in their
The most favorable vapor separation capacity separation effect when operating at equal ve-
v a (m3 m−3 h−1 = h−1 ) is : locity head. When the pressure differs from
100 kPa, the following relationship applies for
40 setting the vapor velocities uD in the vapor sep-
va = 500+ (68)
0.01+ (HV )3/2 aration chamber:
Extending Equation (68) gives Equation (69) ap-      
u2D ·D p1
= u2D ·D p = u2D ·D p (74)
plying to Case B where H w (m) is the height 2 n

of the accumulated liquid level in the vapor Operation of industrial evaporator systems
head and H v and va are as above. Then the shows that, even at comparatively low vapor ve-
most favorable vapor separation capacity vb locities in the vapor separation chamber, some
(m3 m−3 h−1 = h−1 ) is: liquid is always entrained by the flowing vapor
1 if no special measures are taken for their sep-
vb =va + (4500 − va ) (69) aration. Even using liquid separators, it is not
(1 + 1.1·HW )4
always possible to remove the smallest liquid
For Case C, the most favorable vapor separation droplets. In general, relying on the force of grav-
capacity vc (m3 m−3 h−1 = h−1 ) is constant: ity alone achieves a separation effect up to 70 %.
(vc )Hv >H = 7300 (70)
v

For operating pressures different from 100 kPa,

Equation (71), with the help of Equations
(68) – (70) and the pressure factor f read from
Figure 24, permits converting the most favorable
vapor separation capacities va , vb , and vc to the
revised pressure basis:
   
va,b,c =f · va,b,c p=1 (71)

For a given hourly evaporated vapor flow D

(kg/h) with density D (kg/m3 ), Equation (72)
determines the required height of the vapor sep-
aration head H v , where H v is the distance mea-
sured from the liquid surface to the demister pad
or droplet separator for removing entrained liq-
uid particles from the vapor stream:
1 D
HV = ·   (72) Figure 24. Pressure factor f for Equation (71)
d2B π/4 D va,b,c p
The stability of the liquid drops is a deter-
For the vapor separation chamber-free crosssec-
mining factor in designing liquid separators. The
tional area and water vapor at atmospheric pres-
We-ber number is the principal criterion for drop
sure, allowable vapor velocities uD of 1 m/s are
28 Evaporation

Figure 23. Liquid separators

stability. The Weber number is equal to the quo- ity force determines the effectiveness of sep-
tient of the velocity head arising from the va- aration of the liquid particles entrained by the
por flow external to the drop ps and the internal vapor. With an internally installed separator de-
excess pressure of the drop pu caused by the vice, impingement or centrifugal force or both
surface tension along the phase boundary bet- are controlling. Therefore, the degree of sepa-
ween the drop and vapor. In designing liquid ration depends on the extent to which use of
separating devices, the critical Weber number these mechanical forces permits smaller drops
of 22 should not be exceeded so that the larger to coalesce into larger ones. It is self-evident that
drops do not break up. From this condition, the physical properties like large density difference
relationship expressed by Equation (75) results between the phases and high surface tension of
for the highest allowable velocity in the separa- the separated liquid exert a favorable influence.
tor. This equation shows the dependence of the Then for any separator a minimum limiting drop
highest allowable velocity in the separator on the size exists such that drops of smaller size will no
surface tension of the liquid σ (kg/m), the vapor longer be separated.
density D (kg/m3 ), and the diameter d T (m), of Beds of packing are low-pressure drop de-
a liquid droplet. vices especially well suited for separation of liq-
 uid drops measuring down to about 300 µm. For
σ ring or saddle-shaped packings, the preferred
(uD )max = 4.7 (75)
D ·dT sizes to use are those with principal dimension
In industrial evaporator systems, the desired de- 15 – 25 mm. Because of their relatively thin wall
gree of purity of the vapors determines the type thickness, use of metal packings results in a
of separator device. For the most part, separa- lesser pressure drop than that for those manufac-
tors use reversal of the vapor flow and liquid tured from ceramic materials. Supported on ex-
flow or both to create impingement force or panded metal mesh, these packings should form
the many varieties of centrifugal force for liq- a bed of ca. 200 – 300 mm height across the total
uid drop separation. The designs used in prac- vapor head cross-sectional area under the vapor
tice, then, range from simple baffle and reversing head cover.
plates to cyclone type internals as well as packed If very small liquid droplets must be removed
beds and demister pads in the vapor separation from the vapor stream, the recommended device
chambers. Figure 23 shows a sampling of de- to install is a demister pad, comparatively tightly
sign concepts. A simple baffle plate suffices as woven wire mesh packings. At vapor velocities
a liquid separator if a vapor flow no more than 2 – 5 m/s, they can separate drops down to 3 µm
1000 – 2000 m3 /h escapes from each square me- in diameter. Moreover, for these materials, the
ter of liquid surface in the vapor separation drum. pressure drop amounts to 15 – 40 mm water col-
Consequently, in the free space of a va- umn per meter of packed height. Such demisters
por separation drum, predominantly the grav- make possible almost 100 % removal of liquid.
 Evaporation 29

5. Evaporator System Ancillary Likewise, if the condensation heat of vapors

Components from the last stage of a multistage evaporator
is not utilized in some other manner, then they
A number of additional engineered instrument must be condensed in a condenser. The same ap-
or equipment items are necessary for operat- plies to the so-called residual vapors from vapor
ing an evaporator system. Thus, in most cases, recompression evaporators.
fresh feed solution requires preheating in a heat The first objective of vapor condensors is to
exchanger. These are heated either with evap- maintain the boiling pressure required in the
orated vapors, the hot concentrated product, or evaporator stage by continuously condensing
steam condensate from the evaporator heating the vapors developed and removing the noncon-
element. Not uncommonly, it is also necessary densable gases. Therefore, since often pressures
to degas the fresh feed solution before it enters must be held lower than one atmosphere, the
the evaporator to avoid corrosion. Frequently, it methods named are the simplest and most eco-
may also be necessary to free the concentrated nomic to produce the desired lower pressures. To
product from the evaporator of residual solvent the extent that the condenser operates in the neg-
components with a degassing step. Additionally, ative pressure domain, the vacuum pump con-
pumps are required for feeding the systems, to nected downstream serves to remove leakage air
produce recirculating flow, for product disposi- or other noncondensable gases. If the main pur-
tion, as well as for producing vacuum. Finally, it pose of the evaporation is recovery of the evapo-
is necessary to control the total system, consist- rated solvent when it is a valuable product, or to
ing of evaporators and auxiliary equipment, to recover the evaporated solvent in the pure form,
ensure an automatic and essentially upset-free, then condensing the vapors in a surface con-
safe operation. denser is the optimum industrial solution. This
applies to that vapor not condensed in the heat-
ing elements of the stages heated by evaporated
5.1. Indirect Heat Exchangers vapors in multistage evaporator systems.

Preheating, cooling, condensing, and degassing

require installing heat-exchange equipment. 5.2. Equipment for Direct Heat
These may employ direct or indirect heat trans- Exchange
fer as their principle of operation. In the indi-
rect method, the streams involved are sepa-rated Heat exchangers in which tube walls separate
from one another by a wall through which the the streams being cooled from the streams being
heat flows as a result of the difference in tem- heated are not always the optimum conceptual
perature. The direct method brings the streams solution to a heat-transfer problem. If the sub-
into intimate contact. Normally, most equipment stances taking part in the heat transfer are per-
for feed preheating or product cooling employs mitted to come in contact with one another, then
the method of indirect heat transfer. For pre- it may be possible to install equipment for heat
heaters heated by evaporated vapors as well as transfer directly between them. These units may
by product concentrate and condensate cooling, be less expensive than tubular heat exchangers.
units built as tubular exchanger bundles are usu- The so-called barometric condensers for con-
ally preferred. Depending on the operating con- densing vapor by direct heat exchange between
ditions and location factors, one may select ei- vapors and cooling medium belong to this field
ther a vertical or horizontal arrangement of the of evaporator design; likewise, the direct de-
tubes. Inclined tube arrangement applications gassing equipment for removing gases dissolved
remain limited to rare cases only. in the fresh feed solution to be evaporated. If not
Surface condensers for evaporated vapors degassed, corrosion or impairment in heat trans-
have an important position among heat exchang- fer could then result in the evaporator. Lastly,
ers using indirect heat transfer. Insofar as vapor the units for degassing the product concentrate
generated in single-stage evaporator equipment from the last evaporator stage by direct contact
is not used for preheating or degassing the fresh steam stripping are also in this group.
feed solution, it is condensed in a condenser.
30 Evaporation

Comparatively low installed cost distin- t to the final temperature t G . A vacuum pump
guishes the barometric condensers using cooling removes the noncondensable gases after sepa-
water to condense vapors in industrial systems ration of still entrained liquid droplets by a liq-
for evaporating aqueous solutions. The flow di- uid separator located immediately downstream
rection of the two media differentiates cocurrent of the condensing chamber.
(Fig. 25) from countercurrent (Fig. 26) baromet-
ric condensers. Based on economic considera-
tions, the latter are most frequently used.

Figure 25. Cocurrent flow barometric condenser Figure 26. Countercurrent flow barometric condenser
In barometric condensers, a direct heat ex- Through direct heat exchange, under other-
change takes place between vapor and cooling wise the same conditions, using a barometric
medium through intimate mixing of both mate- condenser permits achieving a usefully lower
rials. In barometric condensers operating coun- pressure than with a surface condenser. Equa-
tercurrently, the vapors D to be condensed with tion (76) gives the required cooling water flow
the enthalpy h enter the condenser at the bottom. for a countercurrent barometric condenser:
Of necessity, they rise countercurrent to the cool-
ing water W flowing from above. The condensed D (hD −hK ) +GcG (t−tG )
W = (76)
vapor leaves the unit together with the cooling hK −hW
water through the barometric leg. The cooling In Equation (76), cG (J kg−1 K−1 ) represents
water temperature rises from the inlet value t W the specific heat of the gas, and hW or hK (J/kg)
to the common end temperature t K . In general, are the enthalpies of the cooling water and of
the vapors entering the condenser contain non- the condensate. In this balance, heat losses are
condensable gases G. Especially when operating neglected.
under vacuum, this gas consists predominantly The cooling water consumption necessary for
of air leakage. But, in addition, depending on the required condensing capacity depends criti-
the nature of the solution to be evaporated, this cally on the temperature level of the exit cool-
gas may also contain small quantities of carbon ing water – condensate mixture. A high exit wa-
dioxide or ammonia, for example. In the con- ter temperature t K results in lower cooling wa-
denser, these gas flows are cooled from their in- ter consumption. On the other hand, the non-
let temperature, equal to the vapor temperature condensable gas outlet temperature t G also in-
 Evaporation 31

creases with an increasing value of t K leading to must be added to this minimum water column
an increase in the suction volume to the vacuum height. This takes into account the pressure drop
pump. One may estimate the value of t G from arising from the cooling water and condensate
the empirical equation: flow in the downcomer. The total height of the
liquid column thus determined, H = H min + 0.8
tG =tW +4 + 0.1 (tK −tW ) (77) (m), ensures positive removal of cooling water
and condensate. Simultaneously, it maintains the
In practice, with countercurrent barometric con- operating pressure in the condenser.
densers, an exit water temperature t K that is The barometric leg empties into a receiver
6 – 8 ◦ C less than the vapor temperature at the installed under it. The receiver must be so sized
condenser inlet has proven economical. that its capacity for liquid, beyond that for dis-
A barometric condenser must be designed so charge from the leg, is at least 1.5 times the vol-
that it achieves total vapor condensation. This ume of the leg.
requires a correspondingly large contact surface
area between the vapor and cooling water and
a sufficiently long residence time in the equip-
ment. Obtaining sufficient contact surface bet-
ween evaporated vapors and cooling water is a
matter of installing internal devices in the usu-
ally cylindrically shaped condensation cham-
bers. Suited for this, aside from packings, are
also contact trays as well as disc-and-doughnut
baffles or shower decks. Moreover, in addition,
designs are conceivable which spray the cool-
ing water into the condensing chamber through
atomizing nozzles to produce sufficiently high
contact surface.
With countercurrent barometric condensers,
if available equipment layout space permits suf-
ficient elevation of the condensation system, the
mixture of cooling water and vapor condensate
leaves the condensing chamber through a sim-
ple pipe downcomer or barometric leg. This sim-
ple construction concept makes the condensate
pump otherwise required, unnecessary or sim-
plifies its design, control, or operation. In sizing
the barometric leg, the water column existing in
the leg must compensate for the negative pres-
sure in the condensing chamber, in accordance
with the principles governing ducts connecting
to the surrounding atmospheric pressure. The
minimum height of this water column H min (m) Figure 27. Liquid degasser
is given by the following equation:
Degassing of liquids plays an important part
pu −p
Hmin  ·104 (78) in engineering evaporator systems. Liquids have
W
the tendency to dissolve gases, for example, air,
In Equation (78), pu (Pa) represents the ambient carbon dioxide, ammonia, oxygen and the like,
pressure, p (Pa) the negative pressure prevailing in small quantities. Then, when the liquid warms
in the condenser, and W the density of water, to the boiling point, the gases are almost com-
which, as a practical matter, may be set equal to pletely eliminated. If they are not removed in a
1000 kg/m3 . At a flow velocity of ca. 1 m/s, an timely manner, they may concentrate in the sys-
additional liquid head of a maximum of ca. 0.8 m tem and cause problems, e.g., deterioration in
32 Evaporation

heat transfer in steam heated equipment, or per- the lower portion even above 175 ◦ C. The puri-
haps corrosion, or may damage the product by fied fatty acid exits from the bottom of the unit.
oxidation. Thus, degassing enjoys a special sig- The condensate dropping out in the condenser
nificance, not only for the fresh feed solution, but flows to a downstream separator. There it sep-
also, in many cases, for the intermediate or end arates into a heavy aqueous phase and a small
products. In general, degassing is accomplished quantity of light fatty acid phase enriched in the
through direct heating with evaporated vapor. color and odor carriers.
This warms the liquid practically to the boiling
point prior to vaporization. The degassing pres-
sure may be chosen to be the same as that of the 5.3. Pumps
first evaporation stage, but lower pressures may
also be desirable. Ordinary degasser designs are In designing evaporator systems, special care
conceptually similar to countercurrent baromet- must be given to the selection, arrangement, and
ric condensers. The liquid to be degassed flows operation of pumps for transferring liquids and
countercurrent to steam or evaporated vapors en- for producing vacuum. Pumps recycle the liq-
tering from below for heating. uid in forced circulation evaporators. Suitable
Figure 27 shows a compact assembly of liq- pumps withdraw the concentrated product from
uid degasser integrated with an evaporator. This the evaporator system. The vacuum pump unit
degasser design uses packing to achieve the re- must operate at the highest level of reliability as
quired contact surface between liquid and vapor. pumps withdraw the concentrated product from
Other designs employ shower decks or the well- an indispensable condition for ensuring freedom
known trays used in distillation or a combination from upsets in vacuum evaporator system oper-
of both. ation.
Degassing a liquid or solution is thus synony- Pumping capacity, materials of construction,
mous, in the process engineering sense, with di- and principle of operation are determining fac-
rectly preheating it with steam or vapors almost tors in pump selection. Pumps normally avail-
to its boiling point. This direct condensation of able on the market can fulfill the requirements
steam or vapors results in mixing the condensate for the preponderant number of applications. In
formed with the liquid being degassed. Then, in special circumstances, for example, for oxygen-
general, these degassing methods may be used sensitive products in vacuum operations, only
only when dealing with the same kind of ma- pumps without seals and having submerged
terials for both vapors and liquids. This is the electric motors, so-called “canned pumps”, or
case when the fresh feed solution is degassed pumps equipped with magnetic couplings, suf-
by direct preheating with vapors produced from fice.
its own evaporated solvent. Degassing of liquids Evaporator systems operating under partial
may be required for reasons of maintaining or or full vacuum, with pressure in the condenser
improving product quality. Figure 28 is a sketch under one bar (0.1 MPa) require a vacuum unit.
of an equipment arrangement applied, among This removes the noncondensable gases which,
others, with success in industrial installations for in most cases, consist predominantly of air, from
such cases. This example schematically shows the condensing chamber. In general, this unit
combined degassing, dewatering, and deodoriz- connects directly to the evaporated vapor con-
ing fatty acids in a falling film degasser. The key denser. Aside from mechanically operating vac-
equipment item in the system is an externally uum pumps, steam jet vacuum pump installa-
heated falling film vaporizer charged at the bot- tions have also proven successful. In their prin-
tom with stripping steam. Preheated raw acid en- ciples of construction and method of operation,
ters the upper section. It then flows downward these are comparable to steam jet compressors.
as a thin film on the inner walls of the vapor- A single jet is able to produce only a limited
izer tubes countercurrent to the stripping steam, compression ratio. To obtain higher vacuums
thus not only degassed but also dewatered and requires connecting several jets in series with
deodorized. By previously removing the oxygen one another. A single jet can reach a vacuum
in the upper portion of the vaporizer tubes, no of about 10 kPa absolute pressure; two jets can
damage to the product occurs by oxidation in attain about 4 kPa; and three down to 1.3 kPa.
 Evaporation 33

Figure 28. Degassing fatty acids in a falling film evaporator

A high steam consumption results if the vapors As an example, in multistage recirculating

compressed in a jet stage of a multistage sys- evaporator systems, controllers for the liquid
tem pass on to the succeeding jet. To avoid this, level in the vapor separation chambers, in re-
intercondensers are installed between the jets to ality, control the liquid flow through all units by
condense the vapors as well as the motive steam. means of throttle valves in the feed liquid pip-
Figure 29 schematically shows this mode of op- ing to each stage. Figure 30 shows this concept.
eration. A call for a change in level in any given stage
propagates through the upstream stages.
5.4. Control Instrumentation In principle, the evaporating vapor tempera-
ture in the last stage of a multistage evaporator
Control and surveillance enables determining system is the control variable regulating the heat-
acceptable values of the characteristic process ing steam flow to the first stage. In the concept
and operating variables. The multitude of pro- shown in Figure 30, holding constant pressure in
cess variants, as well as the variations in op- the last stage vapor separation chamber permits
erating conditions and desired product purities, using the temperature difference between heat-
do not permit a generally valid standard con- ing steam and last stage vapors as the control
trol concept applicable for all or any evaporation variable.
processes. Rather, for best control of a particu- A density measurement loop in the product
lar evaporator system, a new control concept is drawoff can be used to achieve uniformity of
developed for that application. the product concentrate. A controller picking up
34 Evaporation

Figure 29. Multistage steam jet vacuum pump

Figure 30. Throughput control in a multistage evaporator system

ISO codes: LIC, level indicating controlling; PIC, pressure indicating controlling; TdIC, temperature difference indicating
controlling

this signal can adjust a three-way valve located tor system serves to reduce local heat losses ex-
downstream of the product drawoff pump. Then, tensively. This prevents partial refluxing of the
deviations from the setpoint density change a evaporated vapors, and rather beyond that, espe-
partial product recycle flow back to the last evap- cially avoids overloading the evaporator heating
orator stage. This makes it possible to achieve a element also.
correction in the product concentration. In this The insulation normally used depend for their
case, the level controllers serve to readjust the effectiveness on their extremely low thermal
operation of the upstream evaporator stages. conductivity. Low thermal conductivity follows
from their low bulk density, characteristic of
their porous or wooly nature.
5.5. Insulation An optimum insulation thickness is usually
determined. For this, the annual costs of both the
Well-conceived and maintained insulation on insulation and the expense resulting as a conse-
vaporizer equipment and piping in an evapora- quence of the heat losses are needed. The annual
 Evaporation 35

cost of insulation is the depreciation. Both costs ing liquid change continuously during the course
depend on the insulation thickness. When the of a run. This is true also for the effective tem-
sum of the annual costs is plotted versus the in- perature difference between heating steam and
sulation thickness, the minimum cost represents boiling liquid when heating steam temperature
the optimum thickness. Determining the opti- is constant. Further, with simple batch evapo-
mum insulation thickness is an especially im- ration, the inventory of solution in the system
portant task in design of evaporation systems decreases with time.
with open-air construction, frequently the case
in chemical plants. During the winter months,
heat loss can be high. 7. Crystallization by Evaporation
and by Evaporation with Reduced
6. Evaporator System Operation Pressure Flashing

Today, most commercial-scale evaporation pro- The enrichment of solids in solutions by evap-
cesses operate continuously. This is advanta- orating the solvent covers a broad scope among
geous for system control since steady-stage op- thermal separation processes. In many cases,
eration, by definition, requires no changes in however, just thickening to higher concentra-
process and operating parameters and conditions tions alone does not suffice. More often, the
during the entire duration of the operation. How- objective is to recover the dissolved solid ma-
ever, if the task involves evaporating small quan- terial in virtually pure form, isolating it com-
tities of solution, then, in many cases, batchwise pletely from the solvent. This job cannot read-
operation may be referred over the continuous. ily be done by adhering strictly to the evapo-
An evaporation system for batchwise operations rator equipment arrangements so far discussed.
differs from a continuous evaporator design es- These have been conceived for a concentrated
sentially in that a comparatively large equipment product that flows and is pumpable. The de-
volume is necessary to hold the initial charge of sign features may need modification, and the
solution to be evaporated. However, due to the method of operation may need alternation es-
often more favorable heat-transfer conditions, pecially when processing solutions whose solu-
the heat-exchange surface in the evaporator heat- bility characteristics make crystallization a pos-
ing element proves to be less than that for a sible method for separating materials. In princi-
comparably operating continuous evaporator. In ple, all salt solutions fall into this classification
intermittent operations, the final concentration in the higher concentration ranges.In the field
and, with it, a low heat-transfer coefficient, is of evaporator engineering, evaporative crystal-
the case only at the end of the operating run. For lization (Fig. 31) and crystallization by evapo-
continuous operation, the same conditions for ration with reduced pressure flashing (Fig. 32)
low heat-transfer coefficient apply during the en- have a special position among separation pro-
tire operating run. Moreover, in batchwise oper- cesses. In practice, frequently the latter is also
ations, the time-average increase in boiling point called vacuum cooling crystallization. With in-
is less than that obtaining for continuous opera- telligent application, both processes can lead to
tion at the same end concentration. Thus, if the an economical system design concept. Now, if
heating steam temperature is the same for both the solubility of the substance to be crystallized
cases, a greater effective temperature difference depends only slightly on the temperature, then,
is available for batch operation. For these rea- in general, the evaporative crystallization pro-
sons, batch operation is still common even for cess (Fig. 31) would be used. However, crystal-
medium-sized evaporator capacities. lization by evaporation with reduced pressure
In general, precise process engineering calcu- flashing (Fig. 32) is a suitable separation pro-
lations prove to be somewhat more difficult for cess for preparing crystalline substances whose
batch evaporators than those for the steady-state solubility in the solvent is strongly dependent on
mode. For batch operation, namely, the concen- temperature.
tration and with it the boiling temperature and
also the film heat-transfer coefficient for the boil-
36 Evaporation

as the ancillary equipment, can be helpful. How-

ever, for a good critical examination of the pro-
cesses occurring in the crystallization charac-
terizing zones and their influence on equipment
sizing, a thorough study is absolutely necessary.
This is especially the case for troublesome prod-
ucts which show a tendency toward severe salt-
ing of the walls of the equipment. For this, the
specialized technical literature offers valuable
advice.

Figure 31. Process steps in evaporative crystallization

Figure 32. Process steps in crystallization by reduced pres-

sure flash evaporation

Figure 33 shows the scheme for a crystallizer Figure 33. Crystallizer for evaporative crystallization
installed mainly in evaporative crystallization
systems in combination with an independent ex- 8. References
ternal evaporator heating element. Recycling the
clear solution and controlling product drawoff 1. Reinhard Billet: Evaporation and Its Technical
hold the degree of supersaturation within the de- Applications, VCH Verlagsgesellschaft,
sired limits. Depending on the nature of the feed Weinheim-New York 1988.
material, the crystal reaches a size in the range 2. Reinhard Billet: Verdampfung und ihre
0.5 – 3 mm. technischen Anwendungen, VCH
In designing systems for evaporative crystal- Verlagsgesellschaft, Weinheim-New York
lization and crystallization by evaporation with 1981.
reduced pressure flashing, the information in the 3. Paul E. Minton, Handbook of Evaporation
above chapters, relative to sizing the heat ex- Technology, Noyes Publications, Park Ridge,
changers and vapor separation chambers as well N. J., 1986.

Evaporators → Evaporation
Exhaust Control → Automobile Exhaust Control
Expectorants → Cough Remedies
Explosive Cladding → Corrosion
Explosive Cladding → Welding and Cutting
 Explosives 1

Explosives
Jacques Boileau, Consultant, Paris, France

Claude Fauquignon, ISL Institut Franco-Allemand de Recherches de Saint-Louis, Saint-Louis, France

(Chaps. 2 and 3 except 2.6)
Bernard Hueber, Nobel Explosifs, Paris, France (Chap. 7)

1. Introduction . . . . . . . . . . . . . . . 1 3.3. Metal Forming and Welding . . . . . 13

2. Physical Properties and Chemical 3.4. Rock Blasting . . . . . . . . . . . . . . 13
Reactions . . . . . . . . . . . . . . . . . 4 3.5. Perforators, Shaped or Hollow
2.1. Detonation . . . . . . . . . . . . . . . . 4 Charges . . . . . . . . . . . . . . . . . . 13
2.1.1. Ideal Detonation . . . . . . . . . . . . . 4 4. Primary Explosives . . . . . . . . . . . 14
2.1.2. Deflagration and Detonation . . . . . . 5 5. Secondary Explosives . . . . . . . . . 15
2.2. Prediction of Detonation Data . . . . 5 5.1. Production . . . . . . . . . . . . . . . . 15
2.2.1. Complete Calculation . . . . . . . . . . 5 5.2. Specific Secondary Explosives . . . . 17
2.2.2. Approximation Methods . . . . . . . . 5 5.2.1. Nitrate Esters . . . . . . . . . . . . . . . 17
2.3. Nonideal Detonation Waves and Ex- 5.2.2. Aromatic Nitro Compounds . . . . . . 19
plosives . . . . . . . . . . . . . . . . . . . 7 5.2.3. N-Nitro Derivatives . . . . . . . . . . . 20
2.3.1. Nonideal Explosive Compositions . . 7 6. High Explosive Mixtures . . . . . . . 22
2.3.2. Detonation of Cylindrical Cartridges . 7 6.1. Desensitized Explosives . . . . . . . . 23
2.3.3. Low- and High-Order Detonation Ve- 6.2. TNT Mixtures . . . . . . . . . . . . . . 23
locity . . . . . . . . . . . . . . . . . . . . 8 6.3. Plastic-Bonded Explosives (PBX) . . 24
2.3.4. The Effect of Confinement . . . . . . . 8 7. Industrial Explosives . . . . . . . . . . 24
2.4. The Buildup of Detonation . . . . . . 8
7.1. Dynamites . . . . . . . . . . . . . . . . . 24
2.4.1. Combustion – Deflagration – Detonation
7.2. Ammonium Nitrate Explosives . . . 25
Transition (DDT) . . . . . . . . . . . . . 8
7.3. Ammonium Nitrate – Fuel Oil Ex-
2.4.2. Shock-to-Detonation Transition
plosives . . . . . . . . . . . . . . . . . . . 25
(SDT) . . . . . . . . . . . . . . . . . . . . 9
7.4. Slurries and Water Gels . . . . . . . . 26
2.4.3. Shock and Impact Sensitivity . . . . . 9
7.5. Explosive Emulsions . . . . . . . . . . 26
2.5. Classification of Explosives . . . . . . 10
2.6. Functional Groups . . . . . . . . . . . 11 7.6. Uses . . . . . . . . . . . . . . . . . . . . . 27
2.6.1. Nitro Group . . . . . . . . . . . . . . . . 11 8. Test Methods . . . . . . . . . . . . . . . 27
2.6.2. Other Groups . . . . . . . . . . . . . . . 11 8.1. Performance Tests . . . . . . . . . . . 28
3. Application . . . . . . . . . . . . . . . . 12 8.2. Safety . . . . . . . . . . . . . . . . . . . . 28
3.1. Energy Transfer from the Explosive 9. Legal Aspects and Production . . . . 29
to the Surroundings . . . . . . . . . . 12 9.1. Safety Regulations . . . . . . . . . . . 30
3.1.1. Shock and Blast Waves . . . . . . . . . 12 9.2. Production of Military Explosives . 30
3.1.2. Casing and Liner Acceleration . . . . 12 10. Toxicology and Occupational Health 30
3.2. High Compression of Solids . . . . . 13 11. References . . . . . . . . . . . . . . . . . 31

1. Introduction 1) Mechanical explosions are caused by the

sudden breaking of a vessel containing gas
An explosion is a physical or chemical phe- under pressure
nomenon in which energy is released in a very 2) Chemical explosions are caused by decom-
short time, usually accompanied by formation position or very rapid reaction of a product
and vigorous expansion of a very large amount or a mixture
of hot gas: 3) Nuclear explosions are caused by fission or
fusion of atomic nuclei

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 143
2 Explosives

4) Electrical explosions are caused by sudden The distinctions between these three classes
strong electrical currents that volatilize metal are not clear-cut because most explosives burn
wire (exploding wire) smoothly if they are not confined. However, if
some fine hunting powder burns under certain
Only chemical explosions are treated in this confined conditions, combustion may become
article. detonation. Dry nitrocellulose fibers can eas-
For an explosion to occur, the reaction must ily detonate, but this tendency is significantly
be exothermic; a large amount of gas must be lower in the gelatinized form. Some composi-
produced by the chemical reaction and vaporiza- tions, such as mixtures of cyclotrimethylenetri-
tion of products; and the reaction must propagate nitramine (RDX) with a binder, can be used as
very fast. For example, gasoline in air burns at a propellant, gunpowder, or high explosive, de-
a rate of ca. 10−6 m/s; a solid propellant, at ca. pending on the type of initiation.
10−2 m/s; and an explosive detonates at a rate of The third class consists of primary and sec-
ca. 103 – 104 m/s (detonation velocity). ondary explosives. Primary explosives (initia-
The two different modes of decomposition tor explosives) detonate following weak external
are deflagration and detonation. Deflagration stimuli, such as percussion, friction, or electrical
exhibits two characteristics: 1) the combustion or light energy. Secondary explosives are much
is very rapid (1 m/s up to a few hundred meters less sensitive to shock. However, they can det-
per second) and 2) the combustion rate increases onate under a strong stimulus, such as a shock
with pressure and exceeds the speed of sound in wave produced by a primary explosive, which
the gaseous environment, but does not exceed may be reinforced by a booster composed of a
the speed of sound in the burning solid. The ma- more sensitive secondary explosive. The vari-
terials are often powdered or granular, as with ous secondary explosives are used militarily or
certain pyrotechnics and black powder. Detona- industrially as shown in Figure 1.
tion is chemically the same as deflagration, but
is characterized by a shock wave formed within Functions and Constraints. Explosives
the decomposing product and transmitted per- can be either pure substances or mixtures. They
pendicularly to the decomposition surface at a function in such systems as munitions, where
very high velocity (several thousand meters per they are a component of a complex firing system
second) independent of the surrounding pressure or as firing devices in quarries or metal forming
(see Chap. 2). equipment. With such systems, the ingredients
Explosive substances can be divided into must fulfill one or more functions, while meet-
three classes. Members of the first class detonate ing various constraints arising in manufacture or
accidentally under certain conditions. These are use. Therefore, tests that represent these func-
explosible substances, some of which are used in tions and constraints are required.
industry as catalysts (e.g., peroxides), dyes, and When an explosive detonates, it generates a
fertilizers. This class includes products or mix- shock wave, which may initiate less sensitive
tures whose formation must be avoided or con- explosives, cause destruction (shell fragments,
trolled, e.g., firedamp, or peroxides in ethers. In blast effect, or depression effect), split rocks
the second class are products normally used for and soils, or cause formation of a detonation
their quick burning properties but which may wave. A detonation wave of special geometry
detonate under some circumstances, e.g., py- (hollow charge effect) may modify materials by
rotechnic compositions, propellants, and some very rapid generation of high pressure; for ex-
kinds of hunting powder. In the third class are ample, shaped charges, metal hardening, metal-
substances intentionally detonated for various powder compaction, or transformation of crys-
purposes. talline forms. A shock wave may be used to
For reasons of safety, acquaintance with the transmit signals, e.g., for safety devices or in
first group of materials is necessary. The second seismic prospecting.
group is described elsewhere (→ Propellants; In general, constraints are related to safety,
→ Pyrotechnics). Pure substances and mixtures stability, compatibility with other elements of
of the third class are described here. the system, vulnerability, toxicity, economics,
 Explosives 3

Figure 1. Differentiation of explosible materials

and, more recently, environmental and disposal The very important contributions of Alfred
problems [21]. Nobel (1833 – 1896) include the use of mercury
fulminate for the initiation of explosives (1859 –
History [1], [4], [87]. Explosives were prob- 1861), the development of dynamites (1873),
ably first used in fireworks and incendiary de- and the addition of 8 % nitrocellulose to nitro-
vices. The admixture of saltpeter with com- glycerin (blasting gelatine, 1876).
bustible products such as coal and sulfur pro- Many new products were developed between
duced black powder, already known in China in 1865 and 1910, such as nitrated explosives, mix-
the 4th century A.C., described in 808 A.C. by tures in situ of an oxidizer and a fuel, explosives
Qing-Xu-Zi, and used as a military gunpowder safe in the presence of firedamp, chlorate explo-
in a book published in 1044. The use in shells sives, and liquid oxygen explosives. Organic ni-
during the mongolian wars around 1270 and a tro compounds for military uses included tetryl,
severe explosion in a factory in 1280 were de- trinitrophenol, and trinitrotoluene.
scribed. The first correct description of the phe- Between the two world wars, RDX, pen-
nomenon of shock waves in air seems to be in a taerythritol tetranitrate (PETN), and lead azide
book by the scientist Song-Ying-Xing in 1637. were produced. After 1945 cyclotetramethy-
Around 1580 first descriptions in Europe are lenetetranitramine (HMX), 1,3,5-triamino-
known (siege of Berg-op Zoom). However, the 2,4,6-trinitrobenzene (TATB), and hexanitros-
difficulties of initiation upon impact against the tilbene (HNS) were developed (see Chap. 5),
target were not overcome until 1820 when ful- as well as “fuel – air explosives”. Ammonium
minate caps were developed. In the early 1600s, nitrate – fuel oil (ANFO) explosives and slurries
black powder was used for the first time to break were developed for industrial uses; some were
up rocks in a mine in Bohemia. This technique improved by adding bubbles or micropores.
spread throughout western Europe during the In the 1880s Berthelot described the phe-
1600s. Ammonium perchlorate was discovered nomenon of detonation. About the same time
in 1832. the hollow-charge effect was discovered, and the
The development of organic chemistry after foundations of the hydrodynamic theory of det-
1830 led to new products, although their explo- onation were established. In 1906, the first ac-
sive properties were not always immediately rec- curate measurements of velocities of detonation
ognized. These include nitrocellulose and nitro- were made. After World War II, the science of
glycerin.
4 Explosives

detonation was further developed and perfected the ideal detonation is given by the model [25–
[17]. 27] represented in Figure 3 by the p – V plane
Recently, new explosive compositions of (Fig. 3A) and the pressure p vs. distance x pro-
low vulnerability (LOVA = low vulnerability file at a given instant of time (Fig. 3B). This
ammunitions) are being developed. Major ef- model relates the explosive at rest (V 0 ), the
forts are being made to use predicted proper- shocked nonreacted explosive (ZND spike (∗)),
ties (e.g., density, ∆H f , sensitivity, themal sta- and the end of the reaction zone (CJ plane (ˆ)).
bility) to avoid unnecessary experiments [18– This model has been recently experimentally as-
20], [94], [102]. certained by tests made by F. Bauer [28] with
a PVDF piezogauge in cooperation with Lynn
Barker by a VISAR system on a mixture PETN-
2. Physical Properties and Chemical binder.
Reactions

2.1. Detonation

The detonation process needed for most uses

is characterized by a shock wave that initiates
chemical reactions as it propagates through the
explosive charge. The shock wave and reaction
zone have the same supersonic velocity; a frac-
tion of the chemical energy is used to support
the shock. Figure 3. Development of the ideal detonation
A) The p – V plane; B) The pressure vs. distance profile;
p pressure; V specific volume; D detonation velocity; H 0
Hugoniot curve of nonreacted explosives; H Hugoniot curve
2.1.1. Ideal Detonation of reaction products; (0) explosive at rest; (1) reaction zone
of length a, an arbitrary quantity; (2) isentropic release of
A model of ideal detonation (ID) is shown in the detonation product
Figure 2, with steady flow to the end of the re-
action zone. In Figure 3A the three states are located on a
straight line (Rayleigh line), with slope equal to
−D2 /V02 .
The loci of the shocked states are termed
Hugoniot curves: H 0 for the unreacted explo-
sives, and H for the completely reacted explo-
sives.
Some relations at the CJ plane can be ex-
Figure 2. Ideal detonation pressed as a function of D and the polytropic
coefficent of the detonation products:
Stationarity requires the plane corresponding

to the end of the reactions to be locally sonic. ∂logˆ
Γ=
This condition, termed the Chapman – Jouguet ∂logV̂ s
(CJ) condition [23], [24], yields the relation The notation ( )s represents the derivative along
D=u+c the isentrope at the CJ point.
needed to solve the equations of conser-
vation of flow (where D = detonation velocity, D D2
û= p̂=0
u = particle velocity, and c = sound velocity). Γ +1 Γ +1
The structure of the reaction zone of the Γ Γ +1
ĉ= D ˆ=0
ID plane detonation can be ignored, and the Γ +1 Γ
mechanical and thermodynamic data can be cal- where  = density These relations are valid for
culated by solving equations between the nonre- most condensed organic explosives Γ ≈ 3, with
acted and fully reacted states. The description of the assumptions that p0 = 0 and u0 = 0.
 Explosives 5

2.1.2. Deflagration and Detonation other is determined by the values of the equilib-
rium constants for (V̂,T̂ ) determined after a first
In a thermodynamic diagram such as Figure 3A, calculation.
there is another point that satisfies the Chap- Inasmuch as (V̂,T̂ ) are a function of the
man – Jouguet condition in the region p <p0 (not loading density 0 , some explosives, for in-
drawn in the figure). It represents the Chapman – stance, pentaerythritol tetranitrate (PETN), pro-
Jouguet deflagration, in contrast to the detona- duce free carbon at high loading densities and
tion: only gaseous products at moderate values of 0 .
Detonation Deflagration
Because of the complexity of the calculation, the
p̂ > p0 p̂ < p0 number and formulation of the equations depend
û > 0 û < 0 on the final result.
V̂ < V 0 V̂ > V 0
The thermochemical equations are solved
with a priori (V,T ) pairs to give gas product com-
Unlike the detonation wave, the deflagration position. The mechanical equations are then ap-
wave is subsonic, and consequently a precur- plied at the Chapman – Jouguet plane with the
sor shock is propagated in front of the reaction geometric condition represented on Figure 3A:
zone. Its intensity and velocity depend on the at the CJ point, the isentropic and the Hugoniot
chemical energy released and on the boundary curves have the same tangent, with a slope equal
conditions; in contrast to detonation, a specific to −D2 /V02 .
explosive does not provide a unique solution for
deflagration.
A precursor shock that is strong enough can, 2.2.2. Approximation Methods
in addition to compressing the explosive, also
heat it sufficiently to initiate reactions just be- A first prediction of the CJ data can be given by
hind its front; a progressive buildup of a com- using methods valid for condensed explosives.
pletely stationary process identical with the
ZND model of the detonation is observed. Con- Chemical Potential. For many organic ex-
sequently, a detonation is equivalent to a shock plosives, D and p̂ can be expressed simply as
followed by a deflagration. a function of a parameter Φ defined as [34]:

Φ=N M̄r Q
2.2. Prediction of Detonation Data
N = number of moles of gaseous products
per gram
2.2.1. Complete Calculation [29]
M̄ r = average molecular mass of these prod-
ucts, g/mol
The quantities D, p̂, û, V̂, and T̂ in the Chapman –
Q = enthalpy of the explosive minus the en-
Jouguet state are needed to evaluate further the
thalpy of the products, J/g
effectiveness of the explosive on the surround-
ings in a given action. The calculation of these The calculation of Φ is made under the as-
quantities requires the equation of decomposi- sumption that:
tion, the heats of reaction, and an equation of
state for the reaction products, which may be the- O + H −→ H2 O
oretical (virial expansion) [30], [31], semiempir- O + C −→ CO2
ical [32], empirical [33], or a constant Γ law. In i.e., the formation of water is considered be-
addition, the equilibrium constants for the reac- fore the formation of carbon oxides.
tion given as a function of V and T are needed. The following relations are then proposed:
For organic explosives, the distinction bet-
√
ween oxygen-positive or weakly oxygen- D=A (1+B 0 ) Φ
negative explosives, which give only gaseous p̂=K 20 Φ
products, and the strongly oxygen-negative ex-
plosives, which also give free carbon, is impor- A good fit with experimental data is found for
tant. In fact, the assignment to one class or the organic explosives by setting
6 Explosives

Figure 5. Sequence of reactions: explosive and oxygen-rich

Figure 4. Sequence of reactions: explosive and combustible binder
additive a) Negative-oxygen-balance explosive; b) Oxygen-
a) Cast organic explosive; b) Aluminum grains or flakes containing binder

n (O) = number of oxygen atoms

A= 1.01 B = 1.3 K = 15.58
n (N) = number of nitrogen atoms
This method, which requires only a knowledge n (H) = number of hydrogen atoms
of the equation of decomposition, is useful for n (F) = number of fluorine atoms
comparing organic explosives. n (HF) = number of hydrogen fluoride
molecules that can form from available
Rothstein Method. An empirical correla- hydrogen
tion has been found between the detonation ve- n (B/F) = number of oxygen atoms in excess of
locity D and a parameter F, which is a function those available to form CO2 and H2 O or
of the explosive molecule [35]. the number of fluorine atoms in excess of
those available to form HF
F − 0.26 n (C) = number of oxygen atoms doubly
D (0 ) = −3 (TM −0 )
0.55 bonded to carbon as in a ketone or ester
TM = theoretical density This correlation ap- n (D) = number of oxygen atoms singly bonded
plies to both organic nitro and fluorinated nitro to carbon as in C–O–R where R = H, NH4 ,
explosives. C, etc.
 ∗ n (E) = number of nitrato groups existing as a
n(H)−n(HF)
n (O) +n (N) +n (F) − 2n(O) nitrate ester or as a nitric acid salt such as
F =100 hydrazine mononitrate
Mr
A n(B/F) n(C) n(D) n(E)
3
− 1.75 − 2.5 − 4 − 5 Molecular masses and atomic composition
+100 −G
Mr for explosive mixtures must be derived as sums
where n (F), n (HF), and n (B/F) are the el- of mass-average molecular mass and of elemen-
emental terms for fluorinated explosives, and tal mole fractions. The prediction of the detona-
where G = 0.4 for each liquid explosive compo- tion velocity is ca. 95 % accurate.
nent, G = 0 for solid explosives, and A = 1 if the
compound is aromatic; otherwise A = 0.
∗ If n (O) = 0 or if n (HF) > n (H), this term = 0.
For 1 mol of composition:
 Explosives 7

2.3. Nonideal Detonation Waves and of the nonideal explosives involves heat transfer
Explosives between components, the specific surface areas
become important. Moreover, because the total
A detonation wave is nonideal if the geome- reaction zone is relatively long, detonation de-
try and dimensions of the charge are such that pends on the dimensions of the charges.
the reaction zone is affected by lateral shock or
rarefaction waves. Consequently, the nonideal-
ity depends strongly on the dimensions of the 2.3.2. Detonation of Cylindrical Cartridges
charge and the explosive composition charac-
terized by a given reaction zone length. In the detonation of cylindrical cartridges, the re-
An explosive composition consisting of com- active flow is two-dimensional, stationary, and
ponents with different reaction kinetics does not relatively easy to model. Many military or engi-
satisfy the ideal detonation model, which as- neering applications use cylindrical geometry.
sumes all the exoenergetic reactions to be com- The basic phenomenon is the interaction of
pleted simultaneously in the sonic Chapman – the inwardly propagating rarefaction fan, orig-
Jouguet plane. Such compositions are nonideal inating at the outer surface as it is reached by
explosives. The ideal detonation model applies the shock wave, with the reaction zone. The first
only as an approximation to most multicompo- consequence of this interaction is freezing of the
nent explosives; however, with data on reaction reactions by cooling, which reduces the released
kinetics under pressure often lacking, calcula- energy. A second effect is a curvature of the det-
tions are commonly based on the ideal detona- onation front and a loss in energy through a di-
tion model. verging flow. The reaction zone length and the
radius of the cartridge are two quantities that
play opposite roles in the process.
2.3.1. Nonideal Explosive Compositions The experimental determination of the det-
onation velocity as a function of the diameter
An example of an organic explosive with a produces a curve limited in two ways:
metallic nonexplosive additive is a dispersion of
aluminum grains or flakes in a cast organic ex- 1) As the diameter increases, the detonation ve-
plosive. The process sequence is shown in Fig- locity D approaches a constant value Di equal
ure 4. The energy effectively supporting the det- to that of the ideal detonation wave.
onation wave has been delivered at time t A . The 2) Below a given diameter d, called the criti-
absorption of energy by aluminum reduces p̂ and cal diameter, d cr , the detonation is no longer
D, but the late combustion of the aluminum al- self-supporting and fails.
lows the pressure to be sustained behind the CJ D
plane, thereby increasing the total impulse trans- Many analytical expressions D i
(d)
mitted to the surroundings. have been proposed in which the explosive is
The possible sequence of an organic explo- characterized by its ideal reaction zone length.
sive (a) with a negative oxygen balance cast or The function D (d) and the critical diameter d cr
pressed with a binder containing oxygen (b) is depend on both the length and the structure of
shown in Figure 5. The relatively slow decompo- the reaction zone, i.e., on factors that affect this
sition of the binder produces oxygen gas, which zone, such as the loading density 0 , grain size
shifts the reaction of the organic explosive to- g, initial temperature t 0 , and composition, espe-
ward better oxygen balance, thus increasing en- cially in the case of mixtures.
ergy production. As an example of the effects of these factors
A typical example of a mixture of two explo- on ideal explosive compositions, the influence of
sive components with different reaction kinetics 0 is shown in Figure 6 for the conventional mili-
is a mixture of trinitrotoluene (TNT) and ammo- tary composition 60 RDX/40 TNT (composition
nium nitrate (AN). The slower reaction of AN B) [36]. In the case of energy-rich explosives,
produces energy and an excess of oxygen, which the effect of the cylinder diameter increases with
shifts the equilibrium of the TNT reaction to a decreasing density, whereas the critical diameter
higher energy release. Because the detonation decreases with increasing density and increasing
8 Explosives

temperature [37]. The influence of mean grain Thus, under steady conditions, a state of shock
size, e.g., that of powdered TNT, is shown in plus reaction would correspond to that appearing
Figure 7 [29], and most nonideal explosive com- in a transient regime in the buildup of heteroge-
positions and some pure explosives exhibit a par- neous explosives to detonation.
ticular behavior (see Chap. 6).

2.3.4. The Effect of Confinement

Confinement usually delays the arrival of the ex-

pansion waves on the axis. A confined charge
is equivalent to a charge having a large diame-
ter. However, two anomalous effects should be
noted: if the velocity of sound in the confinement
exceeds the detonation velocity for the given di-
ameter, a foreshock is propagated ahead of the
wave. This foreshock can accelerate the wave
(increase the density) or stop the detonation, i.e.,
desensitize a porous explosive by compaction,
the explosive becoming homogeneous. An anal-
Figure 6. Detonation velocity D vs. diameter d for two den- ogous desensitizing effect can be generated if
sities  of 60 wt % RDX – 40 wt % TNT there is an air gap between the explosive and the
container. The expanding reaction products adi-
abatically compress the porous explosive. This
effect can stop the detonation of mining charges
embedded in boreholes.

2.4. The Buildup of Detonation

2.4.1. Combustion – Deflagration –
Detonation Transition
(DDT)

Deflagration can generate a shock wave, which

is propagated in the unreacted medium, and if
Figure 7. Detonation velocity D vs. diameter d for several strong enough, can initiate reactions and become
grain sizes g of powered TNT a detonation wave. This transition can occur only
if the explosive charge is confined or is of such
2.3.3. Low- and High-Order Detonation a size that expansion waves do not prevent for-
Velocity mation of a shock wave. Accident reports have
shown that DDT affects a variety of explosives
Some explosives exhibit two different detona- and propellant charges.
tion velocities, depending on the diameter of the However, different phenomena, which de-
cartridge and the initial ignition energy. Such ex- pend on the mechanical properties of the
plosives always have a relatively low energy and medium, may occur [39], [40]: if the explosive
loading density, with great sensitivity to shock is porous or exhibits poor mechanical behav-
waves [36]. Conventional examples are the dy- ior, the gas formed and subjected to pressure is
namites and highly porous explosives [38]. injected between the grains or into cracks, in-
The high sensitivity to shock waves tends to creasing the combustion surface. The resulting
allow the detonation to be sustained. This is true acceleration stops only when detonation occurs.
even when the development of the reactions is The path versus time of the observed ionization
seriously limited by the size of the cartridge. front is continuous. In the case of explosives stiff
 Explosives 9

enough to withstand an elastic wave, a steady energy released upon its passage. Its acceleration
deflagration develops as soon as the pressure ends with the appearence of a detonation wave
makes the medium impervious to the gas. The at point B. This wave is characterized by its lu-
transition to detonation occurs as the pressure minosity, as seen on optical records. Sometimes
of the gas formed behind the deflagration zone a second wave starts from point B and moves
becomes high enough to generate a shock wave. backward in the explosive, which has reacted
Detonation occurs when the shock wave reaches only partially (retonation wave). The macro-
the front of the deflagration wave. As a conse- scopic analysis can be explained by the micro-
quence, a discontinuity is observed in the path scopic heterogeneities of the explosive [42].
versus time of the ionization front.

2.4.2. Shock-to-Detonation Transition (SDT)

If the end of an explosive charge is subjected

to a shock wave, the steady detonation appears
only at a distance s and with a delay τ inside
the explosive charge [41]. For a given compo-
sition, s and τ are inversely proportional to the
intensity of the shock wave. There are two SDT
processes: one for homogeneous (for instance, a
liquid) and one for heterogeneous composition.
Figure 9. Detonation buildup (SDT), heterogeneous explo-
Homogeneous Explosives. The shock wave sive
(a) in Figure 8 propagated at constant velocity
initiates decomposition reactions that are first The energy of the shock wave is converted
completed along the entrance side (b) at time τ , into heat energy by the implosion of occluded
the detonation appearing at point A. The deto- gas bubbles, the impact of microjets, or the adi-
nation wave (c) travels in a compressed medium abatic shearing of the powder grains. All the
heated by shock wave (a). Therefore, the deto- observations allow for two successive phases,
nation wave (c) travels with a velocity exceeding ignition and buildup, that are accomodated by
the normal detonation velocity, which is attained numerical models assuming inward or outward
at point B (wave d) as soon as wave c has reached combustion of the grains [43].
wave a.
2.4.3. Shock and Impact Sensitivity

The sensitivity of the explosives to an applied

load is measured by the maximum load at which
no detonation occurs, or at which there is a 50 %
occurrence of detonation, i.e., a 50 % chance of
failure. The sensitivity to shock loading depends
on the pressure p∗ and its action time τ ∗ . Sensi-
tivity is defined with the aid of the curve p∗ (τ ∗ ),
which separates detonation points from failure
points.
For a variety of explosives and for a certain
Figure 8. Detonation buildup (SDT), homogeneous explo- pressure range, the sensitivity is defined by the
2
sive relation (p∗ ) τ ∗ = ε, where ε is a constant that
depends on the composition and exhibits the di-
Heterogeneous Explosives. In Figure 9, the mension surface energy per unit area [44].
shock wave (a) is gradually accelerated by the
10 Explosives

the mechanical properties of the explosive play

a part.

2.5. Classification of Explosives

For many years the behavior of cylindrical car-
tridges, as described in Section 2.3.2, was re-
garded as typical of ideal explosives. A detailed
analysis has shown, however, that classification
of explosives into two groups is possible, taking
into account the influence of the loading density
0 on the detonation velocity as a function of
the cartridge diameter and the critical diameter
[46].

Figure 10. Initiation energy threshold vs. shock pressure

a, b) HMX plus binder; c, d) Cast RDX compositions

Figure 10 shows that the concept of the en-

ergy threshold is an acceptable approximation
for solid-state compositions [45]. For liquid ex-
plosives, which exhibit different behavior, the
relation τ ∗ (p∗), based on an Arrhenius-type
kinetic theory (with initial temperature T ∗ ex-
pressed as a function of pressure p ∗) accurately
reproduces the experimental findings. The criti-
cal time τ ∗ is equal, for a given shock pressure,
to the time of the shock-to-detonation transition
(see Fig. 8). Except for primary explosives, the
sensitivity to shock-wave action and the shock-
to-detonation transition are both dependent on
the homogeneity of the composition. Sensitivity
is affected by grain size [103] and internal grain
defects [104]. The reaction of an explosive to
impact loading depends on several factors. If the
projectile is a large plate, the reaction is identi-
cal with that observed in the preceding case: the
shock wave induced by the impact depends on
the velocity and acoustic impedance, whereas
the action time is proportional to the plate thick-
ness. In tests of sensitivity to shock-wave action,
the impacting plates are driven by explosives.
If the projectile is a small sphere or cylinder,
the interaction with the target becomes complex
[41]. If the shock wave cannot induce a shock –
detonation transition, it degenerates into an adi-
abatic compression. Frictional and shearing ef-
fects can cause ignition. Finally, a phenomenon
analogous to the deflagration – detonation tran-
Figure 11. Detonation behavior of ammonium perchlorate;
sition (see Section 2.4.1) is observed, in which η = percent of the theoretical maximum density
 Explosives 11

The first group includes a variety of organic Members of the first group have limited explo-
explosives: TNT, RDX, HMX, and their mix- sive properties, except when the number of NO2
tures (see Chap. 5). The second group includes groups equals or exceeds the number of carbon
mixtures of an explosive and a combustible non- atoms, as in some gem-dinitro compounds and
exploding constituent (nonideal composition). derivatives of nitroform, HC(NO2 )3 . The latter
This group also includes some pure explosives are often shock sensitive, with limited heat sta-
such as hydrazine mononitrate (HN), nitrogua- bility. The compounds RCF(NO2 )2 are stable to
nidine (NG), ammonium nitrate (AN), dinitro- heat and rather insensitive [6], [7]. Members of
toluene (DNT), dinitrophenol (DNP), and am- the second group containing two or three NO2
monium perchlorate (AP). The behavior of the groups per ring are valuable; they are often dense
second group is illustrated for ammonium per- and insensitive to impact, with good hydrolytic
chlorate in Figure 11. and thermal stability.

N-Nitro Derivatives (NNO2 ). N-Nitro

2.6. Functional Groups derivatives are often difficult to synthesize. They
exhibit high densities and detonation velocities,
Certain groups impart explosive potential. with some sensitivity to impact. RDX and HMX
are representative.

2.6.1. Nitro Group

2.6.2. Other Groups
The nitro group is present in the form of salts
of nitric acid, ONO2 derivatives (nitrate es- Organic chlorates and perchlorates, perox-
ters), CNO2 derivatives (aliphatic or aromatic ni- ides, metal salts of some organic compounds
tro compounds), and NNO2 derivatives (N-nitro (acetylides and nitronates), and some or-
compounds such as nitramines, nitroureas, etc.). ganic compounds with three-membered rings or
chains of nitrogen atoms or triple bonds have
Salts of Nitric Acid. Salts of nitric acid in- only limited application, except as primary ex-
clude the alkali metal and alkaline earth metal plosives. Most are very dangerous to handle.
nitrates, ammonium nitrate, and the nitrates of Nitroso (NO) compounds are usually un-
methylamine, urea, and guanidine. These are stable. So-called hexanitrosobenzene is an ex-
usually low-density, water-soluble, sometimes ception; however, it is actually not a nitroso
hygroscopic compounds. With the exception of compound but a furoxan derivative (benzotri-
some salts of hydrazines, e.g., triaminoguani- furoxan). It is of interest because it is free of hy-
dine and hydrazine nitrates, they are insensitive drogen (zero-hydrogen explosive). Other furox-
to impact and friction. anes and also furazanes have explosive proper-
ties [88].
O-Nitro Derivatives, Nitrate Esters The difluoroamine group imparts explosive
(RONO2 ). The low molecular mass repre- character, increased density and volatility, a
sentatives are liquids or low-melting solids. lower melting point and detonation velocity,
They are sensitive to impact when the number and often much higher impact sensitivity. These
of carbon atoms and −ONO2 groups are equal compounds resemble primary explosives.
or nearly equal. Densities are in the medium Many metal azides are primary explosives.
range, except for symmetrical molecules such Some organic azido derivatives are being studied
as pentaerythritol tetranitrate (PETN). Heat sta- because of their high density and stability. How-
bility is moderate; they are subject to hydrolysis ever, polyazido compounds can be very sensi-
and autocatalytic decomposition. tive.

C-Nitro Derivatives (CNO2 ). Aliphatic and

cycloaliphatic nitro compounds differ greatly
from the aromatic and heteroaromatic series.
12 Explosives

3. Application decreases and the pressure profile changes. At a

given distance from the charge, compression al-
3.1. Energy Transfer from the Explosive ternates with tension. The mechanical effects are
to the Surroundings a function of the maximum pressure and of the
positive and negative impulses comprising the
The energy available in the gaseous reaction so-called blast wave. The maximum and mini-
products is transferred to the surroundings by mum pressures are represented in Figure 13 as
shock waves. The mechanical effects depend on a function of the reduced distance R/m1/3 from
the geometry of the charge and the surround- the charge.
ings, on the distance from the charge, and on the
acoustic impedance of the media. The explosive
energy is used either to create compression and
tension for engineering applications or to accel-
erate projectiles for military applications.

3.1.1. Shock and Blast Waves

The highest dynamic pressures are produced at

the exit end of the charge, where the detona-
tion shock is transferred to the inert material.
The shock pressure is a function of the shock
impedance. It is defined by the so-called shock
polar curve of the pressure (p) vs. particle ve-
locity (u). By a graphical method (Fig. 12) the Figure 13. Front pressure pf and minimum pressure pmin
induced pressure can be determined at the inter- in air vs. reduced distance R/m1/3 from TNT in air, where
section of a shock polar curve with the detona- R is the distance in meters and m the mass in kilograms
tion gas-product curve passing through the CJ
point.
3.1.2. Casing and Liner Acceleration

A casing or liner in contact with an explosive

charge is accelerated by a three-step process:
1) u1 given by the shock wave
2) u2 ≈ 2 u1 given by reflection of the shock
wave in a release wave at the free surface
3) u3 given by the further expansion of the
gaseous detonation products
The Gurney formula gives an approximate u3
for a casing filled with an explosive character-
Figure 12. Determination of shock pressure p and particle ized by the quantity E, which is given in J/kg
velocity u induced in an inert material by an explosive; [47]:
PMMA = poly(methyl methacrylate)
−1/2
M
u3 (m/s) = (2E)1/2 +α
Even higher pressures can be obtained by C
using converging geometries or, indirectly, by where
a two-stage device. The explosive accelerates
a thin metal plate, which generates an intense M = mass of the casing, kg
shock in the solid specimen as it strikes it in C = mass of the explosive, kg
free flight. During wave propagation in the sur- α = 0.5 for a cylindrical charge and
rounding medium, the intensity of a shock wave α = 0.6 for a spherical charge
 Explosives 13

3.2. High Compression of Solids 3.3. Metal Forming and Welding

Explosives provide the most powerful means for The detonation of an explosive charge is used
compressing solids in spite of the fact that at high to form a metal plate; the shock wave is moder-
pressure the heating limits the volume reduction. ated by a liquid transmitting medium (Fig. 14).
Techniques of free forming (Fig. 14A) or bulk-
Production of New Crystal Phases. The head forming (Fig. 14B) may be used.
large pressure generated by shock waves may A grazing detonation may weld two metal
be used to transform one crystal phase into an- plates with diffusion of metal through the inter-
other (polymorphic transformation). The best face (Fig. 15) [49]. The required collision veloc-
known example of this technique is the transfor- ity, vc , depends on the materials. This process is
mation of graphite into diamond. Unfortunately, called explosive welding or cladding.
the short duration of the shock limits this tech-
nique to the production of small crystals used as
abrasives.

Powder Compaction. The compression of

powders by shock waves produced by explosives
creates high pressures and temperatures simul-
taneously, resulting in grain welding. The main
problem, which has been solved only recently, is
the explosion caused by the interaction of release
waves, which follow the shock; special geome-
tries are required [48]. Rapidly solidified amor-
phous and metastable microcrystalline materials
and ultrahigh-strength ceramics are expected to Figure 15. Explosive welding or cladding
be produced by this technique.

Shock Hardening. The detonation of a thin

sheet of explosive covering a piece of steel cre- 3.4. Rock Blasting [36]
ates great surface hardness by a sequence of
rapid compression, heating, and cooling. In rock blasting the charges are placed in drill
holes, which are usually parallel to the rock
surface. With strong confinement, most of the
explosive energy is usefully employed, even
though much of it is released by afterburning.
Equally good results are given by nitroglyc-
erin in high (6000 – 8000 m/s) or low (2000 –
3000 m/s) explosives. Various types of wedge
cuts are used for tunnel blasting.

3.5. Perforators, Shaped or Hollow

Charges
An explosive can be used to produce a thin, high-
speed metallic projectile capable of perforating
armor [50]. Nonmilitary applications include oil
Figure 14. Setups for metal forming recovery.
A) Free forming; B) Bulkhead forming
A cavity in the explosive (Fig. 16) is lined
with a metal, usually copper. The detonation di-
vides the liner into two parts that move along
14 Explosives

the axis at different velocities. Most of the mass The main function of primary explosives is
of the liner forms the so-called slug at a ve- to produce a shock wave when the explosive is
locity of several hundred meters per second. stimulated by percussion, electrically, or opti-
The remainder forms a thin projectile which is cally (laser), thus initiating a secondary explo-
elongated because of the difference of veloc- sive. Primary explosives are the active detona-
ity between the first formed elements near the tor ingredients. Some are used in primer mix-
apex (ujet max. ≈ 8000 – 11 000 m/s) and those tures to ignite propellants or pyrotechnics. Be-
formed last (ujet min. = 1500 – 2000 m/s). The cause of their sensitivity, primary explosives are
ultimate length of the projectile depends on the used in quantities limited to a few grams, and
ductility of the liner and can be > 10 times the are manufactured under special precautions to
diameter of the charge. avoid any shock or spark. To be used in indus-
try, primary explosives must have limited sen-
sitivity and adequate stability to heat, hydroly-
sis, and storage. Mercury fulminate, azides, and
diazodinitrophenol are among the few products
that meet these requirements and that can det-
onate a secondary explosive. Others, e.g., lead
styphnate or tetrazene, initiate burning or act as
sensitizers.
Properties of primary explosives are given in
Table 1.
Mercury fulminate [628-86-4], Hg(ONC)2 ,
M r 284.65, was first prepared in the 1600s and
was used by Nobel in 1867 to detonate dyna-
mites. It is prepared by the reaction of mercury
with nitric acid and 95 % ethanol, in small quan-
tities because the reaction is difficult to control.
Figure 16. Projectile formation
Mercury fulminate is a gray toxic powder, which
When the projectile strikes a solid or liquid lacks the stability for storage. It reacts with met-
target, it drills a deep, narrow hole. The hole als in a moist atmosphere; in most industrial
depth P is given approximately by the expres- countries its use has been abandoned.
sion Lead azide [13424-46-9], Pb(N3 )2 , M r

291.26, discovered by Curtius (1891) [13],
j was developed after World War I and is now
P =L
t an important primary explosive. It is produced
continuously by the reaction of lead nitrate or
where L is the length of the projectile and j and
acetate with sodium azide in aqueous solution
t are the densities of the projectile and target.
under basic conditions to avoid formation of hy-
drazoic acid, which explodes readily. The crystal
size must be carefully controlled, large crystals
4. Primary Explosives being dangerous, by controlling the stirring and
by using wetting agents. Demineralized water
Under low-intensity stimulus of short duration, must be used. With thickeners such as dextrin,
primary explosives, even in thin layers, decom- sodium carboxymethylcellulose, or poly(vinyl
pose and produce a detonation wave; the activa- alcohol), purities from 92 % to 99 % are pos-
tion energy is low. The stimulus may be shock, sible, the former containing 3 % dextrin and
friction, an electric spark, or sudden heating. 4 – 5 % Pb (OH)2 . The lower sensitivity of the
The deflagration – detonation transition occurs 92 % lead azide to impact and friction compared
within a distance often too short to be measured. to purer lead azides facilitates detonator load-
The released energy and the detonation velocity ing. Lead azide has good stability to heat and
of primary explosives are small. Their formation storage. Contact with copper must be avoided
is often endothermic. because copper azide is extremely sensitive;
 Explosives 15
Table 1. Properties of primary explosives

Property Lead azide, Silver azide DDNP Lead Tetrazene

pure styphnate

Crystal density, g/cm3 4.8 5.1 1.63 3.0 1.7

Detonation velocity, km/s 6.1 ∗ 6.8 ∗ 6.9 5.2
at density 4.8 5.1 1.6 2.9
Impact sensitivity, Nm 2.5 – 4 2–4 1.5 2.5 – 5 1
Friction sensitivity, N 0.1 – 1 20 8 10
Lead block test, cm3 /10 g 110 115 325 130 130
Explosion temperature, ∗∗ ◦ C 345 290 195 265 – 280 160

∗ Theoretical. ∗∗ After 5 s.

aluminum is preferred. Silver azide is used at

high temperature or in miniaturized pyrotech-
nic devices. It is prepared from aqueous silver
nitrate and sodium azide.
Diazodinitrophenol [28655-69-8], DDNP,
C6 H2 N4 O5 , M r 210.06, is obtained by diazo- Now it is a trend in research of new primary
tizing picramic acid and purified by recrystal- explosives in order to replace the compounds
lization from acetone. It is sparingly soluble in containing lead (environmental problem).
water, nonhygroscopic, and sensitive to impact,
but not as sensitive to friction or electrostatic
energy. It is less stable to heat than lead azide. 5. Secondary Explosives
It is most often used in the United States.
5.1. Production
Common high explosives are usually made by
liquid-phase nitration. The overall mechanism
is believed to be ionic, with NO+ 2 generally the
Lead styphnate [15245-44-0], lead trini- reactive species. In some cases, N2 O4 may be
troresorcinate, C6 HN3 O8 Pb, M r 450.27, is pro- added to a double bond or to an epoxy group.
duced continuously by the aqueous reaction of It is also possible to nitrate gas-phase hydrocar-
the magnesium salt with lead acetate, some- bons. The most important nitrating agent is nitric
times in the presence of agents that promote acid → Nitric Acid, Nitrous Acid, and Nitrogen
the formation of the correct crystalline form. Oxides.
Especially sensitive to electrostatic discharge, it Numerous end products of nitration are sol-
is most frequently used to sensitize lead azide uble in concentrated HNO3 , and may be reco-
and in primer compositions to initiate burning. vered by dilution. However, dilution below ca.
55 wt % acid is not economic.
To increase the NO+ 2 content (3 wt % in pure
HNO3 ), lower the solubility of end products, re-
duce oxidative side reactions, and facilitate the
treatment of spent acids, mixtures of sulfuric and
nitric acids (mixed acid) are used. The water con-
Tetrazene [31330-63-9], C2 H8 N10 O, M r tent of a mixed acid may be reduced by adding
188.07, is obtained by the reaction of sodium oleum. In 50: 50 wt % mixed acid, the nitric acid
nitrite with a soluble salt of aminoguanidine is ca. 15 % dissociated.
in acetic acid at 30 – 40 ◦ C. It decomposes in However, sulfuric acid is difficult to remove
boiling water. Its greatest value is for the sensi- from products by washing. Furthermore, some
tization of priming compositions. substances (e.g., nitramines, nitriles, etc.) are de-
composed. Orthophosphoric acid or polyphos-
phoric acid may be used instead of sulfuric acid;
16 Explosives

however, these phosphoric acids are more ex- only a small amount of water, which is recovered
pensive and more difficult to recover. and mixed with spent acid. The acid is recovered
Mild nitration or nitrolysis can be conducted from this mixture.
in mixtures of nitric acid and acetic anhy-
dride or acetic acid; the reactive species may Purification. Treatment with boiling water
be CH3 COONO2 H+ . Mixtures of nitric acid is sometimes sufficient to hydrolyze impurities
and acetic anhydride containing between 30 and and wash out nitric acid. Crystallization elim-
80 wt % HNO3 can detonate [51]. A high con- inates sulfuric acid and produces the desired
centration of acetic anhydride avoids this danger. grain size. The solvent can be diluted with wa-
More recent nitration methods use N2 O5 as a so- ter or removed by steam distillation. Very fine
lution in pure nitric acid (“nitric oleum”) or in crystals are obtained by dilution with high-speed
chlorinated solvents (e.g., CH2 Cl2 ). Three pro- stirring or by grinding in water or an inert liquid.
cesses for the production of nitric oleum are in A fluid energy mill may also be used. Size sep-
operation or in development [90]: aration can be effected by sieving under flowing
1) Oxidative electrolysis of a N2 O4 – HNO3 water or in a classifier. Drying is usually done
mixture as late as possible in the process.
2) Ozonation of N2 O4
3) Distillation of an oleum (H2 SO4 + SO3 ) – Recovery of Spent Acids. Acid recovery in
NH4 NO3 mixture [89] an explosive plant is of great importance in con-
trolling production costs. These acids include
Nitric oleum allows yields to be improved and 55 wt % HNO3 , 63 – 68 wt % H2 SO4 from nitric
permits some syntheses to be performed that are acid concentration, and spent H2 SO4 containing
not possible by other routes; the organic N2 O5 some nitric acid and nitration products.
solutions allow nitration to be performed under To concentrate nitric acid, water is removed
very mild and selective conditions [16], [90]. by countercurrent extraction with 92 – 95 %
These nitrating agents must be used at their site H2 SO4 . At the top, 98 – 99 % HNO3 is produced.
of production. At the bottom, 63 – 68 % H2 SO4 is obtained,
which can be concentrated to 93 % by stripping
Nitration. Reaction is exothermic. Dilution with combustion gases, or to 96 – 98 % by vac-
of the nitric and mixed acids with water liberates uum distillation. Nitric acid can also be concen-
heat [52]. Normally, nitration is rapid. However, trated by distillation over magnesium nitrate.
70 – 85 wt % nitric acid is also an oxidant, and Sulfuric acid is freed of nitric acid and nitro
for this reason the reaction is best conducted con- compounds by heating or steam injection.
tinuously to limit the contact time of the product
with the reactive medium. If the medium is free Pollution Problems. Gaseous pollution may
of solid particles, a tubular reactor can be used; occur during nitrations, with evolution of red ni-
otherwise, reactors in cascade with efficient stir- trous fumes. These can be absorbed in columns
ring are employed. These reactors are made of by recycling water or dilute nitric acid to provide
highly polished stainless steel. Reactors and stir- 50 – 55 wt % acid.
rers must be carefully designed to avoid dead Liquid and solid pollution is created by wash-
zones and friction with crusts of explosives. Re- ing. Usually acids are transferred to decanting
actors are often provided with a valve that opens and settling basins, where product and other
quickly to discharge reactants into a dilution ves- solid particles settle and liquids are neutralized.
sel in an emergency. Some liquid wastes require special treatment;
for example, the red liquors from TNT are best
Product Isolation. If a precipitate is not destroyed by combustion.
highly sensitive to friction, it may be cen-
trifuged. For safe continuous filtration, the prod- Safety [9], [11]. Accidents caused by deto-
uct must be stable in its mother liquor, and the fil- nation are usually very severe. In addition to the
ter design must avoid introduction of the explo- normal precautions required in acid handling,
sive between moving and fixed parts. The pre- the production and use of explosives obviously
cipitate is washed in two stages. The first uses
 Explosives 17

involves special risks. Loss of life and destruc-

tion of property by an accidental explosion must NO+
2 + ROH
RONO2 + H
+

be prevented at all costs, and the detonation of

In an anhydrous medium the equilibrium
explosives stored near populated areas must be
shifts to the right; with dilution, hydrolysis oc-
avoided. Minimum distances between plant and
curs. In 60 – 80 % HNO3 , the unreacted alcohol
nearby structures are regulated.
may be oxidized. Furthermore, a catalytic ef-
The transmission of detonation by pipes or
fect of the nitrous acids produced causes rapid
feeding devices must also be prevented by ap-
decomposition of the reaction medium. This
propriate arrangements. The danger of detona-
decomposition either does not occur or occurs
tion by an accidental fire can be mitigated by
very slowly with an acid concentration below
limiting vessel size. Detonations by shock and
55 %. Nitrate esters are usually less stable if
friction in pipes, pumps, or valves are prevented
traces of acid are present. Traces of sulfuric acid
by suitable measures.
are difficult to remove from solid nitrate esters;
The following principles apply: partition of
therefore, mixed acid should not be used for
risks (e.g., specific buildings for specific oper-
their preparation. Acetic – nitric acid mixtures
ations); limitation of risks (limited number of
are used with sensitive or oxidizable alcohols.
persons present and limited quantities of ex-
Pentaerythritol tetranitrate [78-11-5],
plosives); and installation of two or three inde-
PETN, C5 H8 O12 N4 , M r 316.15, is scarcely sol-
pendent safety devices. Some of these measures
uble in 82 % HNO3 (0.7 wt %). The nitration of
are taken by the manufacturers under the super-
pentaerythritol is practically complete in a few
vision of professional organizations following
seconds and is conducted continuously. Pen-
government regulations.
taerythritol and HNO3 (ca. 1 : 5.5) are fed into
a well-stirred, jacketed reactor, with overflow
in cascade into a second reactor of the same
5.2. Specific Secondary Explosives design. The temperature is maintained below
30 ◦ C. PETN precipitates and may be isolated
Properties of secondary explosives are given in in one of two ways:
Tables 2 and 3.
Table 3. Impact sensitivity of secondary explosives ∗
1) In a third reactor the reaction mixture
is diluted with water to 55 wt % acid
Explosive Value ∗∗ (cPETN = 0.1 wt %) and filtered. The PETN
Insensitive is washed with water
TATB > 2.5 2) The reaction mixture is filtered immediately
TNT 1
Moderately sensitive
and then the 82 wt % spent nitric acid is con-
DINGU 0.8 centrated, a cheaper process but less safe
HNS 0.6
NTO 0.8 Washed PETN is stable. It can be recrystal-
Sorguyl 0.15 – 0.2
CL20 0.15 – 0.2 lized by dilution of a hot acetone solution with
Sensitive water, which removes traces of acid and some
HMX, RDX 0.3 organic impurities, and crystals of desirable size
PETN 0.15 – 0.2 a
NG 0.1 and flow properties for continuous feed purposes
are obtained. Pentaerythritol tetranitrate is fairly
∗ Drop-weight impact test [7].
∗∗ Based on TNT = 1. stable above 100 ◦ C and in alkaline medium. It
a
values are dependent on particle size is a powerful high explosive, with a small crit-
ical diameter, easy to initiate, and sensitive to
impact and friction. But that sensitivity depends
on the crystal size: PETN is more insensitive if
5.2.1. Nitrate Esters ultrafine or in form of a very big monocrystal.
Nanometric PETN was recently obtained by a
Nitrate esters RONO2 are prepared from alco- sol – gel process. It is used in detonators, com-
hols and nitric acid, which may be mixed with mercial detonating cord, boosters (with wax),
sulfuric or acetic acid. The reaction is reversible: sheet explosives (with an elastomeric binder),
18 Explosives

and plastic explosives. In a mixture with TNT, it

CL20 (ε)

is employed in some warheads and in industrial

9300

explosives.
2.04

Nitroglycerin [55-63-0], NG, C3 H5 O9 N3 ,

2.03 – 2.04

M r 227.09, unlike PETN, is a liquid at room

Sorguyl

9300

temperature, totally miscible with HNO3 of

190

<1

higher than 70 % concentration, sparingly sol-

uble (3 wt %) in 50 % HNO3 , and sensitive to
ca. 3900
1.83 d
ADN

4–8

hydrolysis (any contact with hydrolytic medium

92

must be very short) [53]. It is prepared by con-

decomp.

tinuous two-phase nitration of glycerol in anhy-

1.91 d
NTO

8520

drous mixed acid. The mass ratio of pure anhy-

255

drous glycerol (H2 O < 0.5 %) and 50: 50 mixed

decomp.
DINGU

acid is 1: 5. The product is washed with aqueous

1.98 e

8450

6–8
260

sodium carbonate or bicarbonate.

In the Schmid – Meissner and Biazzi pro-
cesses, the reactor is a vessel with overflow and
at 100 ◦ C
−7

1.907 b

good stirring and cooling. The reactants are fed

4×10
HMX

9100
283

480
330

continuously, while the temperature is kept at

10 – 20 ◦ C. The emulsion produced flows into
a separator, which in the Schmid process does
at 110 ◦ C

not have moving parts. In the Biazzi process,

RDX

8850
0.05

1.82
204

480
301

the separator is conical with peripheral feeding,

breaking the emulsion by rotation. The prod-
520 explodes
315 decomp.

uct is washed with alkaline water in columns

at 175 ◦ C
decomp.

(Schmid) or in mixer – settlers (Biazzi).

TATB

>452

7970

6–8
1.94
0.4

In the Gyttorp process, developed in the

1950s, the feeding of acid and alcohol can be
1.3×10−7

interrupted simultaneously. The key feature is

at 100 ◦ C
decomp.

the use of an injector with an axial flow of acid;

HNS

7120
1.74
318

305
0.4

the alcohol is sucked through the neck with ex-

cellent mixing. For good suction and heat ab-
sorption, a volume ratio of acid: alcohol of ca. 8
at 100 ◦ C

at 81 ◦ C
a

is required; it is maintained by recycling part of

1.654

6960
TNT

80.8

1.47

300
470

Liquid.b β-form.c Calculated in some cases.d α-form.e by x-rays 1.99

the spent acid. The glycerol is heated to 48 ◦ C to

14

reduce viscosity. The emulsion that is formed is

cooled to 15 ◦ C, and centrifuged continuously to
220 – 240
at 40 ◦ C

a
1.591

separate the nitroglycerin from spent acid. The

7700
13.5

520
NG

product is emulsified with alkaline wash water

1

by passage through an injector; it is separated

at 100 ◦ C

and washed again until neutral. The final emul-

Table 2. Properties of secondary explosives

0.0011
PETN

141.3

8340

sion can be safely transmitted through pipes. The

1.77

520
225
0.4

quantity of nitroglycerin present at any given

time can be kept low, and safety is further in-
creased by protective walls and the use of remote
Lead block test, 10 g, cm3

control.
Explosion temperature
3

Detonation velocity at

Critical diameter, mm
Melting point mp, C

max. density, m/s c

Crystal density, g/cm

Other liquid nitrates are produced by these

◦

Vapor pressure, Pa

processes; the Gyttorp process requires a liquid

after 5 s, ◦ C

alcohol reactant. The spent acid may be purified

Property

by heating. Nitroglycerin is used in propellants,

gunpowder, and dynamites.
a
 Explosives 19

5.2.2. Aromatic Nitro Compounds The o- and p-nitro compounds give

2,4- and 2,6-dinitrotoluenes and then 2,4,6-
The most common nitro-aromatic explosives trinitrotoluene (meta-directing effect of NO2 ).
contain the picryl (2,4,6-trinitrophenyl) group However, m-nitrotoluene does not give the 2,4,6-
and are usually obtained by nitration. The In- trinitro derivative; other products are formed that
gold mechanism involves nitronium ion, NO+ 2; reduce the stability or lower the melting point of
electrophilic attack occurs with formation of a the TNT. These impurities can be removed by
σ-complex intermediate [22]. the so-called selliting process or by fractional
The introduction of a second and third nitro distillation of the mononitration products. The
group requires increasingly severe conditions, m- and p-nitrotoluenes are used as chemical
including more anhydrous mixed acids and el- intermediates, and the o-nitrotoluene is further
evated temperatures (above 100 ◦ C for trinitra- nitrated to TNT. This method gives a product
tion). that is more easily purified.
Some of these aromatic nitrocompounds are For reasons of safety, quality, and cost, mod-
not used or are abandoned as explosives: among ern high-capacity plants use a continuous pro-
them: cess. The solubility of organic products in mixed
1,3,5-Trinitrobenzene [99-35-4], TNB, ben- acids can be quite low, 0.5 – 15 wt %, depending
zite C6 H3 O6 N3 , M r = 213.11 (I, R = H), attrac- on temperature and sulfuric acid concentration.
tive as high explosive, cannot be obtained by Nitration is believed to occur in the acid phase.
direct nitration of benzene, but only by indirect Consequently, the rate of interphase transfer and
syntheses giving an expensive product used only the intensity of stirring are important.
for preparations of fine chemicals. The plant employs a series of 8 – 16 mixer –
2,4,6-Trinitrophenol [88-89-1] C6 H3 O7 N3 , settlers. The organic phase is transferred from
M r = 229.11 (I, R = OH) TNP, picric acid, melin- the preceding settler together with the acid phase
ite, was extensively used in France during World from a following or preceding settler (coun-
War I because of lack of toluene, but was later tercurrent or parallel nitrators) into a mixer
replaced by trinitrotoluene (tolite), cheaper and maintained at a constant temperature (50 ◦ C for
non acidic. In some ammunitions, the ammo- mono-, 80 ◦ C for di-, and 100 ◦ C for trinitration).
nium picrate is still used. Acids may be added to adjust the composition.
N-Methyl N 2,4,6-tetranitroaniline From the last settler, molten TNT overflows into
[479-45-8] Tetryl C7 H5 O8 N5 , M r = 287 (I, other mixer – settlers that are used for washing
R=N(CH3 )NO2 ) has been used since 1905, no- and selliting.
ticeally for the production of boosters, after The spent sulfuric acid can be concentrated
lubrication by graphite or calcium stearate. But to ca. 96 % but not to oleum. Using oleum in the
it is now practically abandoned because some process leads to a higher yield, a shorter starting
allergic incidents of dermatosis, and replaced time, and a more rapid reaction; consequently,
mostly by RDX – wax mixtures. fewer mixer – settlers are required for a given
Three nitroaromatic products with a picryl output, but a use or customer must be found for
group remain for use as high explosives: TNT, the spent acid.
HNS, and TATB. Selliting is a process of washing with aque-
2,4,6-Trinitrotoluene [118-96-7], TNT, to- ous Na2 SO3 . A preferential reaction with the un-
lite, C7 H5 O6 N3 , M r 227.13 (1, R = CH3 ), is pro- symmetrical TNT isomers gives deep-red water-
duced by successive nitration of toluene, produc- soluble products. Selliting is applied to crude
ing mono-, di-, and finally trinitrotoluenes. The molten TNT above 80 ◦ C, but with some losses.
mononitration products are 60 % ortho, 35 % A continuous process may also be employed at
para, and 3 – 5 % meta derivative. 50 ◦ C, with TNT suspension produced by cool-
ing an aqueous emulsion with vigorous stirring
[54]. The resulting spherules contain pure 2,4,6-
TNT at their center, and a mixture of isomers in
the outer layer. The use of MgSO3 , rather than
Na2 SO3 , has been proposed [55]. The most eco-
nomical treatment of the red spent water from
20 Explosives

selliting is concentration followed by combus- veloped. An extensive review of TATB is given

tion. in [9].
Trinitrotoluene is used alone or mixed with
PETN, RDX, or ammonium nitrate. It is also
used in some industrial explosives. 5.2.3. N-Nitro Derivatives
Hexanitrostilbene [20062-22-0], HNS, N-Nitro derivatives include primary nitramines
C14 H6 O12 N6 , M r 450.24, is formed by oxi- RNHNO2 , secondary nitramines RR NNO2 ,
dation of TNT in methanol – tetrahydrofuran nitramides, nitroureas, nitrourethanes, and
solution with aqueous NaOCl [58]: nitroguanidines. There are no general synthetic
methods. Sometimes it is possible to nitrate
the precursor with HNO3 alone as with tetryl.
Often an N-acetyl, N-tert-butyl, or N-nitroso
derivative is used as starting material. In some
cases, nitric oleum is effective. The nitration
of hexamethylenetetramine (hexamine) to RDX
Yields of 40 – 50 % are obtained in a continuous and HMX is more complicated.
tubular reactor [59], [60]. Hexanitrostilbene can 1,3,5-Trinitro-1,3,5-hexahydrotriazine
be crystallized from HNO3 or acetone. [121-82-4], C3 H6 O6 N6 , M r 222.12, cyclotri-
Hexanitrostilbene has the following unusual methylenetrinitramine, Hexogen, RDX.
properties: the presence of 1 % HNS in molten
TNT prevents the formation of cracks and crazes
during solidification. With its low critical diam-
eter (0.4 mm) it can be used as the core in silver
or other metallic explosive cords. It remains sta-
ble and explosive over a very wide temperature
range (−200 to 250 ◦ C) and is thus usable in
Both RDX and HMX are stable in nitric
space [61].
acid over a wide temperature and concentration
1,3,5-Triamino-2,4,6-trinitrobenzene
range, but are destroyed by aqueous sulfuric acid
[3058-38-6], TATB, C6 H6 O6 N6 , M r 258.15,
and are attacked by alkaline substances. Sulfuric
is obtained by the following sequence:
acid should not be present during the synthesis.
1,3,5-Trinitro-1,3,5-hexahydrotriazine is
manufactured by nitrolysis of hexamine with
nitric acid alone or with acetic anhydride. These
processes were developed before and during
World War II.
The main process, called the Woolwich pro-
The proximity of nitro groups favors the dis- cess, which does not use acetic anhydride, was
placement of chlorine by ammonia. The reaction developed in the United Kingdom and is used
is conducted under pressure at 150 ◦ C in toluene there and in France. The raw materials are hex-
containing a little water. The product is washed amine and 98 – 99 % HNO3 free of sulfuric acid.
with water to remove NH4 Cl. It has low solu- The reaction is complex and not completely un-
bility and is difficult to recrystallize [62], [63]. derstood.
Although discovered in 1887, it first attracted at- Hexamine dinitrate is probably formed first,
tention after World War II. Since the 1950s inter- followed by intermediates that are oxidized
est has increased because of its thermal stability or decomposed, exothermically and often vi-
and outstanding insensitivity. Mixed with HMX olently, to produce RDX, which precipitates.
and a fluorinated binder, it is used as a booster. Large amounts of nitrous gases and CO2 are
It is, however, expensive (ca. 65 $/kg in the mid- evolved along with water. The process must be
1980s in the USA) because of the high cost continuous with careful control of temperature
and low availability of trichlorobenzene. There- and flow conditions. The plant consists of three
fore, alternative synthetic routes have been de- groups of stainless steel cascade-type reactors
 Explosives 21

with efficient stirring and cooling devices (jacket problems are more difficult to solve. The same
or coil). Nitric acid and hexamine are fed into plant can be adapted to HMX production.
the first group at a temperature of 20 – 50 ◦ C. Both RDX and TNT are the basic components
The homogeneous mixture overflows from the of almost all modern high explosives. They are
last reactor into the first one of the second group mixed together, alone or with wax, or formu-
(the decomposers); this reactor is equipped with lated with plastic binders. For a powerful and
a large pipe for the escape of gases and a water heat-stable explosive, RDX is preferred.
feeder. The temperature is maintained between 1,3,5,7-Tetranitro-1,3,5,7-tetraazacyclooc-
75 and 82 ◦ C, and water is continuously added tane [2691-41-0], C4 H8 O8 N8 , M r 296.16
to maintain a HNO3 concentration of 55 wt %. (2, R = NO2 ), octahydrotetranitrotetrazocine,
The gases evolved are condensed in towers, pro- cyclotetramethylenetetranitramine, octogen,
ducing 50 – 55 wt % HNO3 , which is reconcen- HMX, was discovered shortly before World
trated. This first decomposer is the key to the op- War II as a byproduct of RDX synthesis by a
eration. Foam must be avoided as well as thick Bachman-type process. It exists in four crys-
crusts on which the stirrer could scrape, causing talline forms [4], [66], [67]. The β-form has the
an explosion. In the third group of reactors, the highest density ( = 1.907 g/cm3 ) and a shock
suspended product is cooled and then continu- sensitivity similar to that of RDX. Large crystals
ously filtered and washed. The resulting RDX of the α-form are shock sensitive, but microcrys-
contains HMX (1 % max.) and some nitric acid, tals are not.
which can be removed by heating with water at
135 ◦ C for 3 h in an autoclave. The yield based
on hexamine is 78 – 80 %.
The RDX can be recrystallized or used di-
rectly, after desensitizing by wax or 10 % TNT to
permit drying and transportation. Recrystalliza-
tion from cyclohexanone or methyl ethyl ketone
removes traces of acidity (required, for example,
for use with aluminum powder) and produces
crystals of the desired size.
A process without acetic anhydride was also
developed in Germany in 1940 (KH process). A HMX is now obtained directly by a modified
modification is the addition of NH4 NO3 to react Bachman process. In this batch process, acetic
with all CH2 groups of hexamine (K process). anhydride and a mixture of NH4 NO3 and HNO3
The KA process was developed during World are added simultaneously at 44 ± 1 ◦ C to hexam-
War II in Germany, and the Bachman process ine dissolved in glacial acetic acid. After 15 min,
was developed and is used in the United States. the operation is repeated. The reaction mixture
Both processes use acetic anhydride, and the re- is aged at 45 – 60 ◦ C, diluted with hot water, and
actions are very complex. refluxed for up to several hours. The suspended
To a solution of hexamine (1 part) in glacial HMX is filtered off and washed until neutral.
acetic acid (1.65 parts) are added a solution of The HMX is obtained as small crystals of the
NH4 NO3 (1.5 parts) in concentrated HNO3 (2 α-form, which are transformed into the β-form
parts) and acetic anhydride (5.2 parts) at ca. 65 – by recrystallization from acetone or DMSO.
72 ◦ C. The mixture is maintained at that tem- HMX can also be obtained via
perature for at least 1 h, diluted with water, and dinitropentamethylenetetramine (DPT, 3,
heated to hydrolyze impurities. The yield is ca. R = NO2 ) [68]. In another process starting from
80 – 85 %; nitrous fumes are not evolved. hexamine, the diacetyl intermediates DAPT (3,
The product contains ca. 8 – 15 % HMX, R = COCH3 ) [69] and DADN (2, R = COCH3 )
depending on the reaction conditions. An ade- are isolated, and this is followed by nitration
quate source of acetic anhydride must be nearby, with nitric oleum. However, since demand for
where acetic wastes can be dealt with. This pro- HMX is now very low, production by this route
cess is easier to carry out than the process em- has ceased.
ploying nitric acid alone, but its environmental
22 Explosives

The price of HMX is usually 3 – 5 times that duction has begun in pilot plants [91]. It can be
of RDX. It is used when high performance is used as a high explosives and in propellant for-
required (e.g., shaped charges). Both RDX and mulations.
HMX are also used in propellants. Oxynitrotriazole [932-64-9], ONTA, NTO,
3-nitro-1,2,4-triazol-5-one, was first reported in
Other High Explosives. Numerous 1905, but its use as a low-vulnerability explosive
nitramine derivatives have been studied. For was only discovered in 1979 [96],[73]. It has a
example: high density (1.91 g/cm3 ), good detonation ve-
Dinitroglycoluril [55510-04-8] (DINGU or locity, low sensitivity to impact and friction, and
DNGU ; 4, R = H) has a high density good thermal stability (> 200 ◦ C) [97].
(1.99 g/cm3 , X-ray) [100] and explosive prop-
erties close to those of TATB [70], [71], but at a
much lower price. It can replace part of the RDX
in mixtures with TNT and can be introduced as
a component in gunpowder. Some comparative
thermodynamic properties are studied [72].
It is manufactured in two steps: reaction of the
semicarbazide hydrochloride with formic acid
to give the triazolone, which is nitrated with ni-
tric acid. The NTO is recrystallized from water.
NTO is used in LOVA formulations, some of
which were tested in a joint LOVA programme
of the USA, UK, Germany, and France.
Ammonium dinitramide (ADN), NH+ −
4 N(NO2 )2 ,
3 ◦
It is prepared by continuous nitration of gly-  1.83 g/cm , mp 92 C, is a carbon-free ammo-
coluril with 98 wt % HNO3 at 30 – 60 ◦ C in nium salt that was discovered and developed in
cascade-type reactors. the former Soviet Union in the 1960s and has
Tetranitroglycoluril (sorguyl ; 4, R = NO2 ) in the mid 1990s been disclosed [99]. ADN is
prepared by nitration of DINGU with a mixture almost as hygroscopic as ammonium nitrate and
HNO3 – N2 O5 , has a high density (2.01 g/cm3 ), very insentive. It is of interest as a component
and detonation velocity (9300 m/s). Only one of certain explosive mixtures and as a clean
crystalline form is known. It must be coated or propellant.
plastic bonded because it is sensitive to hydro-
lysis [70], [74], [72].
Hexanitrazaisowurtzitane (HNIW, CL-20).
6. High Explosive Mixtures
One way to obtain explosives of high crystal Explosives are used for global or directed
density is the synthesis of cage compounds such destruction (bombs, torpedoes, mines, reac-
as HNIW, which was discovered in 1986 by A. tive armors, and warheads) or for pyrotech-
Nielsen[98]. nics. Among pure compounds, only TNT and
trinitrophenol are sufficiently insensitive to be
loaded in large quantities by casting. Small
quantities of other pure compounds are some-
times used for detonators or cutting or transmit-
ting cords.
For flexible wrapped cords, the pure explo-
sive (e.g., PETN) flows continuously through a
funnel to form a flowing stream that is wrapped
It is prepared by the reaction of benzylamine in a thin plastic band. Thread is immediately wo-
with glyoxal, followed by debenzylation and ni- ven on the plastic-enclosed explosive, and this is
tration. It exists in six crystalline forms [92], again encased with plastic by drawing through a
[93]; the ε-form has a density of 2.04 g/cm3 . Pro- die, which also helps adjust the loading density.
 Explosives 23

For metallic cords, the high explosive (PETN, prepare ternary mixtures of explosive aluminum
RDX, HMX, or HNS) is introduced into a metal- and wax.
lic tube (lead, copper, or silver), which is drawn Detonation velocities can be obtained close to
through dies until the desired size and cross sec- those of the pure explosives; e.g., for a mixture
tion are obtained. of 94.5 % RDX, 5 % wax, and 0.5 % graphite,
Loading Processes. In casting processes, the D = 8600 m/s at  = 1.76 g/cm3 (D = 8850 m/s at
explosive is employed as a solution or a liquid  = 1.82 g/cm3 for pure RDX). However, large
suspension; it is cast into the shell or in the mold, loadings are difficult to carry out because of
where it crystallizes on cooling (physical pro- problems with homogeneity, brittleness, poros-
cess) or solidifies by the cross-linking of a poly- ity, and cost. The process is very useful for au-
mer (chemical process). In pressing processes, tomatic filling of press-loaded small munitions.
the explosive is introduced in granular form into
a mold or shell and pressed with a piston at a
pressure of 10 – 300 MPa; conditions depend on 6.2. TNT Mixtures
the munitions size, the binder, and the required
mechanical properties. Special shapes are pre- Molten TNT (mp 80 ◦ C) is compatible with
pared by laminating or calendering. many explosives and other products, providing
Flexibility is increased by the use of blends, a castable melt above 80 ◦ C. Among the prod-
which can enhance explosive performances ucts most frequently added are ammonium ni-
while preserving safety and reducing cost. Spe- trate, to obtain very cheap munition loadings
cial effects, such as delayed detonation, are pos- (amatols), and nitramines (RDX or HMX) or
sible with improved safety and high-temperature other high explosives (PETN, NTO), to improve
stability. performance. Mixtures containing 50 – 75 wt %
RDX are used in bombs and warheads such as
shaped charges. Some castable blends contain
6.1. Desensitized Explosives aluminum powder (tritonals, ammonals, Torpex,
and HBX 1 and 3).
Because of their sensitivity and high melting Wet and dry processes are employed. The
points, RDX, PETN, and HMX must be desensi- former, the same as that used for desensitizing
tized before casting or pressing. This is achieved with low-melting wax, has cost and safety ad-
by coating the particles with wax, sometimes vantages. Almost the entire process is carried
with addition of graphite as a lubricating and out under water. In France, RDX coated with
antistatic agent. The beeswax used in the past 10 wt % TNT is produced in this manner, be-
has been replaced by paraffin or synthetic waxes, cause its transportation as a dry product is al-
which give more reproducible results. The wax lowed. However, air bubbles on the RDX crys-
content in the explosive mixture is usually 2 – tals can create difficulties in loading.
10 wt %. In the dry process, the components are added
In the simplest process, the particles are dry to molten TNT with stirring, and the mix-
coated in hot water. The explosive (RDX, for ex- ture is cast in shells. Wet RDX can be added to
ample) is vigorously stirred in water and heated TNT at ca. 95 – 100 ◦ C; the water is removed by
slightly above the melting point of the wax, decantation and evaporation.
which is introduced and dispersed on the parti- Blends of TNT are used in the large-scale pro-
cles. The mixture is cooled by the rapid introduc- duction of munitions. Shaped charges can be ob-
tion of cold water, without formation of crusts on tained by controlled sedimentation of the molten
the vessel walls. The suspension is filtered and mixture. Crack formation in TNT during cooling
dried. Coating agents melting above 100 ◦ C are can be controlled by the addition of 1 % HNS.
applied in a solvent (e.g., butyl acetate), which Explosive performance is restricted by the
is removed by steam distillation. If the explosive condition that the mixture must be pourable; for
is sensitive to hot water, the solvent is removed example, for a blend of RDX: TNT of 70: 30
by filtration, possibly preceded by evaporation (wt %), D = 8060 m/s at  = 1.73. (Since theor
under vacuum. These processes are also used to = 1.765, the porosity is ca. 2 %.)
24 Explosives

For blends with higher RDX or HMX con- ing and evacuated molds or shells. The molds
tent, a special apparatus such as a porous piston are cured in an oven for a few days. Two differ-
is used. Because of the danger of detonation by ent compositions may be cast, one over the other
fire, mixtures of RDX with TNT are now forbid- (bicompositions), to produce special detonation
den on ships by some countries. waves.
The main advantage of these formulations is
their low sensitivity, especially against bullets,
6.3. Plastic-Bonded Explosives (PBX) impact, and friction, and the difficulty of the
transition from combustion to detonation. The
Two different procedures are followed which mechanical properties can be excellent, and ther-
improve the performance of new munitions. mal stability is fair.
Among the drawbacks are the slow curing
Desensitized Explosives. Some new war- and high cost when a multimodal particle-size
heads require improved mechanical properties distribution is used to increase the explosive con-
and stability at high temperature. Waxes are re- tent. The detonation velocity is diminished by
placed by thermoplastics or by other plasticized the inert character of the binder; it can be esti-
polymers (nitrocellulose). mated by the Urizar formula [7, pp. 8 – 10], [77].
The manufacture of these plastic-bonded ex- Energetic binders improve the detonation veloc-
plosives resembles the use of waxes dissolved ity, but increase sensitivity. A review of energetic
in a solvent immiscible with water. The molding binders is given in [15], [79]. The use of ther-
powder is pressed, often in a heated and evacu- moplastic elastomers as binders is of interest for
ated mold; for large charges, machining is neces- environmental reasons since they facilitate the
sary to obtain homogeneous charges of complex dismantling of ammunition.
shapes with good mechanical properties at high
temperature.
Examples include RDX or HMX boosters 7. Industrial Explosives
bonded with polyamide and mixtures of HMX
and TATB containing 10 wt % fluorinated poly- For more than 350 years explosives have been
mer [95]. Use is limited by the high cost of the employed to mine ores and minerals. The an-
pressing machines and the length of the process- nual consumption of explosives by each of the
ing cycle, especially for large charges. largest Western European consuming countries
is around 40 000 t. World annual consumption of
Castable Explosives [75], [76]. For larger industrial explosives is at least 5 × 106 t, 75 % of
charges, mixtures are used of an explosive with which is ammonium nitrate – fuel oil (ANFO).
a liquid binder, which is then cross-linked (com- During the first 250 years of this period, only
posite explosives). A similar process is used black powders were known and used, but fun-
for composite propellants. Composite explo- damental changes occurred in the 1860s (inven-
sives are being developed for uses requiring high tion of dynamite and blasting cap by Alfred
accuracy and low vulnerability (LOVA explo- Nobel), 1950s (ANFO), and 1980s (emulsions).
sives). The search continues for less expensive products
The liquid binder is introduced first into a and safer techniques for production and field use
mixer equipped with S-blades. A mixture of in mines, quarries, and road, tunnel, and dam
a diisocyanate and a diol (hydroxy-terminated construction. At the same time, the introduction
polyether or polybutadiene) is usually employed of new products is restrained by the cost of exist-
in a precise ratio, with a precise quantity of ing investments and by safety and environmental
a cross-linking agent such as a triol. The dry regulations.
solid explosive (RDX, HMX, or PETN) is then
added and mixed under vacuum with additives
(e.g., surfactants) and a catalyst providing a pot 7.1. Dynamites
life, i.e., the mixture remains pourable, of a few
hours. During this time the mixture is cast, some- Gelatine dynamites are powerful explosives
times under pressure or by injection, in vibrat- whose main ingredient is nitroglycerin. They
 Explosives 25

were invented opportunely to replace black pow- 7.2. Ammonium Nitrate Explosives
der in the construction of railroad and tunnels
and gave great impetus to the use of explosives. Ammonium nitrate (AN) explosives were devel-
Although diminished in importance since the oped in European countries to replace explosives
1950s and progressively replaced by new types made with chlorates. They appeared later in the
of explosive, dynamites are still widely used be- United States (Nitramon, DuPont, in 1935).
cause of their excellent qualities. The French AN explosives, are made with
A detonation velocity range from 4300 to ammonium nitrate (ca. 80 wt %) sensitized with
7500 m/s provides high brisance. Sensitivity to a nitro compound (TNT, PETN, or their mixture,
initiation by cap or detonating cord is very called pentolite). Formulas include aluminum
good, as is the flashover coefficient. Density powder and additives. These products are char-
(ca. 1.5 g/cm3 ), water resistance, and detonation acterized by their good production safety and
pressure are high. low production cost. They show good sensitivity
The composition of dynamites has changed when set off by caps or detonating cords. How-
only slightly since their origin. Nitroglycerin, ever, they are sensitive to humidity. Properties
gelatinized by nitrocellulose, has been totally or of the representative product Securex 80 are as
partially replaced by nitroglycol to reduce cost follows:
and permit lower operating temperatures. How- Composition, wt %
ever, nitroglycol is more toxic than nitroglyc- Ammonium nitrate 81.5
erin, and its use is limited in some countries. Oxi- High explosive 16
Aluminum 0
dizers such as ammonium nitrate reduce the cost Mass energy, kJ/g 3.51
of low-energy formulas. Combustible compo- Detonation velocity, m/s 4800
Flashover coefficient, cm 2
nents (wood meal, peat, silicon, and aluminum) Detonating pressure 6.34
and other additives (sodium nitrate, ammonium Density, g/cm3 1.10
chloride, and sodium chloride), provide formu-
lations with specialized properties. Ammonium nitrate explosives made in the
The consistency of such mixtures varies ac- United States contain dinitrotoluene but no nitro
cording to the nitroglycerin – nitroglycol con- high explosive. They are produced by blending
tent. Gelatin dynamites containing 20 – 40 wt % and as a result are not cap sensitive. The U.S.
of nitroglycerin – nitroglycol form a plastic Government, followed by other governments,
paste that may be made into cartridges after has established a category with relaxed rules for
cutting or extrusion. Dynamites containing 10 – the transport and storage of these explosives.
20 wt % nitroglycerin – nitroglycol are powdery, This category was first called NCN (nitrocar-
and tampers are required to make cartridges. bonitrate) and is now known as blasting agents.
They have been largely replaced by the new ex- They have been progressively replaced by water
plosives, except for use in coal mines, where gels and emulsions.
the potential presence of dangerous dust and gas
means that only very safe explosives with the
lowest possible detonation temperature should 7.3. Ammonium Nitrate – Fuel Oil
be used. Permissible explosives for these appli-
cations usually contain a large amount of am- Explosives
monium nitrate and sodium chloride, the en-
dothermic melting of which absorbs much of Ammonium nitrate – fuel oil (ANFO) explo-
the energy released by the detonation. Degrees sives have been developed since 1955. They are
of safety in coal mines are defined by national made of porous prills of ammonium nitrate (ca.
regulations. In France the classes are rocher, 94 wt %) soaked in mineral oil, usually domestic
couche, and couche améliorée. The first refers to fuel oil (ca. 6 wt %). In some cases, aluminum
less safe explosives, permitted for underground powder is added to increase explosive strength.
use only. Dynamites are marketed in cylindri- Ammonium nitrate – fuel oil explosives are
cal paper, cardboard, or plastic cartridges. The ordinarily used in bulk, although some countries
characteristics of the leading products of Nobel
Explosifs France are given in Table 4.
26 Explosives
Table 4. Properties of dynamites

Property F16 F19 GDC 16

Nitroglycerin/nitroglycol, wt % 32 40 12
Classification gelatin gelatin powder
Application general and underground general and underground permissible
Mass energy, kJ/g 3.97 4.15 1.78
Detonation velocity, m/s 6000 6500 2200
Flashover coefficient ∗, cm 8 10 10
Cartridging density, g/cm3 1.45 1.45 1.10
Detonation pressure ∗∗ 13.05 15.32 13.31

∗ Maximum distance at which a cartridge of diameter 30 mm and weight 50 g has a 50 % probability of iniating another cartridge.
∗∗ Calculated with the formula 14 AD2 .

limit their use to cartridges. They can be made device (CHUBPACK) in cylindrical plastic en-
on-site in a mobile unit, often mounted on a truck velopes closed by metal clips.
(ANFO truck). They are inexpensive and safe to Slurries and water gels are made of aqueous
handle, but low in strength, detonation velocity, solutions of ammonium nitrate and sodium or
and detonating pressure. In addition, they can- calcium nitrate gelled by the addition of guar
not be used in the presence of water. Because of gum or cross-linking agents. They are sensitized
their very low sensitivity, they require powerful by nitro explosives, organic amine nitrates, or
primer charges, powerful detonating cords, dy- by paint-grade aluminum. Combustible materi-
namite relay cartridges, and boosters. The den- als, such as aluminum, urea, sugar, or glycol, are
sities are low. Properties are listed in Table 5. mixed with these solutions either continuously
or discontinuously.
Table 5. Properties of ANFO explosives for general applications
The presence of reactive aluminum, water,
Property N 135 D7 fuel and ammonium nitrate requires careful control
to avoid chemical side reactions. The properties
Composition, wt %
Ammonium nitrate 91 94.3 of water gel explosives and slurries marketed in
Fuel oil 4 5.7 France are listed in Table 6.
Aluminum 5 0.0
Mass energy, kJ/g 3.43 2.74 Table 6. Properties of water gel and slurry explosives for general
Detonation velocity, m/s 3900 3700 applications
Detonating pressure 3.42 2.84
Density, g/cm3 0.9 0.83 Property Hydrolite AP, Gelsurite 3000,
in bulk in cartridges

Composition, wt %
Nitrates 46 61.6
Water 15 13
Aluminum 0 15
7.4. Slurries and Water Gels High explosive 27 0
Mass energy, kJ/g 2.70 3.87
A new class of industrial explosives, known Detonation velocity, m/s 5100 4000
Flashover coefficient, cm 0 5
as water-explosives has been developed since Detonating pressure 9.75 4.80
1956; they contain no nitroglycerin and are Density, g/cm3 1.50 1.20
based on a solution of nitrates, thus containing
considerable water (10 – 15 wt %). During the
1970s and 1980s, water explosives have took
over much of the market, at the expense of dyna-
mites and AN powders, because of their lower 7.5. Explosive Emulsions
production cost and greater safety during pro-
duction and handling. Since the cost of sensitizer for water gels is
Water explosives are used in cartridges or high, other formulas based on nitrate solutions
in bulk form. The bulk explosives are poured but containing cheaper raw materials have been
or pumped into the blast holes. Cartridges are investigated. This led in 1962 to “water-in-oil”
formed with a continuous through-circulation and “oil-in-water” emulsions, whose sensitivity
 Explosives 27

is due to the presence of air bubbles; these are nating devices with low-charge detonating cords
most efficiently introduced by means of hollow or electronic detonators. The use of comput-
glass bubbles or chemical gassing techniques. ers and sequential blasting machines has op-
Emulsions are produced, like water gels, by a timized firing systems, led to efficient use of
continuous or a batch process and can be used in explosive, and reduced environmental impacts
cartridges or in bulk form. Although the emul- such as noise and vibration.
sions are neither gelled nor reticulated, their stor-
age life has been considerably improved by us-
ing sophicated emulsifiers. 8. Test Methods
Emulsions differ from nitrate-fuel oil, nitrate,
and water gels in their higher detonation ve- Tests of secondary explosives are designed to
locity. The properties of typical emulsion-type study detonation phenomena, to approve a prod-
products of Nobel Explosifs, France are listed in uct, and to verify that manufactured lots meet the
Table 7. The emulsions are sensitized by a chem- requirements (i.e., quality control).
ical gassing process, apart from Iremite 2500s, Detonation phenomena (10−9 to 10−12 s) are
the formulation of which includes microspheri- observed by laser interferometry, streak cam-
cal glass bubbles. eras, and X-ray flashes, all electromagnetic
methods. The very high instantaneous pres-
sures (10 – 40 MPa) are measured, e.g., with
7.6. Uses low-impedance piezoresistive manganin gauges
(Cu–Mn–Ni alloy) [78] or with fluorinated piezo
The energy provided by explosives is used in polymers as shock sensors [101]. Phenomena
a number of ways, including explosive cladding are modelled based on Becker – Kistiakowsky –
(see Section 3.3), metal working (forming, weld- Wilson (BKW) [32] or Jones – Wilkins – Lee
ing, and cutting), and shearing by pyrotechnics (JWL) [33] equations developed in the United
systems. However, the principal nonmilitary use States at the Los Alamos Scientific Laboratories
of explosives is in mining. This application is (LASL) and the Lawrence Livermore National
governed by extensive safety regulations and is Laboratory (LLNL).
subject to competition from increasingly power- Tests to approve a product measure detona-
ful mechanical means of extraction, such as min- tion velocity and pressure, energy released, abil-
ing machines, rippers, and tunnel-boring ma- ity to initiate or transmit detonation, and critical
chines. Although the use of explosives entails diameter. They also determine the safety char-
such drawbacks as noise, vibration, and smoke, acteristics in use, storage, and transportation.
the technique is flexible, easy to use, and low in The verification of a lot is usually based on
capital and material cost. the determination of physical properties (melt-
When using bulk explosives, cost is reduced ing point, particle size, specific area) and chem-
because loading in cartridges is unnecessary. In ical analysis. Safety and storage characteristics
addition, they fill the entire blast hole, allow- must match those of the approved product.
ing the possibility of enlarging the drilling pipe. Codified tests for military use are pub-
These explosives make up half of those used in lished in the United States as military specifi-
Europe, and over three-fourths of those used in cations (MIL), in France as Manuel des modes
the United States. They can be produced on-site opératoires, in the Federal Republic of Ger-
in mobile units (ANFO truck, mix pump truck), many as VTL, in the United Kingdom as DEF.
which, however, are usually not economical for STAN, and at NATO as STANAG. Japan is-
small-scale European operations. It is also pos- sues Japanese Industrial Standards [80]. Uni-
sible to sensitize the bulk explosives just before fied and standardized European explosives tests
filling in the blast holes. In this case, the un- (EXTEST) are published in Explosifs (Belgium,
sensitized product is not entirely subject to the 1960 – 1970), in Explosivstoffe (FRG, 1971 –
regulations for producing, handling, transport- 1973), in Propellants and Explosives (FRG,
ing, and storing dangerous materials. 1977 to 1981), and in Propellants, Explosives,
The safety of explosives has been signifi- Pyrotechnics (1982 to date) (see also [7], [10]).
cantly improved by the use of nonelectric deto-
28 Explosives
Table 7. Properties of explosive emulsions used for general and underground applications

Property Iremite 1000 in cartridges Iremite 4000 in cartridges Iremite 2500s in cartridges Gemulsite 100 for
pumping

Mass energy, kJ/g 3.34 3.92 3.51 3.49

Detonation velocity m/s 5300 5300 5500 5100
Flashover coefficient, cm >5 >5 5
Detonating pressure 8.43 8.43 9.08 7.80
Density, g/cm3 1.20 1.20 1.20 1.20

8.1. Performance Tests The cylinder test has been studied at the
Lawrence National Laboratory, Livermore, Cal-
Detonation Velocity. The Dautriche method ifornia, [82]. The velocity transmitted by a cylin-
is based on a comparison of the velocity in two drical rod of explosive to a tightly fitting copper
parts of a circuit, composed in one section of a tube is measured by a streak camera.
known detonating cord and in the other of a car- For more routine measurements, the
tridge made with the test sample. The detonation Défourneaux test can be used (push-plate test).
wave fronts run in opposite directions in the two A metal plate lies on an explosive plate, which
segments and collide at a precise point [81]. is detonated by a linear wave generator. During
More sophisticated electrical or optical meth- the detonation, the metal plate is continuously
ods are also available. For example, electrical bent to an angle, which is observed, for exam-
wires (switches), inserted into a cylindrical car- ple, by X-ray flash [83]. Among other tests is
tridge at precise locations, are short-circuited underwater explosion, with measurements of
by the passage of the detonation wave, giv- the bubble produced.
ing a signal that is recorded on a chronograph.
Other methods use streak cameras. The deto- Other Performance Tests. In one of the
nation wave is built up at a distance from the critical diameter tests, the detonation propaga-
initiation point, and this occurs only if the car- tion of metal cords (copper or silver) filled with
tridge diameter is large enough. Therefore, this an explosive of known density is observed as
test requires an adequate quantity of explosive. a function of the inner diameter. In another
method, a conical charge is used.
Energy Output [5], [81]. In the lead block Other tests include the determination of the
test, strength or CUP (coefficient d’utilisation coefficient of transmission of detonation, the
pratique) is measured by the expansion of a cav- sensitivity to initiation, the self-excitation co-
ity in a lead block caused by the detonation of a efficient (maximum distance between two car-
sample of explosive, in comparison with a stan- tridges loaded with the same explosive, allow-
dard (PETN, picric acid, or TNT). ing the initiation of one by the other), and the
In the ballistic mortar test, the energy re- plate-dent test.
leased by detonation gases is measured in a steel
mortar consisting of two cavities: the first con-
tains the explosive, and is connected to the sec-
ond, which contains a projectile. The assembly
8.2. Safety
is suspended by a pendulum, and when the pro-
Stability. Aging effects are frequently deter-
jectile is driven out by the detonation, the recoil
mined by the vacuum stability test, in addition
moves the mortar to an angle that is compared
to the usual chemical methods. It can be used to
to that given by a standard explosive.
study the compatibility between explosives and
The Kast method is used to evaluate explo-
other materials.
sive brisance, a value related to the product  D2
The sample is placed in a test tube fitted with
where  = density and D = detonation velocity.
a manometric capillary glass tube; the other end
The crushing of a copper cylinder by the detona-
of the tube dips into a cup of mercury. The tube
tion is compared to that obtained with a standard
is evacuated and the sample is heated, usually
explosive.
 Explosives 29

between 80 and 130 ◦ C. The variation of the in- sive. The sensitivity is expressed by the mini-
ner pressure in the tube is shown by the mercury mum energy required to decompose the sample.
level. Pressure usually increases during the first In addition to differential thermal analysis
few hours with the release of traces of moisture (DTA) and thermogravimetric analysis (TGA),
and volatile substances. Afterward, during a pe- the following heat sensitivity tests are employed:
riod of 100 h, the rise in pressure can be linear
(constant decomposition rate) or more rapid (au- 1) The sample is subjected to a constant in-
tocatalytic decomposition). crease of temperature and the decomposition
or ignition temperature is noted; the result
Sensitivity. The impact sensitivity of an ex- depends on the quantity of explosive and the
plosive is the minimum energy that causes quick rate of heating.
decomposition [5], [13], [84]. The test condi- 2) The sample placed in a small bulb is dipped
tions strongly influence the results, which (given into a Wood’s metal bath maintained at a
in Joules) are only orders of magnitude. The fixed temperature. The time to decomposi-
classification of explosives depends on the ap- tion is noted, or the temperature at which a
paratus and the test conditions. decomposition occurs after 5 s.
In the Bruceton test for impact sensitivity, 3) The sample is ignited in a gutter and the burn-
the stimulus after a positive result is lowered by ing rate measured.
one unit and raised after a negative result. The 4) The sample is externally heated in a closed
value of the sensitivity is obtained as the mean or half-closed vessel. The tendency to burn
of 30 – 50 trials. Probabilistic values are also de- or to detonate is observed (steel-sleeve test).
termined. 5) The sample is heated at a given rate in a
The procedures differ in the size and place- closed vessel. The time of detonation or the
ment of the sample and the use of tools exposed temperature at which the sample detonates
or covered with sandpaper. The reaction may be after a given time is noted (cook-off test).
followed visually, aurally, audiometrically, or by
examination of gas evolution. To test the sensitivity to initation through a
Tests are prescribed by the U.S. Bureau spacer (card-gap test), a sample in a steel tube is
of Mines, Picatinny Arsenal (United States), subjected to the detonation of a standard booster
Explosives Research Laboratory (United explosive separated from the sample by a barrier
States), BAM (Federal Republic of Germany), of cellulose acetate cards of 0.19 mm thickness
Julius Peters (Federal Republic of Germany, [8]. The minimum number (N− ) of cards that
France), Rotter (United Kingdom, Canada), and prevent transmission of detonation fixes the le-
Aubertein (France). Another test is the Susan gal class of the explosive for transportation and
projectile-impact test, where a projectile con- other regulations.
taining ca. 450 g of explosive is directed against To obtain a LOVA agreement (MURAT in
a hard target at selected velocities. France), the following tests must be carried out
The friction sensitivity test is even more dif- on ammunitions: bullet and fragment impact,
ficult to reproduce than the impact sensitivity slow and fast cook-off tests, reaction towards
test. A thin layer of sieved explosive on a fixed a shaped-charge jet, and sympathetic reactions.
surface is rubbed by a hard or abrasive surface The results depend on storage of the ammu-
moved by translation (Julius Peters apparatus) nitions, their design, and on the properties of
or by rotation (U.S. Bureau of Mines) under ad- the propellants and explosives they contain [94],
justable pressure. [19,20]. These investigations are supported by
Impact and friction are combined in the skid the NATO Insensitive Munitions Information
test (Pantex) and the Popolato test; an explosive Center (NIMIC, Brussels).
sphere is projected against a sand-coated target
plate at defined impact angles.
In the electrostatic sensitivity test, a small 9. Legal Aspects and Production
quantity of explosive is placed between two elec-
trodes. A capacitor discharge causes a spark to Governments regulate the possesion, produc-
pass between the electrodes through the explo- tion, storage, packaging, shipping, and trading
30 Explosives

of explosives. Periodic inspections and label- In the United States, research and develop-
ing prevent theft. Tagging the explosive permits ment involving high explosives are often un-
tracing its origin. dertaken in military laboratories. Production is
conducted by arsenals or by private companies
under the GOCO system (Government owned –
9.1. Safety Regulations contractor operated), in which investments and
factories are owned by the government. The
Originally, each country established its own reg- product is government property and cannot be
ulations; the standardization recommended by sold by the operating company.
the United Nations was published in 1984 [85]. In Spain production is shared between a na-
Substances are classified according to the type tional company and private ones. In France mil-
of risk involved, unless they are too dangerous to itary secondary explosives are manufactured by
ship. Explosives are in Class 1, which contains a national company; munition loading is carried
five subdivisions [85]: out by a national and private companies.
1) Substances and articles that present a bulk Production figures and prices are generally
explosion hazard not available.
2) Substances and articles that present a projec-
tile hazard but not a bulk explosion hazard
3) Substances and articles that present a fire 10. Toxicology and Occupational
hazard and a minor blast and/or projectile
hazard without a bulk explosion hazard Health
4) Substances and articles that present no sig-
nificant hazard Raw Materials. Both acids (HNO3 and
5) Insensitive substances that present bulk ex- H2 SO4 ) and benzene derivatives (toluene and
plosion hazard, but very little probability of chlorobenzene) are of concern [4]. The usual
initiation or transition from burning to deto- safety measures must be followed to protect
nation under normal transport conditions eyes, skin, and respiratory tract. Red fumes of ni-
trogen oxides, formed normally or by accident,
Class 1 is restricted, containing only regis- can induce lung edema two days after exposure;
tered substances; for new substances, test re- the use of a gas mask is recommended.
sults must be presented. Simultaneous trans-
port and storage are permitted for “compatibility Explosives. Some primary explosives are
groups”. toxic (mercury fulminate and certain lead salts),
The transportation regulations specify pack- but the toxic hazards are far below those arising
aging, labeling, an identifying insignia on ve- from high sensitivities to detonation. Among the
hicles, compatibilities, and maximum load and secondary explosives, nitroglycerin and other
safety devices on vehicles. liquid nitrates exhibit hypotensive action accom-
Manufacture and storage are governed by the panied by headaches and, in chronic cases, by
TNT equivalency, which is defined as the quan- methemoglobinemia. A tolerance to nitroglyc-
tity of TNT producing the same effects as 100 kg erin can be developed. These substances are usu-
of the explosive [86]. ally absorbed through the skin rather than by in-
The expression d = k Q1/3 gives the safe dis- halation. For nitroglycerin and glycol dinitrate,
tance from a load Q of explosive (expressed as TLV = 1.5 mg/m3 . PETN, which like nitroglyc-
TNT equivalent), where the constant k depends erin is prescribed for heart diseases, has a very
on the presence of walls or other protection. low vapor pressure and is not readily absorbed
by the skin.
The toxic effects of TNT include blood
9.2. Production of Military Explosives changes, cyanosis, methemoglobinemia, and
High explosives are manufactured by private toxic hepatitis. It is introduced by inhalation, in-
companies in many countries, e.g., United King- gestion, and skin absorption; at inhalation level,
dom, Germany, Norway, Sweden, Switzerland,
and Japan.
 Explosives 31

TLV = ca. 1 mg/m3 . Dust in the plant is to be 15. Structure and Properties of Energetic
avoided. Materials, Symp. Proceedings, vol. 296,
Tetryl can induce an allergic dermati- Materials Research Society 1992.
tis,therefore its use is practically abandoned. Composition, Combustion and Detonation
Both RDX and HMX have negligible vapor Chemistry of Energetic Materials, Symp.
pressures. They do not penetrate the skin and Proceedings, vol. 418, Materials Research
their toxicity is very low. However, there have Society, Pittsburgh, USA 1995.
been reports of epileptiform convulsions, with- 16. J. E. Field, P. Gray, Energetic Materials, The
Royal Society, London 1992.
out liver involvement, or carcinogenic or muta-
17. Approches microscopique et macroscopique
genic effects. Dust formation should be avoided
des detonations, Journ. de Physique, Suppl.,
and masks should be worn. 1er atelier int. (31. May – 07. June 1987).
Approches microscopique et macroscopique
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32 Explosives

30. J. O. Hirschfelder et al.: Molecular Theory of 51. J. Dubar, J. Calzia, C.R. Seances Acad. Sci.
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245 – 256.
 Explosives 33

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and 133 – 144. (ONR 33395–12), 1993, 286 – 293.

Extraction → Liquid–Liquid Extraction

Extraction → Liquid–Solid Extraction
 Fats and Fatty Oils 1

Fats and Fatty Oils

Alfred Thomas, Unimills International, Hamburg, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . 3 11.3.1. Physical Methods . . . . . . . . . . 44

2. Composition . . . . . . . . . . . . . 4 11.3.2. Chemical Methods . . . . . . . . . . 45
2.1. Glycerides . . . . . . . . . . . . . . 4 12. Storage and Transportation . . . 49
2.2. Fatty Acids . . . . . . . . . . . . . . 4 13. Individual Vegetable Oils and
2.3. Phospholipids . . . . . . . . . . . . 8 Fats . . . . . . . . . . . . . . . . . . . 50
2.4. Waxes . . . . . . . . . . . . . . . . . 9 13.1. Fruit Pulp Fats . . . . . . . . . . . 50
2.5. Sterols and Sterol Esters . . . . . 9 13.1.1. Palm Oil . . . . . . . . . . . . . . . . 50
2.6. Terpenoids . . . . . . . . . . . . . . 9 13.1.2. Olive Oil . . . . . . . . . . . . . . . . 51
2.7. Other Minor Constituents . . . . 11 13.1.3. Avocado Oil . . . . . . . . . . . . . . 52
3. Physical Properties . . . . . . . . . 12 13.2. Seed-Kernel Fats . . . . . . . . . . 52
3.1. Melting and Freezing Points . . . 12 13.2.1. Lauric Acid Oils . . . . . . . . . . . 52
3.2. Thermal Properties . . . . . . . . 14 13.2.1.1. Coconut Oil . . . . . . . . . . . . . . 52
3.3. Density . . . . . . . . . . . . . . . . . 15 13.2.1.2. Palm Kernel Oil . . . . . . . . . . . 53
3.4. Viscosity . . . . . . . . . . . . . . . . 15 13.2.1.3. Babassu Oil and Other Palm Seed
3.5. Solubility and Miscibility . . . . . 15 Oils . . . . . . . . . . . . . . . . . . . 54
3.6. Surface and Interfacial Tension 17 13.2.1.4. Other Sources of Lauric Acid Oils 54
3.7. Electrical Properties . . . . . . . . 17 13.2.2. Palmitic – Stearic Acid Oils . . . . 55
3.8. Optical Properties . . . . . . . . . 17 13.2.2.1. Cocoa Butter . . . . . . . . . . . . . 55
4. Chemical Properties . . . . . . . . 18 13.2.2.2. Shea Butter, Borneo Tallow, and
4.1. Hydrolysis . . . . . . . . . . . . . . 19 Related Fats (Vegetable Butters) . 56
4.2. Interesterification . . . . . . . . . . 19 13.2.3. Palmitic Acid Oils . . . . . . . . . . 56
4.3. Hydrogenation . . . . . . . . . . . 19 13.2.3.1. Cottonseed Oil . . . . . . . . . . . . 56
4.4. Isomerization . . . . . . . . . . . . 20 13.2.3.2. Kapok and Related Oils . . . . . . 57
4.5. Polymerization . . . . . . . . . . . 20 13.2.3.3. Pumpkin Seed Oil . . . . . . . . . . 58
4.6. Autoxidation . . . . . . . . . . . . . 21 13.2.3.4. Corn (Maize) Oil . . . . . . . . . . . 58
5. Manufacture and Processing . . 22 13.2.3.5. Cereal Oils . . . . . . . . . . . . . . 58
5.1. Vegetable Oils and Fats . . . . . . 22 13.2.4. Oleic – Linoleic Acid Oils . . . . . 59
5.1.1. Storage and Handling of Raw Ma- 13.2.4.1. Sunflower Oil . . . . . . . . . . . . . 59
terials . . . . . . . . . . . . . . . . . . 22 13.2.4.2. Sesame Oil . . . . . . . . . . . . . . 60
5.1.2. Cleaning and Dehulling . . . . . . 22 13.2.4.3. Linseed Oil . . . . . . . . . . . . . . 60
5.1.3. Expelling . . . . . . . . . . . . . . . . 22 13.2.4.4. Perilla Oil . . . . . . . . . . . . . . . 61
5.1.4. Extraction . . . . . . . . . . . . . . . 24 13.2.4.5. Hempseed Oil . . . . . . . . . . . . . 61
5.2. Land-Animal Fats . . . . . . . . . 28 13.2.4.6. Teaseed Oil . . . . . . . . . . . . . . 61
5.3. Marine Oils . . . . . . . . . . . . . . 29 13.2.4.7. Safflower and Niger Seed Oils . . 62
5.4. Synthetic Fats . . . . . . . . . . . . 29 13.2.4.8. Grape-Seed Oil . . . . . . . . . . . . 62
6. Refining . . . . . . . . . . . . . . . . 29 13.2.4.9. Poppyseed Oil . . . . . . . . . . . . 62
6.1. Degumming . . . . . . . . . . . . . 30 13.2.5. Leguminous Oils . . . . . . . . . . . 63
6.2. Deacidification (Neutralization) 30 13.2.5.1. Soybean Oil . . . . . . . . . . . . . . 63
6.3. Bleaching . . . . . . . . . . . . . . . 33 13.2.5.2. Peanut Oil . . . . . . . . . . . . . . . 63
6.4. Deodorization . . . . . . . . . . . . 34 13.2.5.3. Lupine Oil . . . . . . . . . . . . . . . 64
7. Fractionation . . . . . . . . . . . . 36 13.2.6. Cruciferous Oils . . . . . . . . . . . 64
8. Hydrogenation . . . . . . . . . . . 38 13.2.6.1. Rapeseed Oil . . . . . . . . . . . . . 64
9. Interesterification . . . . . . . . . . 40 13.2.6.2. Mustard Seed Oil . . . . . . . . . . 65
10. Environmental Aspects . . . . . . 42 13.2.7. Conjugated Acid Oils . . . . . . . . 65
11. Standards and Quality Control . 42 13.2.7.1. Tung Oil and Related Oils . . . . . 65
11.1. Sampling . . . . . . . . . . . . . . . 43 13.2.7.2. Oiticica Oil and Related Oils . . . 66
11.2. Raw Materials . . . . . . . . . . . . 43 13.2.8. Substituted Fatty Acid Oils . . . . 66
11.3. Oils and Fats . . . . . . . . . . . . . 44 13.2.8.1. Castor Oil . . . . . . . . . . . . . . . 66

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 173
2 Fats and Fatty Oils

13.2.8.2. Chaulmoogra, Hydnocarpus, and 14.1.4. Horse, Goose, and Chicken Fat . . 69
Gorli Oils . . . . . . . . . . . . . . . 66 14.2. Marine Oils . . . . . . . . . . . . . . 70
13.2.8.3. Vernonia Oil . . . . . . . . . . . . . . 67 14.2.1. Whale Oil . . . . . . . . . . . . . . . 70
14. Individual Animal Fats . . . . . . 67 14.2.2. Fish Oil . . . . . . . . . . . . . . . . . 71
14.1. Land-Animal Fats . . . . . . . . . 67 15. Economic Aspects . . . . . . . . . 72
14.1.1. Lard . . . . . . . . . . . . . . . . . . . 67 16. Toxicology and Occupational
14.1.2. Beef Tallow . . . . . . . . . . . . . . 68 Health . . . . . . . . . . . . . . . . . 73
14.1.3. Mutton Tallow . . . . . . . . . . . . 69 17. References . . . . . . . . . . . . . . 73

1. Introduction North Africa, mechanical presses were used in

processing plants that approached the size of
Naturally occurring oils and fats are liquid or modern factories.
solid mixtures consisting primarily of glyc- The processing of oil fruits and seeds in Cen-
erides. Depending on whether they are solid or tral and Northern Europe advanced more slowly.
liquid at ambient temperature, they are referred Oilseeds, primarily linseed, hempseed, and rape-
to as fats or oils, respectively. Naturally occur- seed, were pulped in hollowed stones, and the oil
ring oils and fats always contain minor con- was expelled from the pulp by pressing between
stituents such as free fatty acids, phospholipids, two cloth-covered frames. This domestic-type
sterols, hydrocarbons, pigments, waxes, and vi- process was practiced up to the 16th century.
tamins. The nomenclature rules for glycerides Industrial oil milling developed primarily in re-
have been summarized [18]. gions where linseed was grown extensively. A
wood engraving dated 1568 depicts an oil mill
History. A century ago ecological, religious, with a horse-drawn vertical millstone on a stone
and social factors still played a more important bed. The ground oilseed was heated in a kettle
role than technology in the choice and utilization over an open fire and finally “beaten” in wedge
of oils and fats. presses.
Primeval humans utilized animal fats, mak- Animal fats were obtained by rendering fatty
ing cheese and butter from goat’s milk. Oilseed tissue and by churning cream. Up to the middle
plants were cultivated during the neolithic pe- of the 19th century, tallow and butter were the
riod. Poppy seeds have been found in remains most important edible fats in Europe, lard and
of Bronze-Age bread; rapeseed and linseed, vegetable oils playing only a minor role.
together with millstones, have been found in Toward the end of the 19th century the pro-
Bronze-Age dwellings. duction of oil by hydraulic pressing and solvent
Linseed, almonds, and sesame seed were part extraction was introduced. This process gave rel-
of Egypt’s natural flora. Sesame oil had mythi- atively high oil yields but necessitated posttreat-
cal significance. The oil-bearing safflower plant ment of the oils by neutralization, bleaching, and
is still grown in Egypt. Olive oil came from deodorization.
Palestine, Syria, and Crete. The Phoenicians The invention of margarine in the 1870s gave
and Greek colonists introduced the olive tree to further impetus to the oil-processing industry.
Sicily and Italy. Cotton is one of the oldest cul- With the discovery of oil hydrogenation (hard-
tivated plants; it was grown 2600 years ago in ening) at the beginning of the 20th century, liq-
India as a source of both oil and fiber. Soy and uid oils could be converted into spreadable, con-
hempseed are mentioned as oilseed plants in a sistent fats. In the 1930s, interesterification and
Chinese document of 2838 b.c. fractionation were developed as further methods
The oilseeds were ground with a pestle and to modify the consistency of oils and fats.
mortar or between stones. Simple mills of the Apart from being used for edible purposes,
type still being used in some developing coun- oils and fats are referred to in the Old Testament
tries – a concave stone rotating on a convex one – as cosmetic products and lamp fuel. Anointing
also evolved. The Egyptians developed the sack with oil symbolized royal dignity. Homer and
or expeller press. The Greeks and Romans used Herodotus refer to the use of fats as “process-
a grinding device known as the “trapetum”. In
 Fats and Fatty Oils 3

ing aids” during weaving. The ability of fats to acids. Vegetable oils are liquid at ambient tem-
calm waves was studied by Indian scholars 3000 perature because of their high proportion of un-
years ago. The Egyptians supposedly used fats as saturated fatty acids.
lubricants to transport stone blocks. They were The properties of a triglyceride are also de-
also familiar with the use of drying oils in var- termined by the position of the various fatty acid
nishes and paints. groups in the triglyceride molecule (i.e., 1-, 2-,
The elucidation of the chemical nature of fats or 3-position). The total number N of possi-
was initiated by Scheele, who produced glyc- ble triglycerides (including positional isomers)
erol from olive oil around 1780. Chevreul sub- from x different fatty acids is
sequently (ca. 1815) recognized that fats were x2 +x3
predominantly esters of fatty acids and glycerol. N=
2
Modern research and development is fo- However, the proportions of different triglyc-
cussed on the application of new biotechnologi- erides in a naturally occurring fat generally
cal principles to the production and modification do not conform to a statistical distribution.
of oils and fats [19], as well as on nutritional as- In vegetable oils and fats, unsaturated fatty
pects, problems of trace contaminants, and envi- acids are linked preferentially to the 2-position
ronmental pollution. The breeding of new plant of the glycerol group, whereas in animal fats
varieties is an important method for increasing they appear primarily in the 1- and 3-positions
the types of oils and fats. Examples are new va- (“2-random” and “1,3-random” distributions)
rieties of rapeseed (low erucic acid content), saf- [20]. Extreme examples of nonrandom distribu-
flower, and sunflower (high in oleic acid). New tions of fatty acid groups over the triglyceride
sources of oils and fats are being exploited by molecule are cocoa butter (ca. 40 % 1-palmito-
cultivation of wild plants such as the jojoba and 3-stearo-2-olein) and lard (ca. 20 % 2-palmito-
Cuphea shrubs. 1,3-diolein).

2. Composition 2.2. Fatty Acids

The fatty acids that form the triglycerides of
2.1. Glycerides naturally occurring oils and fats are predomi-
nantly even-numbered, straight-chain, aliphatic
Naturally occurring fats contain about 97 % monocarboxylic acids with chain lengths rang-
triglycerides (triacylglycerides), i.e., triesters of ing from C4 to C24 . Unsaturated fatty acids
glycerol with fatty acids; up to 3 % diglyc- differ in number and position of double bonds
erides (diacylglycerides); and up to 1 % mono- and in configuration (i.e., cis or trans iso-
glycerides (monoacylglycerides). Tri-, di-, and mers). The more common fatty acids are
monoglycerides consist of 1 mol of glycerol es- known by trivial names such as butyric, lau-
terified with 3 mol, 2 mol, or 1 mol of fatty acid, ric, palmitic, oleic, stearic, linoleic, linolenic
respectively. The triglycerides of naturally oc- (→ Fatty Acids). Crude oils contain significant
curring oils and fats contain at least two dif- amounts of free fatty acids.
ferent fatty acid groups. The chemical, physi- The chief fatty acids in some commercial oils
cal, and biological properties of oils and fats and fats are listed Tables 1 (saturated fatty acids)
are determined by the type of the fatty acid and 2 (unsaturated fatty acids). The fatty acid
groups and their distribution over the triglyc- composition of most vegetable oils and fats is
eride molecules. The melting point generally in- relatively simple; they consist predominantly of
creases with increasing proportion of long chain palmitic, oleic, and linoleic acids [20]. The fatty
fatty acids or decreasing proportion of short acids of land-animal fats mainly have a chain
chain or unsaturated fatty acids. Milk fat (but- length of C16 or C18 . They are formed by biosyn-
terfat) and coconut oil, which contain a high thetic conversion of carbohydrates, proteins, or
proportion of C6 – C12 fatty acids, have lower fats, or originate directly from ingested fat.
melting points than fats such as tallow and lard, Ruminant fats contain 5 – 10 % trans fatty
which contain predominantly C16 and C18 fatty acids, which are produced from linoleic and
4 Fats and Fatty Oils
Table 1. Saturated fatty acids in various oils and fats, (main sources: Unilever; Food RA, Leatherhead; ITERG a )

Saturated fatty acids b , g/100 g fatty acids

C10 and C12 C14 C16 C18 C20 C22 C24

lower

Liquid vegetable oils

Almond tr 6.5 – 7 1 – 2.5 tr tr
Avocado tr 10 – 26 0.5 – 1
Corn germ tr – 0.5 tr – 0.3 9 – 12 1–3 ca. 0.5 tr – 0.5 <0.5
Cottonseed tr 0.5 – 2.0 21 – 27 2–3 <0.5 tr tr
Grape-seed 4 – 11 2–5 tr tr tr
Linseed tr tr 5–6 3–5 <0.5 tr – 0.2 tr
Olive 7 – 16 2–4 ca. 0.5 tr tr
Peanut (Africa) tr 7 – 12 1.5 – 5 ca. 1.5 2–4 1–2
Peanut (South America) tr 10 – 13 1.5 – 4 ca. 1.5 3–4 1.5 – 2
Pumpkinseed 7 – 13 6–7 tr
Rapeseed (high erucic) tr tr 2–4 1–2 0.5 – 1 0.5 – 2.0 0.5
Rapeseed (low erucic) tr tr 3–6 1 – 2.5 <1 tr – 0.5 tr – 0.2
Ricebran ca. 0.5 13 – 18 ca. 2 0.5 – 1 ca. 0.5
Safflower tr tr ca. 5 2–3 ca. 0.5 ca. 1 ca. 1
Sesame tr 8 – 10 3–6 ca. 0.5
Soybean <0.5 8 – 12 3–5 <0.5 tr
Sunflower tr tr – 0.1 5.5 – 8 2.5 – 6.5 <0.5 0.5 – 1.0 <0.5
Wheat germ 12 – 14 ca. 1 0.5 tr
Consistent vegetable fats
Babassu oil ca. 12 42 – 44 15 – 18 8 – 10 2–3 tr
Coconut oil ca. 13 41 – 46 18 – 21 9 – 12 2–4 tr tr
Cocoa butter tr tr 23 – 30 32 – 37 <1 ca. 0.5
Palm kernel oil ca. 7 41 – 45 15 – 17 7 – 10 2–3 tr – 0.3 tr – 0.5
Palm oil (Africa) tr 1–2 41 – 46 4 – 6.5 ca. 0.5
Palm oil (Indonesia) tr – 0.5 ca. 1 41 – 47 4–6 ca. 0.5
Animal fats
Beef tallow tr 2–4 23 – 29 20 – 35 <0.5 tr
Butterfat 7–9 2–5 8 – 14 24 – 32 9 – 13 2
Chicken fat ca. 1 20 – 24 4–7
Goose fat 20 – 22 4 – 11
Horse fat tr ca. 0.5 3–6 20 – 30 6 – 10 tr
Lard tr <0.5 ca. 1.5 24 – 30 12 – 18 ca. 0.5
Mutton tallow tr ca. 0.5 1–4 22 – 30 15 – 30 tr tr
Marine oils
Fish oils
Japanese tr tr ca. 6 ca. 16 ca. 3 <0.5 tr tr – 1
Menhaden tr tr ca. 9 ca. 20 ca. 4 tr – 1 tr tr – 1
Scandinavian tr tr 6–8 11 – 15 1–3 tr – 0.5 tr tr – 1
South American tr tr ca. 7 17 – 19 2–4 ca. 0.5 tr tr – 1
Whale oil tr ca. 0.5 4 – 10 10 – 18 1–3 tr
a
ITERG = Institut des Corps Gras, Centre Technique Industrielle, Paris.
b
tr = traces (<0.05 %).

linolenic acid in the rumen. Marine oils contain role in the identification of fats and their detec-
a high proportion of polyunsaturated fatty acids tion in mixtures.
with a chain length of C20 – C24 . Land-animal The fatty acid composition of a naturally oc-
fats and marine oils contain numerous odd- curring fat is determined genetically. The fatty
numbered and branched fatty acids in trace con- acid composition of oleaginous seeds can be
centrations. More than 80 different fatty acids changed by developing new varieties. Exam-
have been found in milk fat, and more than 40 ples are low-linoleic safflower and sunflower
in lard. However, most of these fatty acids occur oils and low-erucic rapeseed oil. Environmental
only in traces. They can be of industrial signifi- factors can influence the fatty acid composition
cance for some oils and fats and they can play a within certain limits. The proportion of unsat-
 Fats and Fatty Oils 5
Table 2. Unsaturated fatty acids in various oils and fats, (main sources: Unilever; Food RA, Leatherhead; ITERG a )

Unsaturated fatty acids b , g/100 g fatty acids

C14 : 1 C16 : 1 C18 : 1 C18 : 2 C18 : 3 C20 : 1 C22 : 1 C20 : x c C22 : x c C24 : 1

Liquid vegetable
oils
Almond <0.5 65 – 69 21 – 25 tr tr – 0.1
Avocado 2 – 12 44 – 76 8 – 25 ca. 1
Corn germ <0.5 25 – 35 40 – 60 ca. 1 ca. 0.5 tr – 0.1
Cottonseed <1 14 – 21 45 – 58 tr – 0.2 tr
Grape-seed 12 – 33 45 – 72 1–2
Linseed tr 18 – 26 14 – 20 51 – 56 <0.5
Olive 1–2 64 – 86 4 – 15 0.5 – 1 0.5
Peanut (Africa) <0.5 50 – 70 14 – 30 tr 0.5 – 1.5 tr
Peanut (South <0.5 35 – 42 39 – 44 tr 0.5 – 1.5 tr
America)
Pumpkinseed 24 – 41 46 – 57
Rapeseed (high ca. 0.5 11 – 24 10 – 22 7 – 13 ca. 10 41 – 52
erucic)
Rapeseed (low 0.1 – 0.5 52 – 66 17 – 25 8 – 11 1.5 – 3.5 tr – 2.5 tr – 0.1 tr
erucic)
Ricebran ca. 44 30 – 40
Safflower tr 12 – 20 70 – 80 tr tr
Sesame tr 35 – 46 40 – 48 tr – 0.5 <0.5
Soybean tr 18 – 25 49 – 57 6 – 11 <0.5
Sunflower <0.5 14 – 34 55 – 73 tr – 0.4 <0.5 tr – 0.3
Wheat germ ca. 30 40 – 55 ca. 7
Consistent
vegetable fats
Babassu oil 14 – 16 1–2
Coconut oil tr tr 5–9 0.5 – 3 tr tr
Cocoa butter ca. 0.5 30 – 37 2–4
Palm kernel oil 10 – 18 1–3 tr – 0.5 tr – 0.5
Palm oil (Africa) <0.5 37 – 42 8 – 12 tr – 0.5 tr
Palm oil ca. 0.5 37 – 41 ca. 10 tr – 0.5 tr
(Indonesia)
Animal fats
Beef tallow ca. 0.5 2–4 26 – 45 2–6 ca. 1 <0.5 tr ca. 0.5
Butterfat ca. 2 3 19 – 33 1–4 2–6 ca. 2
Chicken fat ca. 7 38 – 44 18 – 23 ca. 1 0.5 – 1
Goose fat 41 – 74 7 – 19
Horse fat 3 – 10 36 – 40 6 – 11 4–9 tr – 0.5 tr 1–2
Lard tr 2–3 36 – 52 10 – 12 ca. 1 0.5 – 1 <0.5 tr
Mutton tallow ca. 0.5 3–4 31 – 56 3–7 1–2 ca. 0.5
Marine oils
Fish oils
Japanese tr ca. 7 ca. 14 ca. 2 ca. 1 ca. 7 ca. 6 ca. 15 ca. 12 tr – 1
Menhaden tr ca. 11 ca. 13 ca. 2 ca. 1 ca. 2 ca. 1 ca. 14 ca. 11 tr – 1
Scandinavian tr 6 – 11 12 – 15 1–2 0.5 – 1 9 – 16 14 – 20 6 – 10 5 – 11 tr – 1
South American tr 9 – 11 14 – 15 1–2 0.5 – 1 1–2 1–2 7 – 19 10 – 14 tr – 1
Whale oil 1–3 13 – 20 24 – 33 1–2 tr 10 – 15 4 – 10 1–6 5–7 tr
a
ITERG = Institut des Corps Gras, Centre Technique Industrielle, Paris.
b
tr = traces (<0.05 %).
c
x > 1.

urated fatty acids in the glycerides of linseed, acids and thus a relatively low melting point.
soybean, and sunflower oils, for example, gen- Linoleic acid cannot be synthesized by the ani-
erally increases as the climate becomes colder mal or human organism and is hence referred to
and wetter. The subcutaneous fats of marine an- as an “essential” fatty acid.
imals living in the colder parts of the oceans have Naturally occurring oils and fats are dis-
a particularly high content of unsaturated fatty tributed homogeneously in varying concentra-
6 Fats and Fatty Oils

tions in vegetable and animal tissues. In plants into fat synthesis in the udder explains the occur-
they are found predominantly in the seeds and rence of branched and odd-numbered fatty acids
the fruit pulp where they serve as a source of in milk fat.
energy. Oleic acid appears to play a key role in plants.
It is probably synthesized from short-chain fatty
Biosynthesis. The synthesis of fatty acids in acids and can be dehydrogenated into more
plants and animals generally starts with “ac- highly unsaturated fatty acids; be converted into
tivated” acetic acid, i.e., acetyl coenzyme A, substituted acids such as ricinoleic acid; or elon-
which is derived from carbohydrates via pyru- gated into erucic acid by specific enzyme sys-
vic acid. Animals also synthesize acetyl coen- tems (Fig. 1).
zyme A from amino acids. In the animal organism oleic acid is formed by
A distinction is made between de novo syn- dehydrogenation of stearic acid. Further dehy-
thesis of saturated fatty acids and elongation of drogenation to linoleic and linolenic acid does
a fatty acid chain. De novo synthesis leads pri- not take place. The animal organism can, how-
marily to palmitic acid with smaller amounts of ever, further desaturate linoleic and linolenic
lauric, myristic, and stearic acids. acid by introducing double bonds between the
carboxyl group and the double bond nearest
to it. Together with an elongation of the fatty
acid chain this leads to the formation of γ-
dihomolinolenic acid (C20 : 3 ), arachidonic acid
(C20 : 4 ), and eicosopentaenoic acid (C20 : 5 ),
which are precursors of prostaglandins.
Three activated fatty acids (RCOSCoA) react
successively with a molecule of phosphorylated
glycerol to form a triglyceride molecule. The
factors that determine the distribution of the fatty
acids over the 1-, 2-, and 3-positions of the glyc-
erides are not fully known. Phosphatides are also
synthesized by this route.

The conversion of palmitic into stearic acid

and the formation of longer chain saturated
and unsaturated fatty acids presumably takes
place by elongation, which involves addition
of acetyl coenzyme A to activated fatty acids
(RCOSCoA).

Biodegradation. During digestion and ab-

sorption of fats, triglycerides are successively
The synthesis of fatty acids from C2 units ex- split into di- and monoglycerides, glycerol, and
plains the predominance of even-numbered fatty fatty acids by lipases. The products are absorbed
acids in naturally occurring oils and fats. Bacte- by the intestinal epithelial cells either as water-
rial degradation of feed in the rumen leads not soluble complexes or as micelles. The fatty acids
only to acetic and butyric acids but also to propi- are biodegraded mainly via β-oxidation:
onic acid (C3 ); incorporation of these C3 units
 Fats and Fatty Oils 7

Figure 1. Unsaturated fatty acids derived from oleic acid

Some important phosphatides are phospha-

tidylcholine [8002-43-5] (lecithin), phosphati-
dylethanolamine [5681-36-7] ( cephalin), phos-
phatidylinositol [2816-11-7], and phosphati-
dylserine.

The bio-oxidation of unsaturated fatty acids

involves additional steps.

2.3. Phospholipids [20]

Phospholipids are essential constituents of the

protoplasm of animal and plant cells; they are
mostly present as lipoproteins and lipidcarbo- The plasmalogens are ethers of fatty alcohols
hydrate complexes. Oilseeds, cereal germs, egg and phosphatidic acid; they occur in animal tis-
yolk, and brain are the richest sources of phos- sue.
pholipids. Esters of glycerophosphoric acid ( Sphingolipids are derivatives of the ami-
glycerol 1-phosphate) are usually referred to as no alcohol sphingosine. For example, sphin-
phosphatides (→ Lecithin). gomyelins are constituents of the phospholipids
in the brain, blood plasma, and erythrocytes.

The cerebrosides are derivatives of sphin-

gosine and either galactose ( galactolipids) or
glucose ( glycolipids). They are important con-
8 Fats and Fatty Oils

stituents of the myelin nerve sheath. The gan- in cod liver oil. Other animal and vegetable oils
gliosides are based on neuraminic acid and are contain hardly any vitamin D.
found in the ganglia cells of the brain.
Lecithin, cephalin, inositol phosphatides, and
phosphatidic acid are the principal phospholipid 2.6. Terpenoids
components of plant origin. During pre-refining
of crude vegetable oils, especially soybean and The nonsaponifiable part of most fats also con-
rapeseed oil, most of the phosphatides are re- tains traces of terpenes and terpene alcohols. The
moved as sludge by hydration with water. Dry- triterpene squalene [7683-64-9] occurs in rela-
ing of this sludge yields “lecithin,” which is used, tively high concentrations (up to 0.5 %) in olive
often after further modification, in the food in- oil. Shea butter contains 2 – 10 % of kariten, a
dustry as an emulsifier, antispattering agent, dis- rubber-like hydrocarbon.
persant, or viscosity reducing agent. Lecithin is Carotenoid pigments occur widely in oils and
also used in pharmaceuticals, toiletries, animal fats. Approximately 70 different carotenoids,
feeds, and as a mold release agent and emulsi- ranging in color from yellow to deep red, are
fier – dispersant [21]. The phosphatide contents known. The most well-known carotenoids are
of crude oils and fats are listed in Table 3; the the isomeric tetraterpenes (C40 H56 ) α-carotene
phosphatides are almost completely removed [7488-99-5], β-carotene [7235-40-7], and γ-
during refining of oils and fats. carotene [472-93-5], lycopene [502-65-8], and
xanthophyll [127-40-2]. Crude palm oil contains
up to 0.2 % α- and β-carotene.
2.4. Waxes The bulk of the carotenoids are removed dur-
ing refining, primarily during bleaching and de-
Waxes are esters of fatty alcohols and fatty acids odorization. β-Carotene (provitamin A) can be
(→ Waxes). Free and esterified fatty alcohols oxidized to vitamin A [68-26-8] in the animal
(e.g., cetyl, stearyl, oleyl alcohols) occur in con- organism. Most vegetable oils and fats do not
siderable concentrations in marine oils. Ethers contain significant concentrations of vitamin A;
of glycerol and fatty alcohols (batyl, chimyl, and in most countries margarine therefore contains
selachyl alcohols) are also found in animal tis- added vitamin A. Vitamin A is present in high
sues. The wax in the seed coat of sunflower seed concentrations in fishliver oils. Butter contains
causes the oil to become cloudy at refrigerator ca. 0.003 – 0.0015 % vitamin A.
temperatures and is therefore removed by win- The most important compounds of the vita-
terization (see Chap. 7). min E [59-02-9] group are α-, β-, γ-, and δ-
tocopherols:

2.5. Sterols and Sterol Esters

The major part of the nonsaponifiable matter of
oils and fats consists of sterols present as such
or as fatty acid esters and glycolipids. The most
important sterol in animal fats is cholesterol
[57-88-5]. β-Sitosterol [83-46-5] is the predom-
inant sterol in vegetable oils and fats, although
traces of cholesterol are also present. Total sterol
concentrations are shown in Table 3, and sterol These compounds act as a vitamin (rat fertility
compositions in Table 4. Some of the sterols factor) and as antioxidants. α-Tocopherol has
are removed during the deodorization step of re- the highest biological activity.
fining oils and fats, without, however, changing Tocopherols occur only in traces in animal
their relative composition. Sterols are therefore a fats, whereas vegetable oils contain appreciable
useful tool in checking authenticity. Vitamin D2 concentrations (see Table 5). Refined oils and
[50-14-6] (calciferol) is present in milk and but-
ter, and vitamin D3 [67-97-0] (cholecalciferol)
 Fats and Fatty Oils 9
Table 3. Minor constituents of crude oils and fats

Content, wt %

Phosphatides Tocopherols Sterols

Babassu fat 0.003

Beef tallow <0.07 0.001 0.08 – 0.14
Butterfat <1.4 0.003 0.24 – 0.50
Castor oil 0.5
Cocoa butter 0.1 0.003 0.17 – 0.20
Coconut oil 0.003 0.05 – 0.1
Cod liver oil 0.42 – 0.54
Corn germ oil 1–2 0.1 – 0.3 0.8 – 2.2
Cottonseed oil 0.7 – 0.9 0.04 – 0.11 0.27 – 0.6
Fish oil ca. 0.3
Lard <0.05 0.003 ca. 0.1
Linseed oil 0.3 0.11 0.37 – 0.42
Olive oil 0.01 – 0.03 0.1 – 0.2
Palm oil 0.05 – 0.1 0.02 – 0.12 0.04 – 0.08
Palm kernel fat 0.08 – 0.12
Peanut oil 0.3 – 0.4 0.02 – 0.07 0.19 – 0.29
Rapeseed oil 2.5 0.07 – 0.08 0.5 – 1.1
Sesame oil 0.1 ca. 0.05 0.4 – 0.6
Soybean oil 1.1 – 3.2 0.09 – 0.12 0.2 – 0.4
Sunflower oil <1.5 0.07 – 0.1 0.25 – 0.45
Wheat germ oil 0.1 – 2.0 ca. 0.28 1.3 – 1.7

Table 4. Sterol composition ∗ in crude oils (main sources: Food RA, Leatherhead; Unilever; ITERG ∗∗)

Coconut Corn Cotton- Olive Palm Palm Peanut Rapeseed Soybean Sunflower
germ seed kernel

Cholesterol 0.6 – 2 0.2 – 0.6 0.7 – 2.3 0 – 0.5 2.2 – 6.7 1 – 3.7 0.6 – 3.8 0.4 – 2 0.6 – 1.4 0.2 – 1.3
Brassicasterol 0 – 0.9 0 – 0.2 0.1 – 0.9 0 – 0.3 0 – 0.2 5 – 13 0 – 0.3 0 – 0.2
Campesterol 7 – 10 18 – 24 7.2 – 8.4 2.3 – 3.6 18.7 – 29.1 8.4 – 12.7 12 – 20 18 – 39 16 – 24 7 – 13
Stigmasterol 12 – 18 4–8 1.2 – 1.8 0.6 – 2 8.9 – 13.9 12.3 – 16.1 5 – 13 0 – 0.7 16 – 19 8 – 11
β-Sitosterol 50 – 70 55 – 67 80 – 90 75.6 – 90 50.2 – 62.1 62.6 – 70.4 48 – 65 45 – 58 52 – 58 56 – 63
∆5-Avenasterol 5 – 16 4–8 1.9 – 3.8 3.1 – 14 0 – 2.8 4–9 7–9 0 – 6.6 2–4 2–7
∆7-Stigmastenol 2–8 1–4 0.7 – 1.4 0–4 0.2 – 2.4 0 – 2.1 0–5 0–5 1.5 – 5 7 – 13
∆7-Avenasterol 0.6 – 2 1–3 1.4 – 3.3 0 – 5.1 0 – 1.4 0–5 0 – 0.8 1 – 4.5 3–6

∗ Sterols as percentage of total sterol fraction.

∗∗ ITERG = Institut des Corps Gras, Centre Technique Industrielle, Paris.

fats still contain ca. 80 % of the original toco- in crude cottonseed and kapokseed oils (0.5 –
pherols, the main losses occurring during de- 1.5 %). Gossypol is removed during refining in
odorization. Deodorizer distillates are a valuable the lye neutralization step.
source of natural tocopherols. Crude linseed, rapeseed, soybean, olive, avo-
cado, and many other vegetable oils contain the
green pigments chlorophyll and phaeophytin.
2.7. Other Minor Constituents The chlorophyll content is particularly high in
oil from immature seeds and is generally de-
Sesame oil contains 0.3 – 0.5 % sesamolin
termined by harvesting and climatic conditions.
[526-07-8], a glycoside of the phenol sesamol
Chlorophyll is generally regarded to be indica-
[533-31-3], and 0.5 – 2.0 % sesamin [607-80-7].
tive of inferior crude oil quality; it can be re-
These minor constituents give a characteristic
moved by treatment with acidic absorbents such
color reaction (the basis of the Baudouin test)
as bleaching earth.
and impart stability to oxidation.
Gossypol [303-45-7], a toxic polyphenol
with pronounced antioxidant activity, is found
 10 Fats and Fatty Oils

Crude oils and fats may contain traces of pro-

teins, the concentration depending on process-
600 – 1000

650 – 1000

ing conditions. In addition, vegetable oils may

Sunflower

15 – 35

contain carbohydrates. These compounds are re-

3 – 35
0–7

moved almost completely in refining.

Autoxidation of the fatty acid groups of
900 – 1200

triglycerides leads to the formation of volatile

580 – 740
275 – 320
Soybean

60 – 75
10 – 20

and nonvolatile oxidation products. The type and

quantity of the volatile compounds (ketones, al-
dehydes, and alcohols) depend on the initial fatty
acid composition and the oxidation conditions.
500 – 540

500 – 550
Sesame

2 – 18

These volatile products are responsible for the

<0.5

<0.5

typical odor and taste of oils and fats. One of the

main aims of refining is to remove these odor-
Safflower

ca. 580

ca. 610

iferous compounds, which in some cases occur

ca. 18
ca. 16
<0.5

in concentrations of only 10−3 ppm. The non-

volatile oxidation products generally have little
odor and taste, but they can act as oxidation pro-
230 – 300

400 – 550
Rapeseed

670 – 800
15 – 20

moters.
5 – 10

Most crude oils and fats contain traces of pes-

ticide residues and metals (e.g., Fe, Cu, Pb, As,
100 – 400

175 – 700
50 – 300

Cd, and Hg) as a consequence of crop treat-

Peanut

0 – 20

ment and environmental influences. Whereas

phosphate-based pesticides used to treat oilseeds
Table 5. Tocopherols (mg/kg) in crude oils (main sources: Food RA, Leatherhead; Unilever; ITERG ∗∗ [22] )

decompose with time, chlorinated pesticides are

0 – 123
kernel

0 – 44

stable and gradually migrate into the oil.

Palm

0–6

Peanut oil may contain traces of aflatoxins

produced by growth of Aspergillus flavus on the
200 – 1200
80 – 95 ∗

5 – 15 ∗

seed.
0–5∗

0–5∗
Palm

Most oils and fats, particularly coconut oil,

contain varying concentrations of polycyclic
aromatic hydrocarbons. These hydrocarbons are
100 – 250

110 – 270

introduced during smoke-drying of the raw ma-

8 – 14
Olive

∗∗ ITERG = Institut des Corps Gras, Centre Technique Industrielle, Paris.

<10
0–4

terials prior to storage and further processing.

Crude rapeseed oil contains up to 50 ppm of
410 – 1169

sulfur in the form of elemental sulfur, isoth-

140 – 540

160 – 625
Cotton-

iocyanates, and 5-vinyl-2-oxazolidinethione

0 – 17
seed

∗ Tocopherols as percentage of total tocopherol fraction.

[500-12-9] ( goitrin) derived from glucosino-

lates (sulfur-containing glucosides) in the seed.
1100 – 1300

All of these undesirable contaminants are re-

270 – 370

640 – 860
10 – 16

30 – 50

duced to negligibly low levels in the course of

germ
Corn

refining, if necessary with the aid of additional

steps such as adsorptive treatment with activated
Coconut

charcoal to remove polycyclic aromatic hydro-

0 – 17
0 – 14

0 – 31
0–2

carbons.
α-Tocopherol
β-Tocopherol
γ-Tocopherol
δ-Tocopherol

Total
 Fats and Fatty Oils 11
Table 6. Melting points of fatty acids and glycerides in their stable polymorphic forms

mp (slip point), ◦ C

Fatty acid 1-Monoglyceride 1,3-Diglyceride Triglyceride

Butyric acid −7.9

Caproic acid −3.9 19.4 −25.0
Caprylic acid 16.3 40.0 8.3
Capric acid 31.3 53.0 44.5 31.5
Lauric acid 44.0 63.0 56.5 46.5
Myristic acid 54.4 70.5 65.5 57.0
Palmitic acid 62.9 77.0 72.5 65.5
Stearic acid 69.6 81.0 78.0 73.0
Arachidic acid 75.4 84.0 (72.0)
(75.0)
Behenic acid 79.9 81.0
Oleic acid 16.3 35.2 21.5 5.5
Elaidic acid 45.0 58.5 55.0 42.0
Erucic acid 34.7 50.0 46.5 30.0
Linoleic acid −5.0 12.3 −2.6 −13.1
Linolenic acid −11.0 15.7 −12.3 −24.2
Ricinoleic acid 5.0

3. Physical Properties [23] Table 7. Melting points of some polymorphic triglycerides

◦
3.1. Melting and Freezing Points mp, C

α β β
The melting point of the even-numbered, sat-
Trilaurin 15.0 35.0 46.5
urated fatty acids increases with increasing Trimyristin 33.0 46.5 57.0
chain-length, and decreases with increasing de- Tripalmitin 45.0 56.0 65.5
gree of unsaturation (see also → Fatty Acids, Tristearin 54.5 65.0 73.0
Triolein −32.0 −12.0 5.5
Chap. 2.1.). The glycerides show a similar be- Trielaidin 15.5 37.0 42.0
havior (Table 6). Since the naturally occurring 1,2-Dicapriolaurin 17.5 26.0 30.0
fats are mixtures of glycerides, they melt over a 2-Capriodilaurin 23.0 33.0 38.5
wide range of temperature (for methods of melt- 1-Laurodimyristin 37.0 42.0 46.5
1-Laurodipalmitin 45.0 49.5 54.0
ing point determination, see Section 11.3.1). 2-Laurodipalmitin 47.0 50.0 53.5
The melting point also depends on the poly- 1,2-Dicapriostearin 32.0 38.0 41.0
morphic form of the glycerides, i.e., the crys- 1,3-Dicapriostearin 34.0 40.0 44.5
2-Palmitodistearin 56.0 64.0 68.5
talline structure (Table 7). The packing density 1,3-Dicaprioolein −10.2 0.6 6.2
and the spatial arrangement of the triglyceride 1,2-Dilauroolein −10.0 4.8 16.0
molecules depend on the crystallization condi- 1,2-Dipalmitoolein ca. 18.0 ca. 31.0 34.5
tions. X-ray diffraction patterns (short spacing 1,3-Dipalmitoolein 26.5 33.5 38.0
1,2-Distearoolein ca. 30.0 ca. 40.0
lines) can distinguish between three different 1,3-Distearoolein 37.0 41.5 44.0
polymorphic forms [25]. The lowest melting and 1,3-Dipalmitoelaidin ca. 40.0 53.0 54.0
most labile form is designated α. The most stable 1-Stearodibehenin 61.3 71.0 73.5
form is called β and the intermediate one β  . The 1-Lauro-2-myristo-3-palmitin 37.0 44.0 49.0
1-Lauro-2-myristo-3-stearin 27.5 45.5 49.5
α form is obtained by rapidly cooling the molten 1-Palmito-3-stearo-2-olein 18.2 33.0 38.0
triglycerides, the β  form by suitable temper-
ing. Polymorphic changes induced by process-
ing conditions are of great practical importance The congeal or set point (point of solidifica-
since they can significantly influence the prop- tion) is generally lower than the melting point.
erties of, for example, a margarine (oral melting
behavior, sandiness) or chocolate (fat bloom).
12 Fats and Fatty Oils

Table 9. Specific heat of oils and fats

Specific Temperature,
◦
heat, J/g C

Trilaurin 2.130 66.0

Trimyristin 2.152 58.4
Tripalmitin 2.173 65.7
Tristearin 2.219 79.0
Soybean oil 2.060 80.4
2.000 60.0
Linseed oil 2.050 70.7
Cottonseed oil 2.200 90.0
Hardened cottonseed oil ∗ 2.177 79.6
Olive oil 2.300 110
Palm oil 2.400 140
Sunflower oil 2.500 175.0

∗ Iodine value ca. 6.

Table 10. Vapor pressure of triglycerides (temperatures

Figure 2. Dilatation curves for cocoa butter and lard corresponding to a vapor pressure p of 6.7 Pa (0.05 mm Hg) and
0.13 Pa (0.001 mm Hg)

Temperature, ◦ C
The solids content of a fat at different tem-
p = 6.7 Pa p = 0.13 Pa
peratures is normally determined by pulsed nu-
clear magnetic resonance [24]. Fats exhibit an Tributyrin 91 45
increase in volume (dilatation) on melting that Tricaproin 135 85
Tricaprylin 179 128
is disproportionately larger than that on heat- Tricaprin 213 159
ing a liquid fat; an obsolete method of measur- Trilaurin 244 188
ing solids content at different temperatures was Trimyristin 275 216
based on dilatation. Dilatation or solids content Tripalmitin 298 239
Tristearin 313 253
curves can be used to characterize a fat. Fig- Soybean oil 308 254
ure 2 reflects the large proportion of 1-palmito- Olive oil 308 253
3-stearo-2-olein in cocoa butter and the more 1,3-Distearoolein 315 254
1-Myristo-2-palmito-3-stearin 297 237
complex glyceride composition of lard. 1-Palmito-2-lauro-3-stearin 290 232
The latent heat of fusion increases with in- 1-Myristo-2-lauro-3-stearin 282 223
creasing chain length and increasing degree of 1-Palmito-2-capro-3-stearin 280 223
saturation (see Table 8). Naturally occurring fats 1-Capro-2-lauro-3-myristin 249 189

generally have a lower heat of fusion than simple

glycerides.

3.2. Thermal Properties

Table 8. Latent heat of fusion of some fats

Heat of fusion, J/g The approximate heats of combustion of oils

and fats can be calculated from the following
Butterfat 81.6
Cottonseed oil 86.0
formula:
Fully hardened cottonseed oil ∗ 185.0
Peanut oil 90.9 Heatof combustion (J/g)
Partially hardened peanut oil ∗∗ 103.4 = 47645 − 4.1868 × iodinevalue
Trilaurin (β-form) 193.5
Tripalmitin (β-form) 222.0 −38.31 × saponificationvalue
Tristearin (β-form) 228.0
Using this equation, values ranging from
∗ Iodine value ca. 1. 37 765 J/g (9020 cal/g) for coconut oil to
∗∗ Iodine value ca. 60.
40 528 J/g (9680 cal/g) for a high-erucic rape-
seed oil have been obtained.
 Fats and Fatty Oils 13

The specific heat of liquid oils and fats in- fatty acid content tends to decrease the density of
creases with increasing chain length and degree a crude oil. The following formula can be used
of saturation (see Table 9); it also increases with to estimate the density of an oil:
temperature.
Triglycerides of long-chain fatty acids have d15
15 = 0.8475 + 0.0003 × saponificationvalue
extremely low vapor pressures; typical data +0.00014 × iodinevalue
for some triglycerides and oils are shown in
Table 10. Monoglycerides have significantly Up to 260 ◦ C the density decreases by about
higher vapor pressures (see Table 11). There is 0.00064 g/cm3 per temperature increase of 1 ◦ C.
relatively little information on the heats of va- The following equations apply for the density 
porization of fats (see Table 12). (in g/L) of commercial oils and fats (t = temper-
Table 11. Boiling points of some monoglycerides ature in ◦ C):
Pressure, Pa bp, ◦ C Soybean oil 933.4 − 0.657 t
Sunflower oil 932.7 − 0.680 t
Monocaprin 133.3 175 Sesame oil 933.0 − 0.700 t
Monolaurin 133.3 186 Cottonseed oil 931.7 − 0.755 t
Monomyristin 133.3 199 Peanut oil 927.0 − 0.642 t
Monopalmitin 133.3 211 Olive oil 928.5 − 0.700 t
Monostearin 26.7 190 Palm oil 925.0 − 0.655 t
Monoolein 26.7 186 Palm kernel oil 940.0 − 0.740 t
Coconut oil 932.0 − 0.745 t
Rapeseed oil 925.5 − 0.700 t
Tallow 956.8 − 0.898 t
Table 12. Heat of vaporization of some triglycerides calculated for Fish oil 940.0 − 0.700 t
0.13 – 67 Pa

Heat of vaporization, J/g

Tricaprylin 247.0
Tricaprin 226.1
Trilaurin 213.5 3.4. Viscosity
Trimyristin 205.2
Tripalmitin 201.0 Oils tend to have a relatively high viscosity be-
Tristearin 188.4
Soybean oil 209.3 cause of intermolecular attraction between their
fatty acid chains. Generally, viscosity tends to
increase slightly with increasing degree of satu-
Oils and fats are relatively poor thermal con- ration and increasing chain length (see Tables 16
ductors. Data for thermal conductivity are lim- and 17). There is an approximately linear rela-
ited. Most data lie within ± 10 % of the follow- tionship between log viscosity and temperature.
ing general relationship: The viscosity of oils tends to increase on pro-


longed heating due to the formation of dimeric
Thermalconductivity Wm−1 K−1 = and oligomeric fatty acid groups.
0.181 − 0.00025t

where t = temperature in ◦ C. 3.5. Solubility and Miscibility

The smoke, flash, and fire points of oils and
fats are measures of their thermal stability when Nearly all fats and fatty acids are easily soluble
heated in air (Table 13). in common organic solvents such as hydrocar-
bons, chlorinated hydrocarbons, ether, and ace-
tone. Castor oil is an exception in that it is only
3.3. Density partially soluble in petroleum ether but easily so
in ethanol. The solubility of fatty acids in eth-
The density of fatty acids and glycerides de- anol is greater than that of the corresponding
creases with increasing molecular mass and de- triglycerides. The solubility of fats in organic
gree of saturation (Tables 14 and 15). Oxidation solvents decreases with increase in molecular
generally leads to higher densities. A high free mass and increases with degree of unsaturation.
14 Fats and Fatty Oils
Table 13. Smoke, flash, and fire points of refined oils and fats

ffa ∗, % Smoke point, ◦ C Flash point, ◦ C Fire point, ◦ C

Rapeseed oil 0.08 218 317 344

Peanut oil 0.09 207 315 342
Peanut oil 0.11 198 333 363
Peanut oil 1.0 160 290 –
Cottonseed oil 0.04 223 322 342
Cottonseed oil 0.18 185 318 357
Soybean oil 0.04 213 317 342
Sunflower oil 0.1 209 316 341
Coconut oil 0.1 200 300
Coconut oil 0.2 194 288 329
Coconut oil 1.0 150 270
Palm oil 0.06 223 314 341
Hardened peanut oil (mp 32/34 ◦ C) 0.04 226 314 340
Hardened soybean oil (mp 42/44 ◦ C) 0.04 223 318 342
Beef tallow 0.4 316 344
Beef tallow 5.0 266 344

∗ ffa = free fatty acid.

Table 15. Density of fats and oils

The differences in solubility enable categories of
glycerides to be separated by fractional crystal- 15 , g/cm3 d25
25
lization although complete separation is rarely
Vegetable fats
achieved because of mutual solubility effects. Babassu oil 0.9250
The water solubility of fats is low and de- Castor oil 0.950 – 0.974 0.945 – 0.965
creases with increasing chain length and with Coconut oil 0.919 – 0.937 0.869 – 0.874a
Cocoa butter 0.945 – 0.976 0.856 – 0.864a
decreasing temperature. The solubility of water
Corn germ oil 0.920 – 0.928 0.916 – 0.921
in cottonseed oil is, for example, 0.14 wt % at Cottonseed oil 0.917 – 0.931 0.916 – 0.918
30 ◦ C and 0.07 wt % at 0 ◦ C. Grape-seed oil 0.919 – 0.936
The solubility of gases in oils generally in- Hempseed oil 0.924 – 0.932 0.923 – 0.925b
Linseed oil 0.930 – 0.935 0.931 – 0.936
creases with increase in temperature, the reverse Mustard seed oil 0.912 – 0.923
holding for carbon dioxide (Table 18). Olive oil 0.914 – 0.925 0.909 – 0.915
Oiticica oil 0.9518 – 0.9694 0.978b
Table 14. Density of triglycerides Palm oil 0.921 – 0.947 0.898 – 0.901c
Palm kernel oil 0.925 – 0.935 0.860 – 0.873a
, g/cm3 Peanut oil 0.911 – 0.925 0.910 – 0.915
Perilla oil 0.927 – 0.933 min. 0.932b
80 ◦ C 15 ◦ C 25 ◦ C
Poppyseed oil 0.923 – 0.926
Tricaprin 0.8913 Rapeseed oil 0.910 – 0.917 0.906 – 0.910
Trilaurin 0.8801 Ricebran oil 0.916 – 0.921
Trimyristin 0.8722 Safflower oil 0.923 – 0.928 0.919 – 0.924
Tripalmitin 0.8663 Sesame oil 0.921 – 0.924 0.914 – 0.919
Tristearin 0.8632 Shea butter 0.917 – 0.918
Triolein 0.9162 0.9078 Soybean oil 0.922 – 0.934 0.917 – 0.921
Trilinolein 0.9303 Sunflower oil 0.920 – 0.927 0.915 – 0.919
Trilinolenin 0.9454 Tung oil 0.936 – 0.945 0.940 – 0.943b
Wheat germ oil 0.925 – 0.933
Animal fats
Table 16. Viscosity of triglycerides at 70◦ C Beef tallow 0.936 – 0.952 0.860 – 0.870a
Butterfat 0.935 – 0.943
η, mPa · s Herring oil 0.917 – 0.930
Tributyrin 3.0 Horse fat 0.915 – 0.932
Tricaproin 5.9 Lard 0.914 – 0.943 0.858 – 0.864a
Tricaprylin 8.8 Menhaden oil 0.925 – 0.935
Tricaprin 11.7 Mutton tallow 0.936 – 0.960
Trilaurin 14.6 Sperm oil 0.875 – 0.890
Trimyristin 17.6 Whale oil 0.914 – 0.931 0.910 – 0.920
Tripalmitin 20.5 a
d 99 b
d 15.5 c
d 37.8
15.5 . 15.5 . 37.8 .
Tristearin 23.4
 Fats and Fatty Oils 15
Table 19. Surface and interfacial tension of some oils
Table 17. Viscosity of naturally occurring fats and oils
Surface tension, mN/m Interfacial tension
η, mPa · s
20 ◦ C 80 ◦ C 130 ◦ C at 70 ◦ C, mN/m
20 ◦ C 30 ◦ C 40 ◦ C 50 ◦ C
Cottonseed oil 35.4 31.3 27.5 29.8
Castor oil 1000 454 232 128 Coconut oil 33.4 28.4 24.0
Coconut oil 39 26 19 Castor oil 39.0 35.2 33.0
Cottonseed oil 80 55 38 27 Peanut oil 29.9
Fish oil 60 43 32 22 Soybean oil 30.6
Lard 35 25
Linseed oil 48 33 25 18
Olive oil 80 55 40 30
Palm oil 40 28
Palmkernel oil 43 29 20 3.7. Electrical Properties
Peanut oil 78 50 32 23
Poppyseed oil 63
Rapeseed oil 85 60 40 30 Dry oils, fats, and fatty acids are poor conduc-
(high erucic) tors of electricity. Recorded values for the spe-
Sesame oil 65 25 cific resistance of stearic acid are 0.6×1011 Ω
Soybean oil
Sunflower oil
65
68
45
47
33
35
25
26
at 100 ◦ C and 22.3×1011 Ω at 186 ◦ C, and for
Tallow 25 oleic acid 2×1011 and 83×1011 Ω at compara-
ble temperatures. The dielectric constant of most
oils lies in the range 3.0 – 3.2 at 25 – 30 ◦ C. Cas-
tor and oiticica oil have dielectric constants of
Table 18. Solubility of gases in fats
about 4 in this temperature range because of the
Gas solubility, vol % hydroxyl and keto groups in the fatty acid chains.
t, ◦ C N2 H2 O2 CO2
In emulsion systems, e.g., butter or margarine,
the dielectric constant is affected by both the
Cottonseed oil 30.5 7.11 4.63 emulsion structure and the moisture content.
49.6 7.79 5.40
78.2 8.91 6.73
101.5 9.76 7.83
147.8 11.83 10.24 3.8. Optical Properties
Soybean oil ca. 20.0 ca. 4.95 ca. 2.65
Lard 41.5 7.65 5.218
73.2 8.79 6.58 The refractive index of oils, fats, and fatty acids
111.3 10.38 8.50 generally increases with increasing chain length,
147.3 12.06 10.35
Hardened tallow 64.3 6.14 92.0
number of double bonds, and extent of conjuga-
(iodine value 1) tion (see Tables 20 and 21). The refractive in-
67.0 8.44 14.50 dex of fatty acids is much lower than that of the
84.7 15.35 corresponding triglycerides. Prolonged heating
88.0 79.1
139.4 11.68 9.79 61.9 leads to an increase in refractive index due to the
introduction of polar groups into the fatty acid
chain.
Table 20. Refractive indices of glycerides

3.6. Surface and Interfacial Tension n60

D

Tricaprin 1.4370
The surface and interfacial tensions of some Trilaurin 1.4402
oils are shown in Table 19. The interfacial ten- Trimyristin 1.4428
Tripalmitin 1.4452
sion is markedly reduced by the presence of Tristearin 1.4471
surface-active agents, e.g., phosphatides, mono- Triolein 1.4548
glycerides, free fatty acids, and soaps. Trilinolein 1.4645
1,2-Dilaurostearin 1.4437
1,3-Dilaurostearin 1.4442
16 Fats and Fatty Oils
Table 20. Continued
ever, naturally occurring oils and fats invari-
1,2-Dilauroolein 1.4456 ably contain pigments that have characteristic
1,3-Dilaurostearin 1.4459 absorption bands (carotene at 450 nm, chloro-
1,2-Dipalmitoolein 1.4480 phyll and phaeophytin at 660 nm). Most of these
1,2-Distearoolein 1.4494
1-Stearodiolein 1.4524
pigments are removed during refining. Unsatu-
Monocaprin 1.4443 rated oils and fats absorb in the ultraviolet re-
Monolaurin 1.4462 gion between 200 and 400 nm. Conjugated dou-
Monomyristin 1.4480 ble bonds show characteristic maxima at 232 nm
Monopalmitin 1.4499
1-Lauro-3-olein 1.4472 (dienes, e.g., 9,11-trans,trans-linoleic acid) and
1-Stearo-3-olein 1.4507 at 268 nm (trienes, e.g., β-eleostearic acid). Con-
jugated tetraenoic acids absorb between 290 and
320 nm.
In the infrared region (0.075 – 1000 µm)
Table 21. Refractive indices of naturally occurring oils and fats
chain substituents such as epoxy, hydroxyl, keto,
n20
D
and cyclopropene groups as well as trans double
Babassu oil 1.449 – 1.450∗
bonds exhibit specific absorption peaks:
Beef tallow 1.454 – 1.459∗
monoglycerides 1.43 µm
Butterfat 1.452 – 1.457∗
hydroxy fatty acids 3.20 µm
Castor oil 1.477 – 1.479
ester carbonyl group 5.83 µm
Cocoa butter 1.453 – 1.458∗
trans double bonds 10.0 – 10.35 µm
Coconut oil 1.448 – 1.450∗
isolated trans double bonds 10.35 µm
Corn oil 1.474 – 1.476
Cottonseed oil 1.472 – 1.477
Grape seed oil 1.474 – 1.478
Herring oil
Lard
1.470 – 1.475∗
1.458 – 1.461∗
The fingerprint region around 8 µm can be
Linseed oil 1.479 – 1.481 used to determine the fatty acid chain length.
Menhaden oil 1.480 X-ray spectroscopy is employed to character-
Mustardseed oil 1.470 – 1.474 ize the various polymorphic crystal structures of
Mutton tallow 1.455 – 1.458∗
Oiticica oil 1.4921 – 1.4945
pure glycerides (see Section 3.1).
Olive oil 1.467 – 1.471 Nuclear magnetic resonance of hydrogen
Palm oil 1.453 – 1.456∗ atoms is used in structural identification and to
Palmkernel oil 1.449 – 1.452∗ determine the solids content of fats at different
Peanut oil 1.460 – 1.472
Perilla oil 1.481 – 1.483 temperatures. Nuclear magnetic resonance mea-
Rapeseed oil 1.472 – 1.476 surement of phosphorus and nitrogen atoms can
Safflower oil 1.4754 be employed to analyze the composition of phos-
Sesame oil 1.473 – 1.476
Soybean oil 1.470 – 1.478
phatide mixtures.
Sunflower oil 1.474 – 1.476 The optical activity of enantiomorphic trigly-
Tung oil 1.517 – 1.526 cerides with different fatty acid groups in the 1-
Whale oil 1.463 – 1.471 and 3-positions is usually too small to be mea-
Wheat germ oil 1.469 – 1.478∗
sured [20].
∗ n40 .

There are a number of equations depicting a 4. Chemical Properties

relationship between refractive index and other
data. The following equation has been suggested The chemical reactions of fats are basically those
for fresh, nonhydrogenated oils and fats: of esters and hydrocarbon chains (→ Esters, Or-
n40
ganic). Only those reactions that are primarily
D = 1.4643 − 0.00066 × saponificationvalue
relevant to the processing of edible oils and fats
0.0096 × acidvalue
− are dealt with in this chapter.
saponificationvalue
+0.0001711 × iodinevalue
Pure glycerides do not absorb in the visible
region of the spectrum (400 – 750 nm). How-
 Fats and Fatty Oils 17

4.1. Hydrolysis it enables the physical properties of a fat, e.g.,

melting behavior and consistency, to be modified
Glycerides can be hydrolyzed into fatty acids without changing the fatty acids chemically, as
and glycerol: occurs in hydrogenation (hardening).
Interesterification may be either random or
directed. Random interesterification leads to a
random distribution of the fatty acid groups over
the triglyceride molecules. This is demonstrated
for interesterification of equal proportions of
The reaction is reversible; in practice the equi- tristearin (S – S – S) and triolein (O – O – O):
librium can be shifted to the right by using a
large excess of water, high temperatures, and
high pressures.
Hydrolysis is catalyzed by inorganic and or-
ganic acids, e.g., sulfonated hydrocarbons. In the
enzymatic hydrolysis of glycerides with pancre-
atic lipase, the fatty acid groups in the 1- and
3-positions, are split off preferentially.
In directed interesterification, the tempera-
A fat can also be hydrolyzed with alkali
ture is reduced to such an extent that the highest
(saponification, see also → Soaps):
melting glycerides are continously frozen out of
the reaction mixture, in turn continuously shift-
ing the reaction equilibrium. In this way a fat
can be separated into higher and lower melting
fractions. The higher melting fraction contains
the glycerides of saturated fatty acids (stearin
fraction), whereas the glycerides of unsaturated
4.2. Interesterification fatty acids are found in the lower melting frac-
tion (olein fraction). Directed interesterification
Like other esters, glycerides can be transesteri- of stearodiolein can yield 33.3 % of tristearin
fied by acidolysis or alcoholysis (→ Esters, Or- and 66.7 % of triolein:
ganic, Chap. 3.2.). In the presence of an alkaline
catalyst and an excess of glycerol, triglycerides
form a mixture of mono- and diglycerides (al-
coholysis).
The acyl groups of glycerides can also be ex-
changed inter- and intramolecularly without ad-
dition of acids or alcohols (interesterification).

4.3. Hydrogenation

The double bonds in a fatty acid chain can be

wholly or partially saturated by addition of hy-
drogen in the presence of a suitable catalyst
such as nickel, platinum, copper, or palladium.
Hydrogenation always leads to an increase in
Even at 200 – 300 ◦ C interesterification pro- melting point and is therefore also called “hard-
ceeds very slowly, but the reaction can be ac- ening”. Partial hydrogenation can lead to iso-
celerated by using an alkaline catalyst such as merization of cis double bonds to trans double
a metal alkoxide. With such a catalyst the reac- bonds.
tion is complete within one minute at 80 ◦ C. In- The catalyst, the oil, and the hydrogen must
teresterification is of practical importance since be brought into mutual contact under suitable
18 Fats and Fatty Oils

temperature and pressure conditions. The reac- The double bonds of substituted fatty acids
tion rate depends on mixing intensity, the type such as ricinoleic acid can also be hydrogenated
of oil or fat, temperature, catalyst activity, and under suitable reaction conditions. Cyclopro-
concentrations of catalyst and dispersed hydro- pane or cyclopropene groups behave as double
gen. Hydrogenation is an exothermic process. bonds and lead to branched fatty acids on hydro-
Industrial nickel catalysts are generally obtained genation.
by precipitation of nickel hydroxide or carbon- Iron pentacarbonyl and cobalt octacarbonyl
ate on kieselguhr, silica gel, alumina, or sim- are examples of homogeneous hydrogenation
ilar carriers, followed by reduction to metal- catalysts.
lic nickel, or by in situ production of metallic Reduction with hydrazine does not lead
nickel from nickel formate. Such heterogeneous to isomerization; there is also no selectivity
catalysts have a large activated surface. During (k 1 = k 2 = k 3 ).
hydrogenation the double bonds form transient
complexes with the active centers of the catalyst.
These complexes disintegrate after reaction of 4.4. Isomerization
the double bonds with hydrogen, leaving the cat-
alyst in its original form [26]. The active centers Naturally occurring fatty acids exist predomi-
of the catalyst can be inactivated or poisoned by nantly in the cis form. An equilibrium mixture
a number of compounds such as phospholipids, in which the higher melting trans form predom-
sulfur compounds, organic acids, and oxidized inates can be formed by heating to 100 – 200 ◦ C
lipids. in the presence of catalysts such as nickel, sele-
A fatty acid with several double bonds, such nium, sulfur, iodine, nitrogen oxides, or sulfur
as linolenic acid (C18 : 3 ), is hydrogenated more dioxide.
quickly to linoleic acid (C18 : 2 ) or oleic acid If selenium or oxides of nitrogen and sulfur
(C18 : 1 ) than is linoleic acid to oleic acid or oleic are used in the cis – trans isomerization (elaidi-
acid to stearic acid (C18 : 0 ). The reaction se- nization) of oleic acid, there is virtually no po-
quence occurring during hydrogenation can be sitional isomerization. However, cis – trans iso-
represented schematically as follows: merization of linoleic and linolenic acid leads to
conjugated double bonds.
Nonconjugated systems can be isomerized
into conjugated systems by heating in an alkaline
solution at 200 ◦ C (→ Fatty Acids, Chap. 2.1.).
The term selectivity is used to indicate which If reaction times and temperatures are extended,
of these reactions is fastest. Selectivity I is de- linolenic acid can be converted into cyclo-
fined as the ratio k 2 /k 3 ; it is related to the pro- hexadiene and benzene derivatives:
portion of saturated glycerides formed and to the
melting behavior of the product. Selectivity II,
expressed as the ratio k 1 /k 2 , must be as high as
possible if the concentration of linoleic acid in
the hydrogenated product is to be maximized Isomerization can occur if oils and fats are
[27]. heated at temperatures above 100 ◦ C in the pres-
Selectivity can be influenced by the catalyst ence of bleaching earth, kieselguhr, or activated
type (surface area, pore size, etc.) and by alter- charcoal.
ing the reaction conditions. An increase in selec-
tivity, i.e., an increase in partial hydrogenation,
promotes isomerization of cis to trans double 4.5. Polymerization
bonds.
At temperatures above 200 ◦ C and with a Dimeric, oligomeric, and polymeric compounds
low hydrogen concentration, catalytic hydro- are formed by heating unsaturated fatty acids
genation of polyunsaturated fatty acid groups at 200 – 300 ◦ C [29]. The rate of polymeriza-
can lead to the formation of traces of cyclic aro- tion increases with increasing degree of unsat-
matic compounds [28]. uration; saturated fatty acids cannot be poly-
 Fats and Fatty Oils 19

merized. Thermal polymerization of polyunsat- a particularly fast buildup of radical concentra-

urated fatty acid groups is normally preceded by tion. The formation of singlet oxygen under the
isomerization and conjugation of double bonds. influence of short-wave radiation and a sensi-
Thermal polymerization involves formation of tizer such as chlorophyll or erythrosine probably
new carbon – carbon bonds by combination of plays a key role in this reaction.
acyl radicals and by Diels – Alder reactions, The reactivity of a methylene group in form-
while oxidative polymerization involves forma- ing a hydroperoxide is enhanced by a second
tion of C−O−C bonds. Thermal dimerization is adjacent double bond. Hence linoleic acid ox-
catalyzed by Lewis acids such as boron triflu- idizes 10 to 20 times faster than oleic acid.
oride; industrial processes for dimerizing oleic Linolenic acid reacts about three times faster
acid are based on this principle [30]. Heating than linoleic acid, since two doubly activated
of oils during refining or during household use methylene groups are present. The olefin radical
does not lead to a significant increase in dimeric formed subsequently isomerizes; in a 1,4-diene
triglycerides. Up to 2 % dimeric triglycerides such as linoleic acid, isomerization leads to con-
can be encountered in fresh raffinates; these jugated hydroperoxides:
dimers are not toxic, and are largely excreted
as such.

4.6. Autoxidation
Autoxidation, the oxidation of olefins with oxy-
gen, plays a decisive role in the development
of rancidity, off-flavors, and reversion flavors in
oils and fats during their production and storage.
Autoxidation of oil-containing products such as
oilseeds and spent bleaching earths can lead
to their spontaneous combustion. Autoxidation The intermediate hydroperoxides are labile
of drying oils is an important initial stage of compounds that decompose into a number of dif-
polymerization leading to stable surface films ferent products: epoxides, alcohols, diols, keto
(→ Drying Oils and Related Products, Chap. 3.). compounds, dicarboxylic acids, aldehydes, and
Autoxidation involves the formation of a hy- isomerization and polymerization products. The
droperoxide on a methylene group adjacent to a volatile carbonyl compounds formed in this pro-
double bond; this step proceeds via a free-radical cess are responsible for the taste and odor of
mechanism: oxidized oils and fats.
When the radical concentration has reached
a certain limit, the chain reaction is gradually
stopped by mutual combination of radicals.
Antioxidants prolong the induction period
by reacting with the intermediate products of
the chain reaction, forming inactive radicals.
Tocopherols are naturally occurring antioxi-
dants. Butylhydroxyanisole (BHA), butylhy-
droxytoluene (BHT), and propyl gallate are
among the most effective synthetic antioxidants
Autoxidation is characterized by an induction (→ Antioxidants). Certain organic or inorganic
period during which free radicals are formed. acids (citric, tartaric, ascorbic, phosphoric acids)
This phase is triggered by light (photooxygena- have a synergistic effect without being true an-
tion), heat, and the presence of compounds that tioxidants; this effect is presumably based on the
readily form free radicals (e.g., hydroperoxides, inactivation of trace metals or reduction of oxi-
peroxides, and transition metals). Photooxy- dized antioxidants.
genation, i.e., light-induced oxidation, leads to
20 Fats and Fatty Oils

5. Manufacture and Processing up to 12 m in diameter. The silos are filled from

the top, emptied from the bottom, and normally
Oils and fats are either of vegetable or animal equipped with special vibrating devices at the
origin. The approximate proportions of the cor- bottom to minimize bridging.
responding world production are 55 % vegetable
oils, 40 % land-animal fats, and 5 % marine oils.
5.1.2. Cleaning and Dehulling

5.1. Vegetable Oils and Fats On arrival at the oil mill, oilseeds still contain
plant residues, dust, sand, wood, pieces of metal,
5.1.1. Storage and Handling of Raw and foreign seed, which must be removed prior
Materials to further processing by screening, air classifi-
cation, and passage over magnets.
The handling of oleaginous seeds and fruits dur- Some oilseeds are dehulled (decorticated) be-
ing transport and storage has a decisive influence fore being further processed, especially if only
on the quality of the crude oils. The oils in fruit the oil is to be expelled, since the hulls tend to re-
pulp (e.g., olive and palm) are very susceptible tain part of the oil. Preexpelling and subsequent
to enzymatic hydrolysis since they are finely dis- extraction with solvents is the most common
persed in moist cell tissue. The oils contained in process; a certain proportion of hulls in the ma-
seeds are more stable but can also be attacked. terial to be extracted can be desirable since they
A high moisture content accelerates the uptake facilitate percolation. An excessively high pro-
of oxygen and the corresponding release of car- portion of hulls can, however, impair the quality
bon dioxide due to degradation of starch. The of the crude oil since the solvent also dissolves
heat generated in this reaction promotes lipoly- wax from the seed coat. A further reason for de-
sis, growth of microorganisms (which can lead hulling can be the need to produce so-called high
to the formation of mycotoxins such as aflatox- protein meal, for example from soybeans.
ins), formation of undesirable color and odor, Dehulling is normally preceded by relatively
and – in extreme cases – may result in a coag- intense drying of the seed material to help loosen
ulation of seed in a silo and even spontaneous the seed coat from the meats. Dehulling is nor-
combustion [31], [32]. Damage of seed cells, mally performed by using impact disintegration
mechanically or by pests, also promotes lipoly- or passage through rolls to break up the seeds.
sis and lipoxidation. Free fatty acids, oxidation The hulls are separated by screening and air-
products, and coloring matter formed by lipoly- classification.
sis, lipoxidation, and degradation of protein and
carbohydrate can in general be removed from
the oil only with difficulty, with corresponding 5.1.3. Expelling
yield losses.
In order to minimize these effects, oilseeds Modern processing of oilseeds generally in-
must be dried before storage, preferably under volves a combination of expelling and solvent
mild conditions to avoid cellular damage. The extraction. Seed is normally preexpelled to a
critical moisture content roughly correlates with residual fat content of ca. 20 %, and the expeller
the hygroscopic equilibrium at 75 % relative hu- cake is then extracted to 1 – 2 % fat. Preexpelling
midity and varies between 6 and 13 %, depend- is omitted if the fat content of the seed is 20 %
ing on the protein and carbohydrate content. In or less. High-pressure expelling down to ca. 4 %
the case of copra, rapeseed, and sunflower seed, residual fat is no longer important, mainly be-
the critical moisture content is 7 %; in the case cause of the higher processing costs.
of soybeans 13 %. Most of the fat present in seeds and fruit pulp
Transport and handling in bulk has almost is in the endosperm and hypocotyl cells, with
entirely superseded that in bags. Seed is nor- much less in the seed coat. The processing con-
mally stored in concrete silos that are ventilated ditions are largely determined by the size and
to avoid local generation of heat and water pock- stability of the oil-containing cells. With palm
ets; such silos can be up to 70 m in height and fruit and olives, mere heating or boiling with
 Fats and Fatty Oils 21

water suffices to burst the membranes of the oil- quent percolation in the extractor. Undesirable
containing cells to liberate the oil. Nearly all enzymes and microorganisms are deactivated at
oleaginous seeds must, however, first be com- temperatures above 80 ◦ C and in the presence of
minuted and thermally pretreated to isolate the sufficient moisture [33].
fat in an acceptable yield. Comminution par- By suitably conditioning cottonseed, the
tially destroys the cellular structure, increasing toxic gossypol can be deactivated by association
the total internal surface and facilitating access with denatured protein. In rapeseed, suitably se-
to the oil within the seed. vere conditioning deactivates the enzyme my-
Coarse materials such as copra are first bro- rosinase and hence improves the quality of the
ken by passage through interlocking rolls. Fluted meal and the oil. However, excessive heating im-
rolls are used for nearly all other seeds. Smooth pairs the nutritive quality of the expeller cake as
or so-called flaking rolls are used to complete well as the color and taste of the expeller oil and
seed comminution. These three types of rolls are must be avoided. An excessively high moisture
shown in Figure 3; they can be arranged in paral- content can reduce the yield of expeller oil. Each
lel, diagonally, or sequentially. In the more mod- type of seed must therefore be adjusted to an op-
ern, parallel arrangement, the rotational speed timal moisture content and temperature during
of the two rolls differs by 5 – 10 % to produce conditioning.
an additional shear effect. The separation of the
rolls and their circumferential speed is adjusted
to the type of seed and the degree of cell rup-
ture required for the subsequent expelling and
extraction.

Figure 4. Vertical stack cooker for conditioning oilseeds

(Krupp)
a) Level control; b) Steam heating; c) Insulation; d) Steam
jet; e) Manhole; f) Steam heating; g) Sweep stirrer

Conditioning is performed in horizontal jack-

eted tubes (conditioners) or in vertical stack
cookers. The stack cooker basically consists
Figure 3. Schematic representation of various rolls used for of up to five kettles arranged in a tier and
expelling oilseeds
A) Side view; B) Top view through which the seed material successively
moves from the top to the bottom; each kettle is
The comminuted seed is conditioned prior to equipped with a sweep stirrer and facilities for
expelling by moistening and heating in suitable direct and indirect steam heating (Fig. 4). Gen-
equipment. During this treatment lipoproteins erally, wet cooking with direct steam takes place
decompose, proteins coagulate, and intracellu- in the top kettle, and drying, with increased tem-
lar oil bodies coalesce. The cell walls themselves peratures and venting, in the bottom kettles.
are not macerated during conditioning. Coagu- Expelling (pressing) separates the oil from
lation of protein facilitates expelling and subse- the solid phase, the so-called expeller cake, and
22 Fats and Fatty Oils

can be done in continuous or batch presses. sections of the screw press, the pressure is in-
Levers, wedges, or screws were used to apply creased to about 300 MPa (3000 bar) to expel
pressure in the more primitive types of batch more tightly bound oil and to burst intracellular
presses, but modern batch presses are almost in- oil bodies.
variably operated by a hydraulic system. They Up to 200 t of seed per day per press is nor-
can be divided into the open type, in which the mally preexpelled to a residual fat content of
seed must be wrapped in press cloths, and the 15 – 25 %. The expeller cake is then commin-
closed type, which dispenses with press cloths uted on fluted rolls, and possibly also pelletized,
and confines the material in a cage-type con- prior to solvent extraction.
struction. Open-type presses can be subdivided Screw presses used to reduce the residual fat
into plate and box presses, closed types into pot content to 3 – 6 % are similar in design to pre-
and cage presses. expellers but have a larger compression ratio
Continuous expellers or screw presses (e.g., (1 : 25 instead of 1 : 15) and have a lower worm
Simon – Rosedowns, Krupp) have generally re- speed (9 – 12 rpm versus 30 – 45 rpm).
placed batch presses. Deoiling in these presses is A specific worm arrangement normally gives
efficient and uniform since the layer of material optimal results for only one particular type of
to be expelled is relatively thin and is continu- seed. Difficulties encountered on changing the
ously broken up. Several types exist, all with the type of seed can often be overcome by modify-
common principle of a worm shaft rotating in ing conditioning and comminution. Preexpellers
a cylindrical drainage barrel (Fig. 5). The barrel that do not require seed conditioning of sun-
is composed of armored, rectangular bars that fit flower seed have been developed; however, they
into the barrel bar frame. The individual bars are do not work as well with unconditioned rape-
separated by bar spacing clips, the specific spac- seed.
ings – ranging from 0.1 to 0.4 mm – depending The expeller oil still contains so-called foots,
on the type of seed and degree of expelling re- which must be removed by filtration.
quired. The required pressure is built up either
by a gradual increase in the diameter of the worm
shaft or by a gradual restriction of the barrel di- 5.1.4. Extraction [34], [35]
ameter. Specific pressure profiles and cake thick-
ness can be further controlled by variations in the Very much lower residual fat contents can be
pitch of the worm and choke mechanisms in the achieved by solvent extraction than by expelling.
barrel. The expelled oil is discharged through the Seed material with an oil content of ca. 20 %
barrel spacings while the expeller cake emerges and expeller cake with 15 – 25 % fat are usually
at the end of the barrel. subjected to solvent extraction. Both must be
flaked prior to extraction. This pretreatment cre-
ates a large internal surface and yields thin (ca.
0.3 mm), firm flakes, which form a loose layer
in the extractor and provide uniform, short diffu-
sion pathways. The flakes must have a minimum
moisture content and elasticity to prevent them
from crumbling during transport to the extrac-
tor, which would lead to too dense a packing and
hence poor percolation of solvent. However, a
high moisture content also impairs percolation.
Figure 5. Screw press (Krupp)
a) Drainage barrel; b) Worm shaft Ideally, the extraction solvent should dissolve
only glycerides but not undesirable components
The capacity of screw presses varies widely, such as coloring matter, gums, and phospho-
being dependent primarily on the cross-sectional lipids. The solvents must not contain toxic com-
ratio and the speed of the screw. The pressure ponents, and should be recoverable with min-
should be built up fairly slowly. Initially, the imum loss, be safe in handling, and be read-
channels in the expeller cake are sufficiently ily removable from the extracted material. For
large for ready discharge of oil; in the latter these reasons aliphatic hydrocarbons, especially
 Fats and Fatty Oils 23

hexane, are used almost exclusively. Technical for filling and emptying, a screen in the bottom
hexane with a boiling point range of 55 – 70 ◦ C part, and facilities for pumping solvent in and
has proved to be optimal. Hexane can be read- out, for direct and indirect steam heating, and a
ily removed from the oil at temperatures below sweep stirrer to move the extracted meal during
100 ◦ C in vacuo and can be stripped from the solvent stripping (desolventization) (Fig. 6).
meal with steam. The solubility of hexane in the
condensed water is only 0.1 %.
For special purposes, e.g., the production of
heat-labile pharmaceuticals, lower-boiling hy-
drocarbons such as pentanes are sometimes
used. Extraction with propane or carbon diox-
ide under supercritical conditions is reserved
for special products of high intrinsic value be-
cause of the high equipment costs involved. Cas-
tor oil, being relatively polar, is preferably ex-
tracted with the higher-boiling heptane. Alco-
hols (methanol, ethanol, propanol, and butanol)
and furfural are specially suited for the extrac-
tion of relatively wet materials. Extraction of
oilseeds with alcohols leads to relatively high
concentrations of phosphatides, glycolipids, car-
bohydrates, and similar constituents in the crude
oil, although the glycerides can in principle be
Figure 6. Batch extractor
concentrated by cooling or extraction of the alco- a) Stirrer; b) Screen
holic solutions. Alcohols are generally not used
as primary extraction solvents. However, they After filling the extractor with comminuted
are occasionally used as secondary extraction seed material, the upper opening is closed and
solvents to remove gossypol from cottonseed solvent pumped in. The displaced air escapes via
meal, thioglycosides from rapeseed meal, sugars a circuit; the hexane vapors in the displaced air
from soybean meal (to produce protein concen- are recovered. After the extractor has been filled
trates), and alkaloids from bitter lupine meal. with solvent, the hexane containing the extracted
Chlorinated hydrocarbons such as trichloro- oil is pumped into a second extractor filled with
ethylene and dichloromethane are of interest be- seed material. This process is repeated until the
cause of their safety in handling and high extrac- hexane solution has been pumped through 3 or
tion capacity but do not appear to be used for 4 extractors. The solvent strongly enriched with
extraction of oilseeds because of the potential oil (the miscella) from the last extractor is fil-
toxicity risk from residual solvent in the meal. tered to remove seed particles and then distilled.
Processes in which the oil is displaced by hot wa- In this type of process, exhaustive extraction can
ter are known but have not achieved industrial yield oil concentrations of at least 35 % in the fi-
importance [36]. nal miscella.
Oilseeds are generally extracted in a counter- When the contents of the first extractor have
current process: pure solvent is contacted with been extracted sufficiently, the solvent tap is
material that has already been largely extracted, closed; the pure extraction solvent is then passed
and the oil-rich solution is contacted with nonex- directly to the second extractor while the fifth
tracted material. Such extractions can be per- extractor becomes part of the battery. After
formed either continuously or in a batch process. discharging the solvent, remaining solvent is
stripped from the extracted seed material by
Batch processes. In a discontinuous process passing in steam. When the vapors leaving the
the solvent successively passes through a battery extractor are free of solvent, the extractor is emp-
of up to batch extractors (e.g., from Buss). Each tied via the lower opening.
of these extractors is a cylindrical vessel with a The sequence of filling, extraction, desolven-
large diameter : height ratio and has an opening tization and emptying is repeated for each ex-
24 Fats and Fatty Oils

tractor in a battery in such a way that while one countercurrent extraction, the baskets are emp-
extractor is being filled, the contents of three or tied through hinged sieve bottoms.
four extractors are extracted, residual solvent is
stripped in one or two extractors, and one ex-
tractor is emptied.
The vapors from the extractors and the dis-
tillation are condensed. The resulting hexane –
water mixture is separated mechanically and the
hexane recycled. Such a battery with 10 extrac-
tors of 7 m3 each can reach a daily throughput
of up to 1200 t seed, depending on the type of
Figure 7. MIAG basket conveyor extractor
seed. The quantity of hexane circulated is ca.
100 t. The solvent loss is normally between 0.35 The carousel extractor from Extraktionstech-
and 0.45 %, based on seed input. nik operates on a similar principle (Fig. 8), but
These discontinuous plants can be auto- has a fixed discharge point instead of movable
mated, and have the principal advantage that basket bottoms.
special treatment of meal (e.g., detoxification of
aflatoxin-containing peanut or cottonseed meal
with ammonia) can be carried out fairly easily.
Their capacities cannot, however, match those
of fully continuous plants, which can process up
to 200 t seed per hour.

Continuous Processes. Of the many fully

continuous processes that have been proposed
and developed, countercurrent gravity percola-
tion has become the most popular because of its
high capacity. The comminuted seed material is
transported through the extractor and sprayed
with solvent in the various extraction stations.
The solvent becomes increasingly enriched with
oil and is passed through the seed bed repeat-
Figure 8. Carousel extractor
edly according to the number of extraction sta-
tions. This arrangement has the advantage that In traveling belt extractors, such as the De
the miscella is continuously cleaned by filtration Smet extractor, the seed material is conveyed on
through the seed bed. an endless sieve belt, the height of the bed being
The MIAG basket conveyor extractor (Fig. 7) regulated mechanically. Miscella and solvent are
uses a horizontal arrangement of baskets in sprayed onto the seed material. Miscella perco-
which the flaked seeds are first sprayed with sol- lates throught the belt, falls into compartments
vent or miscella and then passed through a sol- in the bottom of the extractor housing, and is
vent bath. The baskets containing the extracted picked up by a series of pumps and recirculated
and drained flakes are automatically inverted and countercurrent to the flakes.
discharged into a hopper from which the meal is The Lurgi frame belt extractor works on a
conveyed to the desolventizers and dryers. similar principle [37]. The endless frame belt
In modern plants with a capacity of up to runs over two bar-sieve belts which form the bot-
5000 t of seed per day, circular cell and travel- toms of the frames. The flaked oilseeds are filled
ing belt horizontal extractors are generally pre- into the frames of the upper belt, tipped onto
ferred. The Blaw – Knox Rotocel extractor is es- the lower belt after half the extraction time has
pecially popular because it offers a large ca- elapsed, and then discharged after completion of
pacity within a relatively small space. It uses extraction and passage through a dripping zone.
baskets that travel in a horizontal circle. After This separation into distinct extraction steps and
 Fats and Fatty Oils 25

intermediate decompaction effects a particularly drawback is that emersion-type extractors are

uniform extraction. required. In the Direx process the seed material
There are numerous other types of extrac- is only coarsely ground, extracted to 14 – 16 %
tors which are of less practical importance. In residual fat with hexane, flaked, and then ex-
Hildebrandt, Schlotterhose, Ford, Detrex, Adler, tracted to ca. 1 % residual fat in a second extrac-
and Olier extractors, the comminuted seed ma- tion step. The theory is that flaking the hexane-
terial is transported through a solvent bath by moist material bursts the oil cells. This process
a screw; Figure 9 shows the principle involved. has been applied only on a small scale (ca. 5 t/h).
In a Kennedy extractor (Fig. 10), the material to
be extracted is conveyed to various sections of a
trough by means of impeller wheels. In the Sher-
win – Williams process the finely comminuted
seed material is thoroughly mixed with solvent
in three stages and then separated centrifugally
from the miscella. The structure of the seed ma-
terial is not as critical for these extractors as for
basket or belt-type extractors. However, they re- Figure 10. Kennedy extractor
quire a far greater ratio of solvent to seed mate-
rial. Their miscella are also contaminated with A more recent development is the Alcon pro-
fines, which requires a separate filtration step. cess [39] for soybeans, in which the essential
These types of extractors are therefore virtually step is to heat the flakes to ca. 100 ◦ C with
obsolete. direct steam, followed by drying. The special
flake conditioning prior to extraction deactivates
enzymes such as phospholipases and lipoxy-
genase, and presumably dissociates lipoprotein
complexes; this leads to lower residual fat con-
tents in the meal and a more easily deslimable
crude oil with improved oxidation characteris-
tics.
Extracted oilseeds can be desolvized in a se-
ries of horizontal steam-jacketed tubes. The ma-
terial is propelled through the tubes by screws
and is then passed through toasters, similar to
stack cookers, that are heated by both live and
Figure 9. Screw extractor indirect steam. Alternatively, desolventization
Böhm, Tyca, Allis – Chalmers, Bonotto, and can be performed in one step in desolventiz-
Anderson extractors are essentially columns di- ers – toasters. After drying and cooling, the meal
vided into a number of sections in which the is ready for use as an animal feed component.
seed material moves from the top to the bottom, Toasting not only reduces residual solvent to lev-
countercurrent to a rising flow of solvent. These els below the lower explosion limit but also de-
extractors do not match the performance of the activates nutritionally undesirable enzymes such
large basket or belt-type extractors. as urease and trypsin. In some cases, superheated
Several attempts have been made to develop solvent vapor is used for desolventization. This
processes obviating preexpelling. In the Fil- process and flash desolventization are used when
trex process, which is used to a limited ex- minimal protein denaturation is desirable.
tent, oilseeds such as rapeseed, sunflowerseed, Solvent is recovered from the filtered mis-
or peanuts can be extracted directly to about 1 % cella by distillation in multiple-stage evapora-
residual fat without preexpelling, provided the tors, which are constructed to minimize thermal
seed material has been flaked to about 0.1 mm damage to the oil. The miscella is first concen-
(the cell structure is probably destroyed) and trated to 96 % oil and finally stripped with in-
subsequently conditioned by “crisping” [38]. A jected steam in a falling-film evaporator. The
vapors from the toaster, dryer, cooler, and dis-
26 Fats and Fatty Oils

Figure 11. Kontipress system for working up carcasses (Krupp)

a) Raw material; b) Cooker – sterilizer; c) Buffer; d) Dryer; e) Condenser aggregate; f) Screw press; g) Meal grinder; h) Buffer

tillation unit are condensed and separated into 5.2. Land-Animal Fats
water and hexane, which is recycled. Vented air
is passed through special adsorbents such as ac- Animal fats can be readily isolated from tissue
tivated charcoal or mineral oil to recover solvent. by heating since the cell membranes of animal
Total solvent loss is 0.2 – 0.3 %, based on seed cells are much weaker than those of plant cells.
input. The intracellular fat expands on heating and
bursts the membrane. Extraction with solvents is
limited to offal. Fatty tissue is particularly sus-
ceptible to decomposition so that rapid process-
ing is necessary if refrigeration is not possible.
Microbial and autolytic degradation rapidly lead
to oxidation, hydrolysis, color deterioration, and
unpleasant odors and flavors, which are difficult
to remove from the fat. The free fatty acid con-
tent therefore serves as a convenient, primary
quality criterion.
In dry rendering, the comminuted fatty tissue
is digested by cooking in steam-jacketed vessels
equipped with agitators [40]. Local overheating
of fatty tissue must be avoided since this can
easily lead to unpleasant off-flavors. In modern
automated plants for working up animal byprod-
ucts, the raw material is first heated and sterilized
in a dry-rendering vessel. The resulting sludge
is then separated, possibly after predrying, into
crude meal (cracklings) and a liquid phase con-
taining fat and water by a continuous screw press
Figure 12. Alfa – Laval Centriflow rendering plant
a) Cutter; b) Renderer; c) Buffer; d) Propeller pump;
(see Fig. 11, Krupp Kontipress process) or by a
e) Steam heater; f) Decanter; g) Buffer; h) Propeller pump; decanter, i.e., a centrifuge with a built-in screw
i) Separator (centrifuge); k) Plate heat exchanger; l) Cooling conveyor (Alfa–Laval Centrimeal process). The
water fat is finally separated from the aqueous phase
by centrifuging. The 7 – 12 % residual fat con-
 Fats and Fatty Oils 27

tent of the meal can be reduced to 1 – 4 % by Africa employs liquefied propane as the extrac-
solvent extraction. tion solvent. This method can also be used to
Wet rendering, which involves treating the fractionate fishliver oils and to isolate vitamin
fatty tissue with direct steam, tends to give better concentrates.
yields and quality than dry rendering. In mod-
ern continuous rendering plants (e.g., as built by
Alfa – Laval, Westfalia, and Sharples) selected 5.4. Synthetic Fats
tissue is coarsely comminuted and heated to 50 –
60 ◦ C. It is then heated quickly to 80 – 90 ◦ C with Pure synthetic glycerides [20] and phospho-
direct steam to deactivate oxidizing enzymes. lipids have few industrial uses. Synthetic fats
The greaves are then separated in a decanter for edible purposes are of little importance with
centrifuge, and the fat is clarified by further the exception of specific dietary products such
centrifuging, cooled, possibly texturized, and as medium-chain triglycerides of C8 and C10
packed (Fig. 12). Fat obtained by this method fatty acids (MCT fats), which are administered
in up to 99 % yield contains 0.1 – 0.2 % mois- in some postsurgical cases [42].
ture; the content of free fatty acids is virtually
identical with that of the raw material. This mild
processing technique minimizes the formation 6. Refining
of off-flavors. Further refining of lard or tallow
for edible purposes is controlled by national leg- Crude oils and fats obtained by expelling, ex-
islation. traction, or rendering contain trace components
which are undesirable for taste, stability, appear-
ance, or further processing. These substances in-
5.3. Marine Oils clude seed particles, dirt, phosphatides, carbo-
Whale oil is isolated by rendering. The blub- hydrates, proteins, fatty acids, trace metals, pig-
ber is cooked with live and indirect steam, and ments, waxes, oxidation products of fatty acids,
the oil is then separated by centrifugation from and toxic components such as polycyclic aro-
insoluble tissue and water-soluble matter. matic hydrocarbons, gossypol, mycotoxins, sul-
Similar processes are used to isolate fish oils fur compounds (in fish and cruciferous oils), and
[41]. Crushed fish (herring, menhaden, sardines, pesticide residues. The aim of refining edible
pilchards) with a dry matter content of 15 – 22 % fats and fats for industrial purposes is to remove
is first cooked in closed vessels at relatively low these undesirable components as far as possible
pressure. This operation sterilizes the fish and without significantly affecting the concentration
coagulates the protein to produce a fish mass that of desirable constituents such as vitamins and
can be easily pressed. Subsequent screw press- polyunsaturated fatty acids, and without signif-
ing separates most of the water and oil from icant loss of the major glyceride components.
the press cake. The press water is prepurified Some oils, such as olive oil, butterfat, and cold-
over screens or with a decanter (desludger) and pressed sunflower oil or linseed oil, are not re-
then separated by centrifugation into crude fish fined in order to preserve their typical flavors.
oil and stickwater (or glue water). The press Refining usually involves the following
cake (ca. 50 % water) is dried, sometimes also stages:
extracted with a solvent, and ground into fish 1) Precleaning to remove phosphatides (degum-
meal. Evaporation of the stickwater gives sol- ming)
ubles which are added to the meal. Industrial 2) Neutralization by treatment with lye or by
plants are offered by Alfa – Laval ( Centrifish) distillation
and Westfalia (see Fig. 13) 3) Decolorization by adsorptive treatments
Liver oils are usually obtained on board ship (bleaching)
by mild rendering of crushed liver, sometimes 4) Deodorization or stripping in vacuo
assisted by pressure-release disintegration of
the oil cells, and subsequent separation in cen-
trifuges. The Solexol process used in South
28 Fats and Fatty Oils

Figure 13. Fish meal and fish oil plant (Westfalia)

a) Cooker; b) Power press; c) Crusher; d) Eccentric screw pump; e) Preheater; f) Decanter for clarification of press water;
g) Press water preheater (92 ◦ C); h) Rotary brush strainer; i) Separator with self-cleaning bowl (1st stage, press water deoiling);
j) Crude oil preheater (92 ◦ C); k) Separator with self-cleaning bowl (2nd stage, oil polishing)

6.1. Degumming [43] Some technical oils such as linseed oil can be
degummed by heating to 240 – 280 ◦ C; the pre-
Phosphatides, gums, and other complex col- cipitation of gums on heating is referred to as oil
loidal compounds can promote hydrolysis of an “breaking.”
oil or fat during storage and also interfere with Precleaning of a crude oil by treatment with
subsequent refining. They are therefore removed bleaching earth or other adsorbents, normally in
by degumming or desliming. combination with acids such as phosphoric or
The degumming method depends on the type citric, can be advantageous.
of the oil and the phosphatide content. In hydra- Oils that are refined by distillation (physical
tion degumming, which involves treating the oil refining, see page 32) should have a very low
or fat with water or steam, phosphatides absorb phosphatide content. This can be achieved by
water to form a sludge that is insoluble in the special degumming techniques involving the ad-
oil. This process is used to remove soy lecithin dition of citric acid followed by hydration at ca.
(1 – 3 %) from soybean oil: 2 – 5 % water, based 20 ◦ C for several hours before centrifugal sep-
on oil, is intimately mixed with the crude oil aration [44]. Another “superdegumming” tech-
at 70 – 80 ◦ C; after a contact time of 1 – 30 min nique involves separating the phosphatide mi-
the phosphatide sludge is separated by centrifug- celles from a solution of the crude oil in hex-
ing. The degree of hydration can be increased by ane by ultrafiltration using special polysulfone
using acids such as citric or phosphoric, bases, or polyacrylonitrile membranes [45].
or salts but at the expense of lecithin quality.
Such modified hydration processes are therefore
confined to post-degumming and to oils whose 6.2. Deacidification (Neutralization)
lecithins have little commercial value. Degum-
Commercially available crude oils and fats con-
ming and neutralization can also be carried out
tain on average 1 – 3 % free fatty acids. Whereas
together but usually with increased losses of neu-
a soybean oil can have as little as 0.5 % free fatty
tral oil owing to the formation of emulsions. The
acids, some palm and fish oils can contain up
use of sulfuric acid is generally restricted to in-
to 10 %. The free fatty acid content of refined
dustrial oils that are not to be further refined.
fats should be below 0.1 %. Although longer
 Fats and Fatty Oils 29

chain fatty acids do not generally affect taste, free fatty acids are neutralized with strong lye
the short-chain acids can impart a soapy, rancid in order to limit the total volume. The required
flavor. When the free fatty acids are removed as amount of lye, including a slight excess, is based
soaps by treatment with lye, other undesirable on the free fatty acid content (ffa).
constituents such as oxidation products of fatty
acids, residual phosphatides and gums, phenols
(e.g., gossypol), and aflatoxins are also “washed
out.” In practice, deacidification is performed
mainly by treatment with lye or by distillation.
Deacidification by esterification with glycerol,
by selective extraction with solvents, or by ad-
sorbents is not industrially important.

Alkali Neutralization [46]. The usual

method of alkali neutralization is treatment with
weak lye, either batchwise or continuously. The
more concentrated the lye, the more readily are
undesirable constituents taken up in the soap-
stock. Dilute alkaline solutions (ca. 1 N) do not
saponify the oil, but greater neutral oil losses
occur due to occlusion in the soapstock. The
losses increase with increasing content of free Figure 14. Combined neutralizer – bleacher
fatty acids. Concentrated lye (4 – 7 N) yields
a relatively concentrated soap which takes up After neutralization and discharge of soap-
little neutral oil, but it can saponify substantial stock, the oil is washed with dilute lye (ca. 0.5 N)
amounts of the neutral oil, especially in those and then with water in order to reduce the soap
oils that have a relatively high proportion of content below 500 ppm. Incomplete removal of
short-chain fatty acids. The optimum lye con- soap impairs the color of the oil and the effi-
centration therefore depends on the quality of cacy of the following refining steps. Polyunsat-
the crude oil and the desired quality of the re- urated oils such as soybean oil are sometimes
fined product. The neutralization process can subjected to posttreatment with sodium carbon-
be further influenced by temperature, residence ate – silicate to remove residual traces of ox-
time, and mode and intensity of mixing the lye idized glycerides and phosphatides. Although
and the fat phase. soapstock can be utilized as such in chicken
Batch neutralization is done in an open or broiler feed, it is normally converted into “acid
closed vessel (up to 75 t content) with a conical oil” (a mixture of fatty acids and neutral oil) by
base. The reactor is fitted with a heating man- batch or continuous treatment with 30 % sulfuric
tle, heating coils, and facilities for injecting live acid at 70 ◦ C.
steam (Fig. 14). Lye and oil can be mixed with- The quantity of acid oils is a measure of the
out undue emulsification by using special coil refining efficacy. A refining factor of 2 means
and frame stirrers. Soap settles in the conical that for each mass unit of free fatty acid in the
bottom of the neutralization vessel. Discharge crude oil, 2 mass units of acid oil are produced.
of neutral oil with the soap can be minimized The difference between acid oil and free fatty
by using ultrasonic or dielectric measurement acid content is mainly due to occluded neutral
of the phases. Closed vessels can also be used oil. Acid oils are used for technical purposes and
for bleaching if they can be evacuated. Whereas as energy carriers in animal feeds [47].
weak lye is generally sprayed onto the oil at ca. Batch neutralization is more flexible than
90 ◦ C without stirring, stronger lye is normally continuous neutralization but gives lower refin-
stirred into the oil at 40 – 80 ◦ C. Sodium carbon- ing yields.
ate is sometimes used instead of caustic soda; Continuous processes achieve the same or
it does not saponify but tends to lead to foam- greater capacities in a smaller space with bet-
ing. Oils with a relatively high concentration of ter yields, provided long continuous runs can
30 Fats and Fatty Oils

Figure 15. Flow diagram of continuous neutralization of oils and fats

a) Crude oil storage tank; b) Gum conditioning mixer; c) Neutralizing mixer; d) Separator (centrifuge); e) Re-refining mixer;
f) Water-washing mixer; g) Vacuum dryer

be maintained. Continuous plants from Alfa – ping, gums, phosphatides, and trace metals must
Laval, Westfalia, and Sharples are widely used be almost completely removed since these com-
(Fig. 15). In these plants, the oil is generally pounds impair the oil quality during distillation.
first conditioned by addition of citric or phos- They are preferably removed by treatment with
phoric acid in small continuous mixing cham- acids and bleaching earth.
bers and then brought into contact with lye. Soap The economics of distillative neutralization
and gums are separated in centrifuges. After re- improve with increasing content of free fatty
refining and passage through a washing cen- acids. The fatty acid factor is approximately 1.1,
trifuge, the oil is practically free of fatty acid and thus the neutral oil losses are far lower than with
soap. The Sharples plant uses high-speed open alkali neutralization. An added advantage is the
centrifuges with a high separation efficiency, avoidance of soap-stock splitting and the conse-
while the Alfa – Laval short-mix lines employ quent effluent problems. Distillative neutraliza-
completely closed centrifuges with a mean res- tion was formerly restricted to fairly saturated
idence time of only a few seconds. The capac- oils with a high free fatty acid content (e.g., co-
ity can be increased considerably by using self- conut oil, palm oil, and tallow). However, it is
discharging centrifuges (e.g., from Westfalia). now being extended to polyunsaturated oils such
The Zenith process employs a different prin- as rapeseed, soybean, and sunflower oil because
ciple: a fine stream of oil rises through a vessel techniques are available for reducing the phos-
filled with dilute caustic soda and is skimmed phatide content of the crude oils to sufficiently
off continuously at the top. The spent lye must low levels to obviate lye neutralization [50].
be replaced. This type of neutralization requires Temperatures between 240 and 270 ◦ C are
efficient pre-degumming and has the advantage normally used to achieve free fatty acid con-
of relatively low losses of neutral oil [48]. tents of less than 0.1 %. At these temperatures
Neutralization with aqueous ammonia is an decomposition and removal of carotenoid pig-
old process which is being reexamined because ments result in a significant bleaching effect,
of environmental pollution problems with lye. this is particularly noticeable in palm oil. Older
The ammonium soaps can be separated by cen- plants such as those built by Wecker and Feld
trifuging and split into fatty acids and ammonia & Hahn have now been generally superseded by
by heating, the ammonia being recycled [49]. modern plants (e.g., Lurgi, Girdler, HLS, and
EMI), which have the advantage of a smaller
Distillative Neutralization. In distillative spread in residence time and hence better pro-
neutralization (physical refining) the free fatty cess control (especially in combined deacidifi-
acids are continuously removed from the crude cation, deodorization, and heat bleaching). The
oil with water vapor in vacuo. Prior to this strip- latter plants are very similar to the corresponding
 Fats and Fatty Oils 31

deodorizer plants (see Figs. 20 and 21) except for these undesirable compounds can be removed
an additional fatty acid condenser between the by suitable degumming and neutralization, there
deodorizer and the vacuum assembly. is an interdependence between the pretreatment
conditions and the treatment with adsorbents.
Other Processes. Esterification of the free This interdependence can also involve deodor-
fatty acids with glycerol may be economically ization (heat bleaching) where, for example, the
feasible for highly acid oils. The esterification carotenoid content is reduced.
is carried out at 160 – 210 ◦ C in the presence of The adsorption of pigments follows Freund-
catalysts such as magnesium oxide, alkali sili- lich’s isotherm: the amount of pigment adsorbed
cates, or metals (Zn or Sn). decreases with decreasing concentration of the
Solvent extraction of free fatty acids is of in- pigment in the oil. Although adsorption should
terest only for highly acid oils. Olive oil with be most efficient if the oil is passed through a
22 % ffa can be deacidified to ca. 3 % ffa by liq- layer of adsorbent, in practice the adsorbent is
uid – liquid extraction with ethanol. Furfural can normally stirred into the oil and then filtered off
be used to dissolve polyunsaturated glycerides after a certain residence time.
and fatty acids. The choice of the adsorption process and the
In the Solexol process, liquefied propane is type and concentration of adsorbent is governed
used as solvent. Saturated glycerides are taken by factors such as pretreatment, desired quality
up in the propane phase while nonsaponifi- of the fully refined product, filtration speed of the
able matter, fatty acids, oxidation products, oil, and oil retention by the adsorbent. Oil reten-
and polyunsaturated glycerides remain largely tion can be up to 50 wt % on bleaching earths
undissolved. This process has been used to frac- and nearly 100 wt % on activated charcoal.
tionate fish and fishliver oils and may increase Natural and activated earths are the most
in importance with the advent of supercritical frequently used adsorbents in the refining of oils
fractionation and extraction techniques. and fats. Activated earths are obtained by leach-
Various adsorbents such as silica gel and alu- ing natural earths (predominantly aluminum
mina have been proposed for the selective ad- silicates containing montmorillonite) with hy-
sorption of free fatty acids [51]. Adsorption on drochloric acid followed by washing with water,
strongly basic ion-exchange resins has also been drying, and sizing. This process increases the in-
used. Plant-scale application of such processes ternal surface of the bleaching earth by partial
has, however, not been reported. dissolution of the aluminum and iron oxides; cal-
cium and magnesium ions are partially replaced
by hydrogen ions.
6.3. Bleaching The amount of bleaching earth to be used and
the optimum bleaching conditions must be deter-
Degumming followed by alkali neutralization mined empirically. Lower concentrations (0.5 –
generally does not lead to significant decoloriza- 1.0 %) are required for activated earths than for
tion of an oil or fat. A bleaching step with solid natural earths. Activated earths catalyze oxida-
adsorbents such as bleaching earth or activated tion of the oil. For this reason bleaching should
charcoal is normally employed. Bleaching with be done below 100 ◦ C in vacuo, and the subse-
air or chemicals is not used for edible fats. quent filtration should be carried out with lim-
The aim of adsorptive treatment is to remove ited access of atmospheric oxygen. Bleaching
pigments such as carotenoids and chlorophyll is sometimes performed in two steps: a condi-
but also residues of phosphatides, soaps, trace tioning and adsorption stage at relatively low
metals, and oxidation products such as hydroper- temperature (ca. 65 ◦ C), and a second stage at
oxides and their nonvolatile, polar decomposi- elevated temperature (ca. 100 ◦ C) to fix the ad-
tion products. These compounds can have a dele- sorbed components onto the adsorbent surface
terious effect on the course of further processing [52].
(especially hardening and deodorization) and on In physical refining, bleaching is often pre-
the quality of the final product. Some of the ox- ceded by addition of citric or phosphoric acid to
idation products that are removed by adsorption chelate trace metals and to precipitate hydrated
can promote oxidation of the oil. Since some of
32 Fats and Fatty Oils

phosphatides. This can also be achieved by using Continuous bleaching is especially relevant
bleaching earths containing added acid. when the other refining steps are also performed
The moisture content of bleaching earths lies continuously. The degummed or degummed and
between 5 and 10 %. Except for some types of neutralized oil is normally dried and deaerated in
natural earths, the moisture content does not ap- vacuo and charged together with bleaching earth
pear to have a significant influence on bleaching into an evacuated vessel where the oil – earth
capacity. slurry is fed through various compartments, pos-
Activated charcoal (0.1 – 0.4 %) is some- sibly at different temperatures, and is then fil-
times used in combination with bleaching earth tered in a closed-disk system (Fig. 17).
for oils that are difficult to bleach. Activated
charcoal has also assumed importance as an ad-
sorbent for removing polycyclic aromatic hy-
drocarbons from oils and fats [53]. It has been
recommended for use in a fixed-bed process for
the physical refining of soybean oil [54].
Bleaching and filtration is still mostly done
batchwise. The oil is first dried in vacuo at
ca. 30 kPa (30 mbar) to an optimum moisture
content, frequently in the same closed vessels
in which the oil was neutralized and washed
(Fig. 14). The required amount of adsorbent is
then drawn into the oil at 80 – 90 ◦ C, prefer- Figure 17. Alfa – Laval bleach system
ably through a pipe reaching into the oil. Af- a) Plate heat exchanger; b) Bleacher; c) Filters; d) Polishing
ter stirring for a few minutes to half an hour in filters; e) Bleaching-earth dosage equipment; f) Bleaching-
earth storage tank, g) Cyclone
vacuo, the oil – earth slurry is pumped over fil-
ter presses. Automated frame and plate presses Bleaching with oxygen or chemicals is not
or centrifugally dischargeable, closed-disk fil- practiced for edible fats and is used only occa-
ters of the Funda (Fig. 16) and Schenk type are sionally for technical fats. Oxidizing agents such
preferred; these also have the advantage of lim- as hydrogen peroxide, sodium peroxide, ben-
iting access of air. The filter cake, containing zoyl peroxide, potassium permanganate, chro-
30 – 50 % oil, is often extracted with hot water mium salts, hypochlorite, and chlorine dioxide,
(Thomson process) or with hexane to recover and reducing agents such as sulfurous acid and
the bulk of the adsorbed oil. The quality of the sodium dithionite have been proposed. Hydro-
recovered oil depends on the degree of unsatu- gen peroxide is used when adsorptive methods
ration, the type of extraction, and the age of the do not suffice. Castor, coconut, peanut, and olive
spent earth before extraction. It is normally not oils and certain types of tallow and bone greases
economic to regenerate spent bleaching earth. can be successfully bleached with 0.05 – 0.1 %
of a 20 % aqueous solution of sodium chlo-
rite. Fats such as red palm oil are sometimes
bleached by very slight hydrogenation which de-
stroys carotenoid pigments.

6.4. Deodorization
Deodorization is the last step of the refining se-
quence, in which odors and flavors are removed
from the bleached oil or fat. It is essentially a
steam distillation process in which volatile com-
Figure 16. Closed disk filter with centrifugal discharge pounds are separated from the nonvolatile glyc-
(Funda) erides. The odoriferous compounds are primar-
ily aldehydes and ketones formed by autoxida-
 Fats and Fatty Oils 33

tion during handling and storage and can have ten injected into the oil toward the end of the
a flavor threshold value of a few ppm. Other deodorization.
volatile components such as free fatty acids, al- The deodorizer is normally constructed of
cohols, sterols, or tocopherols are also partially stainless steel if temperatures of 190 ◦ C are
removed by deodorization. to be exceeded. Deodorizing temperatures up
Deodorization is not, however, a purely phys- to 270 ◦ C are employed, for example, to com-
ical process. During deodorization, flavor com- plete removal of pesticide residues [55], to heat-
pounds can be formed by hydrolysis and ther- bleach palm oil, and to complete removal of
mal decomposition, and peroxides are decom- free acids during physical refining. Since dimer-
posed by heat. These reactions presumably play ization and isomerization of fatty acid groups
a major role in the flavor stability improvement increase with time and temperature [56], a de-
achieved by deodorization, especially in veg- odorization at 270 ◦ C should not last more than
etable oils. In practice, therefore, the residence 30 min.
times and steam volumes required are signifi- Batch deodorizers are still widely used
cantly greater than those calculated for normal (Fig. 18). They are about twice as high as they are
steam distillation. At the relatively high deodor- wide and are normally half-filled to provide suf-
ization temperatures used, traces of air can ini- ficient head space. Their capacity can vary from
tiate oxidation with severe impairment of taste 5 to 25 t. The bottom part is fitted with heating
and flavor stability. Because thermal decompo- coils and a steam distributor through which strip-
sition products of proteins, carbohydrates, phos- ping steam is injected into the oil. The vacuum
phatides, and soaps can also interfere with de- system (0.6 – 1.2 kPa) comprises a booster and
odorization, the oil must be well prerefined, i.e., ejector assembly. Barometric condensers can
freed from phosphatides and soap. be eliminated by using dry condensing plants.
Deodorization is performed in vacuo because When deodorization is completed, the oil is
of the low partial vapor pressure of the com- cooled to ca. 90 ◦ C in the deodorizer and to 40 –
pounds to be removed. Consumption of stripping 60 ◦ C in a subsequent vacuum cooler; cooling
steam increases with decreasing vapor pressure minimizes oxidation that occurs on contact with
of the volatile components and with increasing atmospheric oxygen at elevated temperatures.
pressure in the deodorizer, it ranges from 5 to The total cycle of charging, heating, deodor-
10 wt % (based on the oil) for batch processes ization, cooling, and discharging requires up to
and from 1 to 5 wt % for continuous processes. 8 h, the deodorization process itself up to 4 h.
Deodorization temperatures range from 190 to The deodorizer distillate has the appearance of
270 ◦ C and the pressure from 0.13 to 0.78 kPa a milky emulsion and contains calcium soaps,
(1 – 6 mm Hg). The volume of stripping steam nonsaponifiable matter, and a small fraction of
required is 10 – 20 m3 per kilogram of oil [24]. neutral oil.
Carry-over losses of oil are minimized by lim-
iting the velocity of the injected steam, by pro-
viding a sufficiently large headspace, and by baf-
fles. The distillate removed during deodorization
is about 0.2 % of the oil, and contains very little
neutral oil. In a batch process a deodorizing time
of at least 2 h is required for saturated or hydro-
genated fats; about 4 h is needed for other oils
and fats. Although attempts have been made to
determine the end point of deodorization by an-
alytical data, in practice this is done organolep-
tically.
The steam injected into the oil must be dry
and oxygen-free. In order to deactivate proox-
idative trace metals, aqueous citric acid solution Figure 18. Batch deodorizer
a) Barometric condenser; b) Fat trap; c) Heating steam;
(2 – 5 mg of citric acid per 100 g of oil) is of- d) Stripping steam; e) Steam distributor
34 Fats and Fatty Oils

Semicontinuous and continuous deodoriza- Fully continuous deodorizers generally com-

tion systems are replacing batch deodorizers prise a high cylindrical column fitted with a num-
because of the savings in steam resulting from ber of trays with bubble caps or similar devices,
more efficient stripping and heat recovery. down which the oil flows countercurrent to the
The semicontinuous Girdler deodorizer stripping steam. The oldest continuous deodor-
(Fig. 19) consists of an iron shell fitted with izer is probably that built by Foster – Wheeler.
stainless steel trays. At defined time intervals Modern versions [57] are made by EMI, Gi-
(e.g., every 30 min), a certain quantity of oil anazza, Mazzoni, Wurster & Sanger, Votator,
flows into the top tray of the deodorizer where de Smet, Ex-Technik, HLS, Lurgi, and Krupp
it is deaerated in vacuo and then heated to ca. (Fig. 21). An alternative construction is that of
170 ◦ C by exchange with the hot effluent oil. Af- EBE in which the oil flows countercurrent to the
ter 30 min the oil is discharged into the second stripping steam in horizontal tubes. The Campro
tray where it is heated to the operating tempera- deodorizer has a continuous tray-in-shell design
ture (normally 230 – 250 ◦ C). Injection of steam that combines plug flow with a unique thin-film
(at 0.6 – 1 kPa) takes place in the 3rd and 4th stripping concept.
trays, and cooling in the 5th tray. Operation of
the unit is made fully automatic by use of a tim-
ing device which opens and closes the oil valves. 7. Fractionation
The semicontinuous Lurgi plant works on a sim-
ilar principle (Fig. 20); the stripping steam is in- The aim of fractionating fats is to remove ei-
jected through special orifices and further dis- ther undesirable components or to isolate de-
tributed through the oil by steam-lift pumps. sired components with special properties. Edi-
These types of deodorizers have capacities of ble oils can, for example, be winterized by re-
up to 20 t/h. moving waxes and saturated components; cocoa
butter substitutes can be obtained from palm oil.
Except for the molecular distillation of mono-
glycerides, distillative techniques cannot be em-
ployed. Industrial fractionation techniques are
based on crystallization or liquid – liquid extrac-
tion. Separation of glycerides by selective ad-
sorption is only used occasionally for purifi-
cation purposes. Fractional crystallization can
be subdivided into dry processes, processes em-
ploying solvents, and processes involving selec-
tive wetting of fat crystals. Directed interester-
ification combines selective fractionation with
interesterification (see Section 4.2).
The oldest example of dry fractionation is
the separation of tallow into stearin and olein by
pressing; this separation came into use toward
the end of the 19th century in connection with
the production of margarine. The lower-melting
glycerides (olein) were squeezed out of the crys-
tal network of the higher-melting glycerides by
pressing blocks of tallow wrapped in filter cloth.

Figure 19. Semicontinuous deodorizer (Girdler)

a) Heating steam; b) Vacuum aggregate; c) Cooling water;
d) Stripping steam
 Fats and Fatty Oils 35

Figure 20. Flow diagram of a semicontinuous deodorization plant (Lurgi)

a) Measuring tank; b) Heat exchanger; c) Stripping steam; d) Heating steam; e) Filter; f) Pipe emptying

motes selective crystallization of the higher-

melting glycerides and avoids the formation of
mixed crystals containing both high- and low-
melting glycerides. The difference in melting
point must be at least 10 ◦ C to achieve a suf-
ficiently sharp, reproducible separation.

Figure 21. Continuous deodorizer (Krupp)

a) Pump; b) Filter; c) Meter; d) Deaerator; e) Preheater
(low-pressure steam); f) Preheater (high-pressure steam);
g) Kreuzstrom – Konti deodorizer; h) Cooler; i) Filter;
k) Vacuum aggregate; l) Steam kettle

This method has been superseded by mod-

Figure 22. Dry fractionation plant
ern processes (Fig. 22) in which the fat is slowly a) Crystallizers; b) Circulating unit; c) Feed pump; d) Recy-
chilled to the required temperature under con- cling pump; e) Florentine filter
trolled conditions in tempering vessels fitted
with low-speed agitators, or in scraped coolers. Winterization of edible oils such as sunflower
Relatively large crystals of the higher-melting or cottonseed oil involves removing waxes,
glycerides are obtained which can readily be fil- which cause turbidity at refrigerator tempera-
tered off in filter presses or drum filters. Slow tures. After bleaching or deodorization, the oils
cooling is important to obtain a relatively small are kept at ca. 10 ◦ C for at least 1 h and then fil-
number of nuclei which can then grow into tered. An alternative process is to combine de-
large crystals. In addition, slow cooling pro- waxing with superdegumming of the crude oil
36 Fats and Fatty Oils

(see also Section 6.1) [44]. Peanut oil is not nor- formance drying oils from soybean and linseed
mally winterized because its turbidity is caused oils.
by small glyceride crystals that are difficult to
filter.
The separation of higher- and lower-melting 8. Hydrogenation [61], [62]
glycerides can be improved by fractionation us-
ing solvents such as hexane, acetone, or meth- Hydrogenation of the carbon – carbon double
anol, in which the unsaturated fats are more bonds of unsaturated glycerides leads to an in-
readily soluble. Costs are much higher than crease in melting point ( hardening, see also Sec-
for dry fractionation because of the need for tion 4.3). The combination of hydrogenation, in-
solvent recovery. This relatively sharp frac- teresterification, and fractionation offers the op-
tionation method is generally only economi- portunity of economically meeting the increas-
cal for preparing specialty products. For ex- ing demand for specialty products for foodstuff
ample, fractionation of palm oil with acetone and technical applications from available raw
gives a fraction (ca. 40 % of the feed) consist- materials.
ing of disaturated-monounsaturated glycerides, Trans fatty acids produced by isomerization
primarily 1,3-dipalmito-2-olein. during hydrogenation also occur in animal fats
The separation of relatively small fat crystals such as butterfat and tallow. Although there are
can be facilitated by selective wetting, for exam- indications that trans fatty acids may be metab-
ple with sodium lauryl sulfate or decyl sulfate in olized differently from their cis isomers [63],
aqueous solution. The crystal suspension, pro- long-term studies have demonstrated their tox-
duced either batchwise or continuously, is mixed icological safety [64]. As far as their effect on
with an aqueous solution containing the wetting blood lipid levels is concerned, they are compa-
agent and normally also an electrolyte such as rable with saturated fatty acids.
magnesium sulfate. The crystals covered with The selectivity of hydrogenation is deter-
wetting agent migrate to the aqueous phase as mined by the type and activity of the catalyst
a suspension that can be separated by centrifu- [65] (controlled poisoning and a large pore size
gation. Alfa – Laval recommends such a process increase selectivity), the operating temperature
(Lipofrac process) for the fractionation of palm (both selectivity and cis – trans isomerization in-
oil and for the winterization of other oils. crease with increasing temperature), stirring –
Selective extraction [58] has long been used mixing efficacy (increasing the hydrogen con-
in refining mineral oil. Liquefied hydrocarbons centration at the catalyst surface by intensive
or furfural are used as selective solvents in the stirring – mixing reduces selectivity), and the
separation of fats and fatty acids. This technique hydrogen pressure (increasing the pressure re-
not only permits the separation of fats and fatty duces the selectivity).
acids according to the degree of unsaturation or Neither absolute selectivity nor complete iso-
the molecular mass, but also effects the partial merization (or complete suppression of isomer-
removal of coloring matter, gums, and vitamins. ization) can be achieved. However, the process
Liquefied propane preferentially dissolves can be steered in a desired direction by suitable
saturated components ( Solexol process; see also choice of the above parameters to produce fats
page 33) [59]. This process has been used to with different degrees of saturation and melting
fractionate tallow. The solubility of fats and properties from a given oil. For example, peanut
fatty acids increases with decreasing molecular oil can be hardened nonselectively to an iodine
mass. Furfural preferentially dissolves unsatu- value of 70 – 90 yielding a soft, semiliquid fat.
rated components. It is miscible with fatty acids If the same oil is hardened to the same iodine
and monoglycerides at room temperature, but value under conditions that promote isomeriza-
with triglycerides only at elevated temperatures. tion, a firm, plastic fat with a melting point of
Depending on the operating temperature, fur- ca. 33 ◦ C is obtained. Palm oil is sometimes
fural is used alone or together with hexane. The hydro-bleached, i.e., hydrogenated under very
selective solubility behavior is less pronounced mild conditions that lead to selective hydrogen-
for differences in molecular mass [60]. The fur- ation of carotenoids.
fural process has been used to produce high-per-
 Fats and Fatty Oils 37

The oil should be at least degummed and with a nickel salt such as the carbonate, hydrox-
bleached prior to hydrogenation and preferably ide, or sulfate, which is converted into nickel
neutralized and bleached as well. Catalyst poi- oxide by roasting. The oxide is then reduced
sons include phosphatides, sulfur compounds, to metallic nickel in a stream of hydrogen at
soaps, and oxidation products from poor han- 300 – 400 ◦ C. Other routes involve decomposi-
dling and/or bleaching. Free fatty acids do not tion of nickel formate at 240 ◦ C or dissolution of
poison the catalyst but tend to slow down the aluminum from a nickel – aluminum alloy with
hydrogenation reaction. alkali (Raney catalyst). In addition, there are a
The hydrogen must be pure and dry and can number of mixed catalyst systems (copper, chro-
be produced by various routes. The most im- mium, cobalt) with special selectivities.
portant industrial process is decomposition of Batch hydrogenation (Fig. 23) is normally
natural gas or propane by passage over a nickel performed on a scale of 5 – 25 t. The dry oil
catalyst in the presence of steam at 800 – 900 ◦ C. is pumped into the hydrogenation vessel that
Electrolysis of water is used to a lesser extent. has been previously flushed with hydrogen, and
The hydrogen must be specially purified to re- heated to just below the required operating
move hydrogen sulfide and carbon monoxide, temperature (100 – 180 ◦ C). The catalyst (0.01 –
which are strong catalyst poisons. 0.1 % active nickel) is then introduced and the
hydrogen pressure increased. Alternatively, the
oil is vacuum-deaerated while it is heated be-
fore the catalyst and hydrogen are introduced.
Hydrogenation is an exothermic reaction; a de-
crease in the iodine value of one unit causes
a temperature increase of 1.5 – 2.0 ◦ C. The re-
quired operating temperature is therefore main-
tained by controlled cooling. Hydrogen is in-
troduced through a sparge ring at the bottom of
the hydrogenation vessel, pumped out at the top,
and recirculated. Sparging and fast stirring en-
sure adequate dispersion of the catalyst in the oil
and optimum mass transport. The usual working
pressure is 0.15 – 0.3 MPa (1.5 – 3 bar).

Figure 23. Flow diagram of a batch hardening plant

a) Converter; b) Filter press; c) Catalyst tank; d) Catalyst
pump

Nickel, platinum, and palladium are preferred

catalysts. Platinum and palladium are especially
suited for laboratory-scale and low-temperature
hydrogenations. Only nickel is used on a produc-
tion scale. Many different types of nickel cata-
lysts are available (→ Heterogeneous Catalysis
and Solid Catalysts). They essentially consist of Figure 24. Hydrogenation converter (dead-end design)
metallic nickel on a carrier such as silica gel, a) Heating and cooling coil; b) Turbine agitator; c) Baffle
silicic acid, or alumina. The carrier is treated
38 Fats and Fatty Oils

In hydrogenation autoclaves that operate tially (e.g., Alfa – Laval system). In fully con-
without hydrogen recirculation (“dead-end” tinuous plants, either the preheated oil and hy-
process), spent hydrogen is replaced at a some- drogen are passed over a stationary catalyst bed,
what higher pressure [66]. The intensive stirring or all three components are mixed prior to en-
required can be achieved with a turbine agitator tering the reactor (see Fig. 26). In the Procter
or similar device (Fig. 24). & Gamble process, the reactor contains a spe-
So-called loop hydrogenation reactors (e.g., cial stirrer to ensure intensive mixing in a thin
Buss, Fig. 25) have become increasingly popu- film. The Girdler Corporation developed a pro-
lar. The oil – catalyst mixture is constantly cir- cess in which three Votator heat exchangers are
culated through an external heat exchanger dur- arranged sequentially; the first vessel serves as
ing heating and cooling. This loop reduces total preheater, the second as a hydrogenator, and
cycle time; it also gives better temperature con- the third as a cooler. Continuous hydrogenation
trol and thus less product variation from batch of miscella at low temperatures over a catalyst
to batch. bed produces little isomerization but has not
achieved industrial importance.

Figure 26. Continuous hydrogenation of fatty acids and fatty

oils (Lurgi)
a) Dryer; b) Reactor

Figure 25. Loop hydrogenation reactor

The course of hydrogenation is normally
a) Autoclave; b) Mixing and reaction zone; c) Reactant – monitored by changes in analytical data such
solvent – catalyst suspension; d) Primary loop recirculation as iodine value or refractive index. The hydro-
pump; e) Primary loop heat exchanger genated products are characterized primarily by
When hydrogenation is complete, the product melting point and solids content at different tem-
is cooled to 80 – 90 ◦ C and the catalyst is filtered peratures.
off. Since the acid value tends to increase slightly
during hydrogenation, the crude hardened fat is
usually postneutralized with lye and bleached 9. Interesterification
before it is deodorized. Posttreatment with cit-
ric or phosphoric acid, followed by bleaching Prior to interesterification, fats must be neutral-
prior to deodorization, is an alternative to lye ized to less than 0.1 % ffa and dried to avoid ex-
posttreatment. In either case the residual nickel cessive deactivation of the catalyst, which is nor-
content is reduced to <0.2 ppm. Deodorization mally sodium ethoxide (see also Section 4.2).
of a hardened fat is essential since hydrogenation The catalyst (0.1 – 0.3 %) is finely dispersed in
leads to typical hardening flavors which must be the fat. After completion of the interesterifica-
removed. tion reaction, which is carried out at 80 – 100 ◦ C,
Continuous hydrogenation is primarily suit- excess catalyst is deactivated by addition of wa-
able for the production of one particular prod- ter. The resulting soap is removed by washing
uct over a longer period of time. Fully continu- with water and bleaching. During interesterifi-
ous processes are the exception rather than the cation, sodium ethoxide is converted into fatty
rule. In semicontinuous processes several reac- acid ethyl esters, which are removed during the
tion vessels or autoclaves are arranged sequen- final deodorization step.
 Fats and Fatty Oils 39

Interesterification can be performed batch- esterified palm oil; the glyceride composition is
wise (Fig. 27), usually in a neutralization– given in Table 22.
bleaching vessel, or continuously. In the contin-
uous process, fat with suspended catalyst passes Acidolysis. An example of the industrial ap-
through a tubular reactor (Fig. 28) [67]. In di- plication of acidolysis is the transesterification
rected interesterification (see Section 4.2) the of coconut oil with acetic acid and the subse-
fat is cooled, for example, in a scraped-surface quent esterification of excess acid with glycerol.
cooler to crystallize the higher-melting glyc- A mixture of aceto fats (laurodiacetin, myristo-
erides. diacetin, etc.) is obtained which are used as plas-
ticizers and coatings. Transesterification of co-
conut oil with higher fatty acids, employing con-
tinuous distillation of the liberated lower fatty
acids (C6 – C10 ), yields fats with properties sim-
ilar to those of cocoa butter. Acidolysis is usually
performed in the presence of an acid or base cat-
alyst; no catalyst is required at temperatures of
260 – 300 ◦ C.

Figure 27. Batch reactor for interesterification

Figure 29. Solids content of native and interesterified palm

oil (Alfa – Laval)
a) Native palm oil; b) Randomly interesterified palm oil;
c) Directedly interesterified palm oil

Alcoholysis. The replacement of the glycerol

Figure 28. Continuous interesterification moiety of a fat with lower monohydric alcohols
a) Heat exchanger; b) Dryer; c) Homogenizer; d) Tubular proceeds at lower temperatures. The Bradshaw
reactor; e) Mixer; f) Centrifuge; g) Dryer process [68] utilizes transesterification of fats
with methanol as the first step in the continu-
New types of fats can be created by suit-
ous production of soap. Fat with an acid value
able choice of interesterification components.
of less than 1.5 is stirred with excess methanol
Depending on the starting components, the melt-
for a few minutes in the presence of 0.1 – 0.5 %
ing point of the fat after interesterification can
caustic soda at ca. 80 ◦ C. On subsequent stand-
be lower or higher. Figure 29 shows the solids
ing, practically dry glycerol settles at the bottom
content (dilatation) curves of native and inter-
of the reaction vessel. The same principle is em-
40 Fats and Fatty Oils
Table 22. Fatty acid and glyceride composition of native and interesterified palm oil ∗

Native palm oil Interesterified palm oil

Random interesterification Directed interesterification

◦
mp, C 42 47 52
Fatty acid composition, mol %
S 51 51 51
U 49 49 49
Glyceride composition, mol %
S3 7 13 32
S2 U 49 38 13
SU2 38 37 31
U3 6 12 24

∗ S = saturated fatty acid. U = unsaturated fatty acid.

ployed in the preparation of fatty acid methyl Wastewater from lye neutralization and from
esters for laboratory analyses. If the acid value the barometric condensers of deodorizers can be
is higher than 1.5, boron trifluoride is normally discharged into communal sewage systems or
used as a catalyst. surface waters only if certain limits for resid-
The exchange of glycerol with other poly- ual fat, pH, sediment, sulfate, and chemical and
hydric alcohols, such as pentaerythritol, is best biological oxygen demand are met. Otherwise
done under conditions at which glycerol can be biological pretreatment is required. Since the
distilled off, i.e., at 200 – 250 ◦ C and 5 – 40 kPa cost of biological or other pretreatment of waste-
(50 – 400 mbar), in the presence of an alkaline water can be considerable, there has been a trend
catalyst. toward physical refining (i.e., refining without
The production of mono- and diglycerides by lye neutralization) by employing special degum-
reacting fats with an excess of glycerol is a spe- ming techniques, bleaching, and distillative de-
cial case of transesterification of fatty acid esters odorization.
with polyhydric alcohols. These glycerides are Bleaching earth is normally extracted before
especially important as emulsifiers. The produc- being deposited or burnt. The extracted fats can
tion process consists of heating a fat with 25 – be recycled.
40 % glycerol at 205 – 245 ◦ C in the presence Deodorizer distillates [55] can be used in ani-
of sodium hydroxide or a sodium alkoxide. Part mal feeds, as a source of vitamin E, for technical
of the catalytic effect is probably based on soap applications, or simply burnt.
enhancing the solubility of glycerol in fat. In-
dustrial products contain 40 – 50 % monoglyc-
erides. Oxidation and undesirable color effects 11. Standards and Quality Control
can be minimized by working in vacuo or under
an inert gas, and by using stainless steel reaction Standardized methods for quality control have
vessels. Monoglyceride concentrates can be pro- been issued by the following organizations:
duced by molecular or high-vacuum distillation. Association Française de Normalisation
(AFNOR), American Oil Chemists’ Society
(AOCS), Association of Official Agricultural
10. Environmental Aspects Chemists (AOAC), American Society for Test-
ing and Materials (ASTM), British Standards In-
Crude oils and fats can be contaminated with stitution (BSI), Deutsche Gesellschaft für Fet-
traces of various substances such as metals (e.g., twissenschaft (DGF), Deutsches Institut für
lead, arsenic, cadmium, selenium, mercury), Normung (DIN), International Association of
chlorinated organic pesticides (DDT, dieldrin), Seed Crushers (IASC), International Union of
mycotoxins (e.g., aflatoxins), and sulfur com- Pure and Applied Chemistry (IUPAC), Interna-
pounds. These trace contaminants are removed tional Standards Organization (ISO), the Nether-
in the course of refining [55]. lands Normalisatie Instituut (NNI), and the Fed-
 Fats and Fatty Oils 41

eration of Oils, Seeds, and Fats Associations prior to analysis. Larger oilseeds are commin-
(FOSFA). uted prior to analysis.
There is an increasing trend for the various
national and international methods to be uni-
formly standardized as ISO procedures; these 11.2. Raw Materials
are generally adopted as official methods within
the European Community. Buying – selling contracts for oilseeds, crude
The IASC (8 Salisbury Square, London oils, and fats normally specify a maximum per-
EC 4P 4 AN, UK) has issued a list of associations missible concentration of impurities. If this level
dealing with or issuing standard forms of con- is exceeded the buyer receives a discount. The
tract and/or quality standards for oilseeds, oils, key parameters in oilseeds are fat and moisture
and fats. This association has also drawn up a list contents.
of official institutions and associations that deal To determine the fat content of oilseeds, ex-
with or issue methods for grading, sampling, and peller cakes, and meals, the comminuted sam-
preparing samples for analysis, as well as meth- ple is extracted with a solvent and the fat taken
ods for analysis that are referred to in standard up by the solvent is determined refractometri-
forms of contract or usually applied in the trade cally, gravimetrically, densitometrically, or by
of oilseeds, oils, and fats. the change in dielectric constant. The gravimet-
ric methods are time-consuming but most reli-
able. Each method gives reproducible but dif-
11.1. Sampling ferent values, depending on the type of solvent
(usually hexane or petroleum ether) and the ex-
Correct sampling is a difficult process requiring traction method. The fat content can also be de-
careful attention; it must take into account that termined directly without solvent extraction by
separation can occur during storage of fats and nuclear magnetic resonance or by near infrared
fatty products. Hulls, for example, tend to sepa- absorption.
rate from oilseeds because of their lower density. According to ISO 659, the oilseeds are ex-
Oils and fats tend to form a sediment of water tracted with n-hexane or petroleum ether in a
and dirt; for this reason a representative average Bolton extractor. After extraction for several
sample is often taken in bypass during pumping. hours, the sample is removed from the extrac-
A special zone sampler consisting of a metal tor thimble, reground, and reextracted. This is
cylinder with a valve at both ends is often used repeated a third time. The extract is evaporated
for sampling the contents of a tank. The sampler and the residual oil dried to constant weight at
is lowered into the tank, the valves being oper- 103 ± 2 ◦ C.
ated with a cord. Starting from the bottom of the Unilever has developed a far quicker method
tank, the oil is sampled at various depths up to which gives identical values to those obtained
the surface. Smaller containers (drums) are sam- with the ISO method. The sample is first com-
pled with a tube or shutter scoop; solid fats in minuted in a ballmill in the presence of petro-
retail packs are sampled with a sampling scoop. leum ether, and then extracted for 2 h in a Bolton
Special sample dividers are used for oilseeds. extractor.
Sampling apparatus for bags includes sack-type When determining the fat content of fruit
spears or triers, cylindrical and conical sam- pulps and animal tissues, predrying of the sub-
plers, and hand scoops. Shovels, scoops, cylin- strate at 105 ◦ C in vacuo is recommended. When
drical and conical samplers, or mechanical sam- extracting animal tissue polar solvents such as
plers are used for drawing small periodical sam- ether – HCl or ethanol – chloroform are used to
ples from a flow of oilseeds. Shovels, quartering facilitate liberation of fat from lipoprotein com-
irons, or riffles are used for mixing and dividing. plexes present in aqueous dispersion.
Samples for analysis of oilseeds, expeller Water and volatile matter are generally de-
cakes, and meals should preferably be at least termined by weighing a sample before and after
2 kg, and of oils and fats at least 250 g. The heating under standardized conditions, usually
samples should be homogenized immediately 103 ◦ C. Crude oils are normally analyzed for
water and volatile matter, color, particulate dirt,
42 Fats and Fatty Oils

phosphatides, and free fatty acids. Up to 0.5 % butter and substitutes, are conditioned at higher
moisture and impurities are generally regarded temperatures for up to 18 h.
as technically unavoidable. Inferior oils usually The point of incipient fusion is the tempera-
have a dark color and a high content of free fatty ture at which a sample placed in a U-tube begins
acids and oxidized components that is indicated to flow on being warmed. The point of complete
by a relatively high absorption at 232 nm, high fusion is the temperature at which a sample be-
anisidine and totox numbers, and a high con- comes completely clear.
centration of oxidized fatty acids. These analyt- Flow and drop points are primarily of impor-
ical data give an approximate indication of the tance for technical greases and some plastic fats.
expected yield and quality of the fully refined They are determined in an Ubbelohde apparatus.
product. Admixture can be detected within cer- Flow point is the temperature at which a drop
tain limits by determining the composition of begins to be clearly formed at the end of a ther-
fatty acids, sterols, and tocopherols. Very severe mometer, and drop point is the temperature at
admixture can be detected by iodine value, re- which the drop falls.
fractive index, and saponification value. Dilatation, i.e., the increase in volume of a
fat on passing from the solid to the liquid state
at a given temperature, can be used to deter-
11.3. Oils and Fats mine the concentration of solid components at
a certain temperature (Solid Fat Index, SFI).
11.3.1. Physical Methods This type of measurement has been replaced by
the much quicker nuclear magnetic resonance
The density or specific gravity at a given temper- method which is based on the difference bet-
ature is determined by weighing a known vol- ween the response from the hydrogen nuclei in
ume, by determining the buoyancy, or by elec- the solid phase and that from all the hydrogen
tromagnetic excitation of the natural frequency nuclei in the sample.
of the sample. Differential thermal analysis permits the
The refractive index is normally determined quantification of changes in the solid phase
with an Abbe refractometer at 20 ◦ C for oils of a fat on being heated. A sample is placed in
which are liquid at this temperature and at 40, 60, a metal block which is heated at a constant rate.
or 80 ◦ C for fats. The temperature coefficient is The difference between the temperature of the
ca. 0.0036 K−1 . A correlation exists between re- block and that of the sample is characteristic of
fractive index and iodine value (see Section 3.8); crystal modifications occurring during melting
for this reason the refractive index is often used [69].
to follow the course of hydrogenation. On passing from the liquid to the solid state,
Most oils and fats rotate polarized light by the temperature remains constant for a certain
only a few tenths of a degree; higher values are period of time because of the liberated heat of
observed with substituted fatty acids such a ri- fusion; with sufficient insulation an increase in
cinoleic acid. temperature can be observed. The titer value of
In melting a distinction is made between the a fat is the maximum value to which the temper-
slip point, the point of incipient fusion, and the ature rises in the cooling curve. Cooling curves
point of complete fusion. The slip point, the usu- are frequently used to check the purity of fats
ally cited melting point, is the temperature at which consist predominantly of a few triglyc-
which a sample plug placed in an open glass eride types, e.g., cocoa butter.
capillary begins to rise when gradually heated The cloud point is the temperature at which
in a water bath or by other means. This method an oil or molten fat begins to become turbid when
can be automated. The slip point value is influ- cooled under controlled conditions. The temper-
enced by the method of cooling used prior to ature stability of an oil is normally assessed after
melting. Whereas for conventional fats the sam- keeping a carefully dried sample at 0 ◦ C for 5 –
ple is normally solidified by chilling the sample 8 h.
and capillary at − 10 ◦ C for a few minutes, fats The smoke, flash, and fire points of oils and
that exhibit distinct polymorphism, e.g., cocoa fats are measures of their thermal stability when
heated in air. Table 13 shows some typical data.
 Fats and Fatty Oils 43

The smoke point is the temperature at which 11.3.2. Chemical Methods

smoke is first detected in a standard appara-
tus with specially designed, draft-free illumina- For preliminary identification and evaluation,
tion. The flash point is the temperature at which determination of chemical data such as the io-
volatile products are evolved at such a rate that dine value (see below) and the fatty acid com-
they can be ignited but do not continue to burn. position often suffice. In many cases, however,
The fire point is the temperature at which the pro- it is necessary to test for characteristic minor
duction of volatile products is sufficient to sup- constituents directly or by specific chemical re-
port continuous combustion after ignition. The actions. Table 23 gives some examples.
smoke point is important in the assessment of The complexity of oils and fats makes the
refined oils and fats used for deep frying. It is determination of their precise composition diffi-
governed primarily by the free fatty acid content. cult. For this reason analytical values are used to
The flash point is a measure of residual solvent express certain properties. Analytical values in
in crude oils, although gas – liquid chromato- this sense are defined as the equivalent amounts
graphic methods are now generally preferred for of certain reagents which react with specific
this determination. groups in the lipid molecules. Many of the older
The viscosity of an oil can be determined analytical values are no longer used because of
in a flow (Engler), capillary (Ubbelohde), fall the introduction of modern analytical techniques
(Höppler), or shear (Haake) viscometer. such as column, paper, gas – liquid, and high –
There are a number of different methods for performance liquid chromatography, and spec-
determining the color of an oil or fat. In the trophotometry. However, the principle of deter-
Lovibond tintometer the color of the sample in mining analytical values is still valid since it can
a standardized cell with a length of 1 (2.45 cm) authenticate and assess the quality of an oil or
or 5 1/4 (13.3 cm) is matched – either manu- fat relatively quickly with modest laboratory fa-
ally or automatically – with the color of standard cilities.
yellow, red, and blue color slides. Other colori- The saponification value is the number of
metric scales are based on standard iodine or milligrams of potassium hydroxide required to
potassium dichromate solutions. The most ob- saponify (hydrolyze) 1 g of fat and is related to
jective way of assessing color is to determine the molecular mass of the fat.
the absorption at specified wavelengths in the The hydroxyl value is expressed as the num-
range 370 – 780 nm. ber of milligrams of potassium hydroxide re-
The characteristic absorption maxima of spe- quired to neutralize the acetic acid needed to
cific lipid groups in the infrared and ultraviolet acetylate 1 g of fat.
ranges can be used qualitatively and quantita- The carbonyl value is defined as the num-
tively (see Section 3.8). Fatty acids with iso- ber of milligrams of CO (carbonyl groups) per
lated double bonds such as linoleic, linolenic, gram of fat. The basis for this value is the con-
and arachidonic acids do not exhibit specific UV version of the carbonyl group into an oxime with
absorption. After isomerization with alkali they hydroxylamine in alcoholic KOH:
can, however, be determined by the characteris-
tic absorption maxima of the corresponding con- RCO + NH2 OH −→ RC=NOH + H2 O
jugated fatty acids. Infrared spectroscopy is used
primarily for the identification of specific groups Hydroperoxides interfere with this determi-
such as hydroxyl and trans double bonds. nation.
Optical rotatory dispersion spectroscopy The acidity of an oil or fat arises from free
is used only in studies of biosynthesis and inorganic or organic acids. The acid value is de-
metabolism of lipids. fined as the number of milligrams of potassium
Mass spectroscopy, especially in combina- hydroxide required to neutralize 1 g of fat. The
tion with gas chromatography and other meth- content of free fatty acids (ffa) expresses how
ods of separation, is often used to determine the many parts of free fatty acids are contained in
structure of oxidation products and substituted 100 parts of fat. This content is – depending on
fatty acids. the type of oil or fat – expressed as % oleic acid
Table 23. Detection of oils and fats

44
Oil/Fat Characteristic Specific reaction or Limit of detection Remarks
constituent detection procedure

Animal fats cholesterol isolation of sterols from the unsaponifiable 1 % in vegetable oils and fats Vegetable oils and fats contain traces of
matter by TLC or HPLC, and separation by cholesterol in addition to phytosterols while in
HPLC, TLC, or GLC animal fats only cholesterol but no phytosterols
have been found.
branched C13 – C17 fatty acids GLC of fatty acid methyl esters ca. 2 % in vegetable oils and fats The branched fatty acids may have to be
and odd-numbered, unbranched concentrated, e.g., by urea adduct formation.
C11 – C19 fatty acids

Lard palmitic acid in the glyceride isolation of the glyceride fraction with 1 1 % lard in tallow Determination of the fatty acid composition in
2-position saturated and 2 unsaturated fatty acid groups, the 2-position without prior glyceride

Fats and Fatty Oils

followed by determination of the fatty acid fractionation gives a significantly higher limit
composition in the glyceride 2-position of detection.

Partially hardened and highly unsaturated C20 – C24 Tortelli – Jaffe reaction (green coloration ca. 2 % in other oils and fats Not strictly specific; highly unsaturated
unhardened marine oils fatty acids with bromine in chloroform/acetic acid) GLC vegetable oils can also react.
of the fatty acid methyl esters

Vegetable oils and fats phytosterols isolation of sterol esters and separation as ca. 2 % in animal fats Sterols occur in vegetable oils and fats in the
sterols by TLC, HPLC, and GLC free and esterified form, while in animal fats
they are only present in the free form.

Castor oil ricinoleic acid TLC; IR spectroscopy ca. 1 % in other oils and fats Hydroxy fatty acids can be formed during
autoxidation of oils and fats.

Coconut oil and palm kernel oil lauric acid GLC of the fatty acid methyl esters ca. 2 % in other vegetable oils
except oils and fats rich in lauric
acid, e.g., babassu fat

Cottonseed oil and other oils of malvalic acid Halphen reaction (red coloration on heating depending on extent of refining Hardened cottonseed oil does not give this
the malvaceae, tiliaceae, and with sulfur in CS2 ) reaction; malvalic and sterculic acid are
bombaceae families converted into saturated, branched fatty acids
during hardening.
Table 23. Continued

Oil/Fat Characteristic Specific reaction or Limit of detection Remarks

constituent detection procedure

Crude palm oil α- and β-carotene isolation from nonsaponifiable matter by HPLC Indicative of distillative or other heat treatment.

Peanut oil lignoceric and arachidic acid GLC of the fatty acid methyl esters 4 Hardened marine oils and certain vegetable oils
also contain higher molecular mass fatty acids.

Olive oil α-tocopherol isolation and separation by HPLC ca. 5 % other oils in olive oil

Partially hardened fats trans fatty acids IR spectroscopy ca. 2 % in vegetable oils Animal fats contain up to 10 % trans fatty acids.

Rapeseed oil erucic acid GLC of the fatty acid methyl esters ca. 1 % of “high erucic acid” Admixture with “low erucic acid” rapeseed oil
rapeseed oil in other vegetable cannot be detected satisfactorily this way.
oils Marine oils also contain erucic acid.

brassicasterol isolation and separation of sterols by TLC, ca. 5 % in other vegetable oils Independent of erucic acid content.
HPLC, and GLC

Sesame oil sesamol and sesamin Baudouin reaction (red coloration with ca. 0.5 % in other oils and fats
furfural and HCl)

Soybean oil linolenic acid GLC of the fatty acid methyl esters ca. 10 % in e.g., sunflower oil

δ-tocopherol isolation and separation by HPLC ca. 5 % in e.g., sunflower oil

Teaseed oil Fitelson test (modified Liebermann – Burchard e.g., 5 % in olive oil
test)

Tung oil eleostearic acid GLC of the fatty acid methyl esters ca. 1 % in other oils and fats
Fats and Fatty Oils
45
46 Fats and Fatty Oils

(M r 282), % palmitic acid (M r 256), or % lauric

acid (M r 200). If not specified, it is calculated as 2 H2 O + SO2 + I2 −→ H2 SO4 + 2 HI
oleic acid.
Impurities such as dirt and seed particles are
Peroxides are determined iodometrically ac-
not dissolved on treating the sample with petro-
cording to Wheeler (cold) or Sully (hot) and are
leum ether or hexane and can be collected and
expressed as milliequivalents of active oxygen
weighed as filter residue.
per 1000 g of fat. The peroxide value can also
Traces of residual solvent are best determined
be expressed in millimoles per kilogram (Lea
by gas chromatography, either by direct injection
value, 1 mequiv/kg = 0.5 mmol/kg) or in mil-
or after enrichment by the so-called headspace
ligrams per kilogram (1 mequiv/kg = 8 mg/kg).
technique [71].
It is important to use fresh reagents and to ex-
Nonsaponifiable matter is defined as that ma-
clude oxygen as far as possible during the deter-
terial which is a soluble constituent of the fat and
mination.
which remains insoluble in the aqueous phase
The reaction with anisidine is often used to
after saponification of the fat and can be ex-
determine the carbonyl compounds produced
tracted with petroleum ether or diethyl ether;
during autoxidation. The anisidine value is de-
diethyl ether tends to give higher values. Non-
fined as 100 times the absorption of a 1 % sample
saponifiable matter consists primarily of sterols,
solution in a 1-cm cell after reaction with ani-
alcohols, hydrocarbons, and vitamins.
sidine. This value has been recommended for
Oxidized fatty acids contain one or more hy-
monitoring the refining of oils and fats. It is also
droperoxide, hydroxyl, or keto groups in the
used in combination with the peroxide value to
fatty acid chain and can be determined by their
characterize the overall autoxidative state of an
reduced solubility in petroleum ether. Only part
oil or fat ( totox value):
of the oxidized fatty acids are detected by this
Totoxvalue = 2 × peroxidevalue+ type of analysis. Thus, the separation of fats into
1 × anisidinevalue polar and nonpolar fractions on silica gel tends
to be preferred when, for example, characteriz-
The iodine value denotes the percentage by
ing used frying fats [72].
weight of iodine bound by 100 g of fat and is an
To determine resin acids in the presence of
approximate measure of the degree of unsatura-
fatty acids, the sample is esterified with meth-
tion. The usual method is that of Wijs. The rate
anol in the presence of an acid catalyst; resin
of addition of iodine to double bonds depends
acids escape esterification.
on their distance from the carboxyl group. Con-
Inorganic acids can be detected by extract-
jugated unsaturated fatty acids are only partially
ing the sample with hot water and testing the
halogenated; substituted fatty acids such as keto
aqueous extract with methyl orange.
acids and cyclic acids can also react. Trans fatty
Free alkali can similarly be detected by dis-
acids react more slowly than the cis isomers.
solving the sample in ether – ethanol and adding
The oxidative stability of oils and fats is deter-
phenolphthalein (red coloration). Traces of soap
mined by their composition and their previous
can be detected down to 10 ppm by dissolving
history. A number of empirical methods have
the sample in ether – ethanol, adding bromophe-
been developed to express oxidative stability
nol blue (which gives a green-blue color in the
[70]. These tests are performed at elevated tem-
presence of soap), and titrating with very dilute
perature and do not necessarily correlate with
HCl.
organoleptic stability at ambient temperature.
Many crude seed oils contain considerable
The most frequently practiced methods are the
concentrations of phosphatides. These can be
Schaal test and the Swift test (or Active Oxy-
determined by dry digestion of the sample with
gen Method); automated versions of the latter
magnesium oxide and photometric determina-
are popular, e.g., the Rancimat apparatus.
tion of the resulting phosphate after addition of
The moisture content can be determined by
molybdate [73]. An alternative is the direct de-
weighing before and after drying or by codistil-
termination of phosphatides by atomic absorp-
lation with toluene. It is most conveniently de-
tion or plasma emission spectroscopy.
termined by the Karl Fischer titration, which is
based on the following reaction:
 Fats and Fatty Oils 47

Methods for determining traces of mineral Monoglycerides can be isomerized into the
oil in edible oils are based on the fluorescence 1-isomers prior to addition of periodic acid by
of mineral oils, their insolubility in acetic anhy- treating the sample with perchloric acid.
dride, and the fact that they are not retained on
alumina. Headspace gas chromatography is also
used. 12. Storage and Transportation [75]
The gas chromatographic determination of
the fatty acid composition of an oil or fat has Crude Oils and Fats. If crude oils and fats
replaced the time-consuming, chemical tech- are to be stored for a long time, removal of in-
niques of fractionating fatty acids into single soluble impurities by sedimentation, filtration,
components or groups. Analytical values such as or centrifugation is advisable. Seed particles
the Reichert – Meissl, the Polenske, the Kirch- and cell fragments contain fat-splitting enzymes,
ner, and the butyric acid number (as measures which can gradually hydrolyze glycerides in the
of the concentration of lower molecular mass presence of moisture and produce an increase in
or steamvolatile fatty acids) are now virtually free fatty acid concentration. Proteins are good
obsolete. Prior to gas chromatographic analysis, nutrients for microorganisms.
the fatty acids are converted into their methyl Further measures for avoiding undue quality
esters either by direct transesterification of the deterioration include drying the crude oil to less
sample with methanolic KOH (acid values <2) than 0.2 % moisture and storage without heating;
or by saponification (acid values >2) followed consistent fats should be stored at not more than
by esterification of the fatty acids with metha- 10 – 15 ◦ C above the melting point. Frequent
nol in the presence of BF3 . Full details of these pumping should be avoided to prevent saturation
procedures and of the various types of columns, of the oil with air and consequent autoxidation.
column packings, and detectors are given in The addition of antioxidants is useful primar-
ISO 5508/5509. If a marker fatty acid is used as ily for animal fats; most vegetable oils contain
an internal standard, quantitative determination sufficient concentrations of natural antioxidants.
of the total amount of monomeric, nonoxidized Most crude vegetable oils can be stored for some
fatty acids is possible; nonsaponifiable matter, months without significant loss in quality if the
oxidized, and polymerized fatty acids are re- above precautionary measures are observed. An-
tained on the gas chromatographic column. imal fats can be stored for only relatively short
Polymeric fatty acids are conveniently deter- periods of time without loss in quality. Contin-
mined by special high-performance liquid chro- ual monitoring of the acid value, peroxide value,
matography (HPLC) or gel permeation chro- and other data that characterize the state of oxi-
matography [74]. dation during storage is recommended.
The glyceride structure may have to be de-
termined to authenticate an oil or fat. The meth- Raffinates. Since natural antioxidants, such
ods for determining positional isomers are based as tocopherols, phenols, and synergists, are par-
on fractional crystallization, selective oxida- tially removed during the refining process, semi-
tion, chromatographic separation, or enzymatic and fully refined oils often have lower oxida-
hydrolysis of the fatty acid in the 2-position; they tion stability than the crude oils. This is espe-
are normally too expensive for routine control cially true for oils with a relatively high con-
unless specialty products are involved. tent of polyunsaturated fatty acids. Therefore,
Mono- and diglycerides are formed by hydro- raffinates must be protected as far as possible
lysis of fats and therefore occur in higher from light, air, moisture, relatively high temper-
concentrations in fats from damaged seeds. atures, and trace metal prooxidants if they are to
Mono-, di-, and triglycerides can be separated be stored for long periods.
by column or thin-layer chromatography. 1- Raffinates are best stored in closed contain-
Monoglycerides can be determined directly in ers with a relatively small ratio of surface area to
fats by oxidative fusion with periodic acid: volume in order to minimize access and infusion
of air. Any heating should be uniform without lo-
RCOOCH2 CHOHCH2 OH + H5 IO6 −→
cal overheating; the temperature should not be
HCHO + RCOOCH2 CHO + HIO3 + 3 H2 O
48 Fats and Fatty Oils

higher than 10 ◦ C above the melting point. Aer- 13.1.1. Palm Oil [76]
ation can be further reduced by using a bottom-
loading pipe and a nitrogen atmosphere during Palm oil [8002-75-3] is obtained from the fruit
both storage and transportation. Immediately af- pulp of the oil palm (Elaeis guineensis). The fruit
ter deodorization, nitrogen should be introduced bunches, weighing 10 – 25 kg, contain 1000 –
into the suction side of the loading pump that 2000 plum-sized fruits which are dark red be-
feeds the storage or transport vessels. cause of their carotene content. The fruits con-
The storage containers are preferably made of tain 35 – 60 % oil, depending on the moisture
aluminum or stainless steel, although mild steel content. The oil palm is native to West Africa,
can be used if access of air is limited and if cool- and is extensively cultivated in Malaysia, In-
ing is adequate. Raffinates can be kept stored in donesia, and Central Africa. The oil yield has
large tanks for several weeks without an increase been increased to 4.5 t of oil per hectare and
in peroxide value; however, the peroxide value year by the introduction of insect pollination and
tends to increase each time the oil is pumped. by selecting and cloning high-yielding cultivars.
Raffinates are transported in bulk in ships and Malaysian palm oil production was 4.13×106 t
trucks, in drums, tins, and bottles; consistent fats in 1985 and is expected to reach 6×106 t/a by
can also be transported in block or powder form 1990.
if the melting point is sufficiently high. Saponification value 195 – 205
Iodine value 44 – 58
Nonsaponifiable matter 0.5 %
mp 36 – 40 ◦ C
13. Individual Vegetable Oils and n40
D 1.453 – 1.456
Fats Carotene 500 – 2000 ppm

Vegetable oils and fats are normally divided into For fatty acid composition see Tables 1 and
fruit pulp fats and seed oils. Although there are 2.
few fruit pulp fats (e.g., palm oil and olive oil), Palm oil contains up to 40 % oleodipalmitin,
the number of seed oils is considerable. Seed consisting primarily of 2-oleodipalmitin.
oils can be conveniently subdivided according
to their characteristic fatty acids: Production. The fresh palm fruits con-
tain very active fat-splitting enzymes (lipases),
1) Lauric acid oils (e.g., coconut and palm ker-
which must be deactivated as quickly as possible
nel oil)
prior to isolating the oil. Since lipases are partic-
2) Palmitic – stearic acid oils (e.g., cocoa butter)
ularly active in damaged fruits, the whole fruit
3) Palmitic acid oils (e.g., cottonseed and corn
bunches are sterilized by heating with live steam
oil)
in autoclaves; this deactivates the enzymes and
4) Oleic – linoleic acid oils (e.g., sunflower and
loosens the fruit from the bunches.
linseed oil)
The sterilized fruit bunches are threshed in
5) Leguminous oils (e.g., soybean and peanut
a rotary drum stripper consisting of longitudi-
oil)
nal channel bars; the fruit falls through whereas
6) Cruciferous oils (e.g., rapeseed oil)
the empty bunch stem is retained in the drum.
7) Conjugated oils (e.g., tung oil and oiticica
The separated, sterilized fruit is then converted
oil)
into an oily mash by a mechanical stirring pro-
8) Substituted fatty acid oils (e.g., castor oil)
cess known as digestion. The digested fruit mass
is passed through screw presses, and the liquor
from the press is clarified by static settling or by
13.1. Fruit Pulp Fats using decanter centrifuges. After washing with
hot water and drying, the oil can be stored and
Palm oil and olive oil are the most important transported.
products within this group. High-grade palm oil contains ca. 3 % free
fatty acids, inferior grades up to 5 %. Crude plan-
tation oils obtained from palm fruits processed
 Fats and Fatty Oils 49

under conditions that minimize autoxidation and stearin and olein fractions followed by repeated
lipolysis contain ca. 2 % free fatty acids and can fractionation.
be readily bleached; such oils are traded as super
prime bleachable (SPB) grades. Use. Palm oil is used predominantly for ed-
ible purposes. Refined palm oil is used exten-
Refining. Lye neutralization of palm oil may sively in shortenings and margarines. Carotene
entail relatively high losses of neutral oil since concentrates from crude oil have been largely re-
inferior crude oils contain high concentrations placed by synthetic carotene as coloring agents
of mono- and diglycerides, which exert a strong for margarines.
emulsifying effect. Palm oil is therefore of- Palm stearin can be used in margarine and
ten neutralized by distillation at temperatures shortening blends whereas palm olein is used
up to 270 ◦ C and 0.5 – 0.8 kPa (5 – 8 mbar) af- primarily in liquid frying fats and shortenings.
ter pretreatment with phosphoric or citric acid Technical applications of palm oil include
and bleaching earth to remove foreign mat- tempering of metal and production of soap.
ter and traces of copper and iron compounds.
During distillative neutralization (stripping), the Other Palm Oil Varieties. These are com-
oil is also bleached (i.e., heat-bleached), since mercially relevant only in their countries of ori-
carotenes are decomposed and removed. The gin. Tucum oil (saponifaction value 200, iodine
carotenes in palm oil mainly consist of α-and value 40) is obtained from the fruit pulp of As-
β-carotene, with lower concentrations of γ- trocaryum vulgare, a palm growing in Central
carotene, lycopene, and xanthophylls. America.
Distillative neutralization can be performed
under conditions that simultaneously deodor-
ize the oil. For very light raffinates, distilla- 13.1.2. Olive Oil
tive neutralization is often followed by posttreat-
ment consisting of a lye wash, bleaching with Olive oil [68153-21-9] is obtained from the fruit
earth, and deodorization. Color and stability are of olive trees (Olea oleaster, Olea europaea
largely a function of the quality of the crude oil. oleaster) and some related varieties such as Olea
“White” palm oil, e.g., for biscuit fats, can gen- americana which is grown in South America.
erally only be made from crude SPB oils and by Saponification value 185 – 196
using fairly large amounts of bleaching earth. Iodine value 80 – 88
Bleaching with oxidizing agents, with air in- Nonsaponifiable matter <1.4 %
jected at 110 – 115 ◦ C, or with activated earth mp −3 ◦ C
n25 1.466 – 1.468
at 140 – 160 ◦ C is used only for technical appli- D

cations. Palm oil can be effectively decolorized

by mild hydrogenation at temperatures below For fatty acid composition see Tables 1 and
100 ◦ C (hydrobleaching). 2.
Palm oil can be separated into a solid and a Olive oil has a yellow to greenish-yellow
liquid fraction. Two-stage cooling to 32 – 34 ◦ C color and becomes cloudy below −5 ◦ C. Va-
and 25 – 27 ◦ C followed by separation over filter rieties with a higher cloud point can be made
presses yields 20 – 25 % palm stearin, mp 50 – by winterization. The glycerides consist of
52 ◦ C, and 75 – 80 % liquid palm olein. The liq- 45 – 60 % monosaturated dioleins, 25 – 34 % di-
uid glycerides can be separated from the solid oleolinolein, and 4 – 29 % triolein. Saturated
fraction by centrifugation after addition of sur- triglycerides are present at <1 %. The non-
factant solutions. Fractionation in the presence saponifiable material contains saturated and un-
of solvents (acetone, hexane) gives 10 % of a saturated hydrocarbons, including 0.1 – 0.7 %
stearin melting at ca. 55 ◦ C, 60 % olein, and 25 – squalene.
30 % of an intermediate fraction with proper-
ties similar to those of cocoa butter. The yield Production. The quality of olive oil depends
of the intermediate fraction can be increased to on the ripeness of the olives, the type of harvest-
ca. 50 % by interesterification of the combined ing (picking, shaking), intermediate storage, and
type of processing. Olives contain 38 – 58 % oil
50 Fats and Fatty Oils

and up to 60 % water. Ripe olives should be pro- Sanza or Orujo oil with glycerol, can be detected
cessed as quickly as possible since lipases in the by the glyceride composition.
pulp cause rapid hydrolysis of the oil, impairing
its quality for edible purposes. Top-grade oils
are made from fresh, handpicked olives by com- 13.1.3. Avocado Oil [77]
minution, pasting, and cold pressing. Avocado oil is isolated from the pulp of the
Traditionally, olives were ground into a paste pearlike fruit of the tree Persea gratissima L.
with stone mills; today modern milling equip- growing in Southern Europe, South Africa, the
ment is used. Milling is followed by mash- Middle East, and Central America. Its composi-
ing, possibly with addition of salt. The pulp is tion and properties are similar to those of olive
then pressed and the press oil clarified by set- oil (see Tables 1 and 2). The oil is used in cosmet-
tling or centrifuging. Open-cage presses are be- ics; in California smaller quantities of avocado
ing replaced by continuous screw expellers. The oil are used as special salad oil. The avocado
mashed pulp can also be separated in a horizon- fruit weighs up to 1.5 kg and contains 40 – 80 %
tal decanter, the crude oil being recentrifuged af- oil in dry matter. World production of avocado
ter addition of wash water. An alternative is the fruit is ca. 1.5×106 t/a, but only a small fraction
use of machines to remove the kernels from the is used for oil production.
pulp; the residue is separated in self-discharging
centrifuges.
Cold pressing, which yields vierge grades 13.2. Seed-Kernel Fats
(also referred to as virgin, Provence, or Nizza
oil), is generally followed by warm pressing at Oilseeds are the major source of oils and fats.
ca. 40 ◦ C, which gives an oil with a less delicate
flavor. The yields depend on the equipment used.
The press cake (pomace) contains 8 – 15 % of a 13.2.1. Lauric Acid Oils
relatively dark oil, called Sanza or Orujo, which Coconut, palm kernel, and babassu oil are the
can be extracted with hexane and is used for most important lauric acid oils. They contain
technical purposes; after refining it is also fit for >40 % of lauric acid and ca. 15 % of myristic
edible consumption. acid.
Olive kernel oil is obtained by pressing and
solvent extraction of cleaned kernels. It is simi-
lar to olive oil but lacks its typical flavor. 13.2.1.1. Coconut Oil [76]
Use. Cold-pressed olive oil is a valuable ed- The coconut palm (Cocos nucifera or Cocos bu-
ible oil. Trade specifications are based primar- tyracea) is cultivated in coastal areas around the
ily on the content of free fatty acids and flavor world within 20 ◦ of either side of the equator.
assessment. In some countries, warm-pressed The Philippines, Indonesia, Southern India, Sri
olive oil with a high acidity is refined by neutral- Lanka, Equatorial Africa, and the West Indies
ization, bleaching, and deodorization, and fla- are important producers. Around 1820 coconut
vored by blending with cold-pressed oil. oil [8001-31-8] was introduced to Britain (veg-
etable butter).
Testing for Adulteration. Because of its
Saponification value 250 – 262
high price, olive oil is sometimes admixed Iodine value 7 – 10
with other oils. Some oils can be detected by Nonsaponifiable matter 0.15 – 0.60 %
specific color reactions: cottonseed oil by the mp 20 – 28 ◦ C
Halphen test, sesame oil by the Baudouin re- n40
D 1.448 – 1.450

action, teaseed oil by the Fitelson test (see Ta-

ble 23). Gas chromatographic determination of For fatty acid composition see Tables 1 and 2
the fatty acid and sterol composition is gener- The glycerides contain 50 – 60 % caprylo-
ally used to quantify the degree of adulteration. lauromyristin and up to 20 % myristodilaurin
Olive-pomace oil and re-esterified olive oil, ob- in addition to smaller concentrations of lau-
tained by esterification of olive oil fatty acids or rodimyristin.
 Fats and Fatty Oils 51

Production. In plantations the coconut palm Coconut stearin, mp 27 – 32 ◦ C, and coconut

reaches a height of 30 m and from its 6th to 30th olein can be obtained by fractional crystalliza-
years annually yields 50 – 70 coconuts with a tion and pressing of prerefined coconut oil. Co-
diameter of 10 – 12 cm. The hard shell, covered conut stearin is used in couverture for confec-
by a fibrous husk, encloses the white endosperm tionery products.
tissue 1 – 2 cm thick, the copra. To obtain a light, Hydrogenated coconut oil (iodine value 2 –
flavor-stable coconut oil, the fresh copra with a 4, mp 30 – 32 ◦ C) is produced from prerefined
water content of 60 – 70 % is dried in the sun coconut oil with fresh nickel catalyst at 140 –
or with hot air. This treatment prevents bacte- 180 ◦ C. In the summer months it is often used
rial decomposition and lipolysis of the fat. Dry in admixture with unhardened coconut oil to
copra contains 60 – 67 % oil. raise the melting point of couvertures and simi-
The dried copra is processed in an oil mill in lar products.
two steps. About two-thirds of the oil is first ob- Crude coconut oil, meeting certain color
tained by expelling broken and rolled copra in specifications, is also used in the manufacture
continuous screw presses. The residual fat con- of special soaps.
tent of the expeller cake can be reduced to ca.
5 % by high-pressure expelling and to 2 – 4 % by
subsequently extracting the expeller cake with 13.2.1.2. Palm Kernel Oil [76]
hexane.
In order to obtain an edible oil of good qual- Palm kernel oil [8023-79-8] is derived from the
ity, the crude coconut oil must be neutralized, kernels of the oil palm (Elaeis guineensis) (see
bleached, and deodorized. Normally, the crude Section 13.1.1).
oil contains ca. 5 % free fatty acids but it can be Saponification value 242 – 254
lye-neutralized without great loss of neutral oil. Iodine value 16 – 19
The neutralized, washed, and dried oil contains Nonsaponifiable matter 0.2 – 0.8 %
only small amounts of pigments, phosphatides, mp 23 – 30 ◦ C
n40
D 1.449 – 1.452
and other constituents. It is decolorized with 1 –
2 % of bleaching earth and 0.1 – 0.4 % of acti-
vated charcoal. Activated charcoal also serves For fatty acid composition see Tables 1 and 2
to remove polycyclic aromatic hydrocarbons de- The properties of palm kernel fat are very
posited on the copra by drying with flue gases similar to those of coconut oil. However, it con-
[53]. Crude coconut oil with a relatively high tains more oleic acid and only half as much C8
content of free fatty acids can be advantageously and C10 fatty acids. The glycerides of palm ker-
neutralized and deodorized by distillation after nel oil consist of 60 – 65 % trisaturated, ca. 25 %
pretreatment with phosphoric acid and bleach- disaturated – monounsaturated, and 10 – 15 %
ing earth – activated charcoal. monosaturated – diunsaturated components. Its
stability is similar to that of coconut oil.
Uses. Coconut oil is used for cooking, and
is also an important component of vegetable Production. The palm nuts are separated
margarines. Because of its high latent heat of by air classifiers from the fibers of the press
fusion, it produces a pronounced cooling ef- cake obtained on pressing palm fruit (see Sec-
fect in the mouth on melting. This effect also tion 13.1.1). After drying in silo dryers, the nuts
makes it a valuable fat for biscuit filling, con- are cracked with centrifugal crackers, and the
fectionery products, and confectionery coatings shell is separated from the kernel with air and
(couvertures). Coconut oil can undergo enzy- water separation systems. The kernel, 1 – 2 cm
matic hydrolysis in foods containing relatively in size, is dried from an initial moisture content
high concentrations of water leading to so-called of 20 – 25 % to about 4 – 7 %; it then contains
perfume rancidity. This reaction can be counter- 44 – 57 % oil. Following cracking and rolling,
acted by incorporating at least 30 % sugar or by the palm kernels are passed through a screw ex-
drying. Coconut oil has a high resistance to ox- peller. The residual oil in the press cake can be
idative deterioration. further reduced by high-pressure expelling or,
more commonly, by extraction with hexane.
52 Fats and Fatty Oils

Crude palm kernel oil often has a higher Saponification value 242 – 253
free fatty acid content than coconut oil (up to Iodine value 10 – 18
15 %, calculated as oleic acid). Palm kernel oil Nonsaponifiable matter 0.2 – 0.8 %
with a free fatty acid content <5 % can be lye- mp 22 – 26 ◦ C
n40
D 1.449 – 1.451
neutralized without significant neutral oil losses.
At higher contents of free fatty acids, distillative
neutralization (possibly followed by lye post- For fatty acid composition see Tables 1 and 2
neutralization) is generally preferred. Treatment
with 1 – 2 % activated bleaching earth yields a Use. Refined babassu oil is known in South
light, yellowish oil. Deodorization generally re- America as an edible fat. In European countries
quires a longer period of time than for coconut it is used in place of palm kernel oil in margarine
oil in order to obtain a stable, bland raffinate. blends. The export of babassu kernels is only of
minor economic importance; total production is
Use. Top-grade palm kernel raffinates are likely to be around 150 000 t/a.
used in couvertures and margarines. Palm ker- Other palm seed oils are used as edible fats
nel stearin and olein are obtained by fractional in their countries of origin and do not play a role
crystallization of prerefined palm kernel oil at in international trade. Some of their properties
ca. 25 ◦ C. Palm kernel stearin, mp 30 – 32 ◦ C, are listed in Table 24. Cohune oil is obtained
is often used as such, or blended with coconut from the kernels of the cohune palm (Attalea
stearin, as a filling mass or couverture for con- cohune), a native of Mexico and Honduras. Its
fectionery products. Hydrogenated palm kernel properties are similar to those of coconut oil.
oil (mp 39 ◦ C, iodine value 1) is made in the Murumuru oil, somewhat harder than coconut
same way as hydrogenated coconut oil and is oil, is contained in the kernels of the palm Astro-
mostly used in the confectionery trade. The melt- caryum murumuru, which is found in the North-
ing point of hydrogenated palm kernel oil can be ern provinces of Brazil. It contains ca. 40 %
reduced from 39 ◦ C to 33 – 35 ◦ C by interesteri- lauric acid, 35 % myristic acid, and only little
fication. Interesterified, hydrogenated palm ker- caprylic and capric acids. Ouricuri oil, from the
nel oil increases the range of special tailor-made kernels of the Brazilian palm Syagrus coronata,
products for application in confectionery prod- has a lower melting point than murumuru oil.
ucts. It contains 45 % lauric acid and 10 % myris-
tic acid in addition to 20 % fatty acids with 6,
8, and 10 carbon atoms. The kernels of Astro-
13.2.1.3. Babassu Oil and Other Palm Seed caryum tucuma, a native of Guyana, Venezuela,
Oils and Northern Brazil, yield tucum oil.

The babassu palm (Orbygnia speciosa, Attalea

funifara) is a native of the great forest regions of 13.2.1.4. Other Sources of Lauric Acid Oils
the Brazilian states Maranhão, Piauı́, Pará, and
Minas Geraes. The number of babassu trees in Up to 43 % of lauric acid is contained in the seed
these forests is estimated at >109 . Collecting oil of the evergreen laurel tree (Laurus nobilis),
and transport of the babassu nuts to the oil mills from which the name of this acid was derived.
and removal of the extremely hard shell prior to Laurel oil contains about 30 % trilaurin; it has
expelling make it difficult to exploit this inter- no commercial importance.
esting source of lauric oil. A bunch holds 200 – The seed oils of Myristica species contain
600 fruits; 1 t of fruit yields about 125 kernels relatively high concentrations of myristic acid.
containing 63 – 70 % fat after drying to ca. 4 % Nutmeg butter [8008-45-5] is made by expelling
moisture. The fat can be isolated by expelling ground and boiled seed kernels of Myristica
and subsequent extraction with hexane. officinalis; it contains 39 – 76 % myristic acid.
Myristica otoba yields otoba fat. Ucuhuba fat is
obtained from Virola surinamensis, a native to
Brazil. Dika fat is contained in the seed kernels
of Irvingia gabonensis and I. barteri, native to
 Fats and Fatty Oils 53
Table 24. Properties and analytical data of seed oils of some South American palm varieties

Cohune oil Murumuru oil Ouricuri oil Tucum oil

◦ 3
Density (60 C), g/cm ca. 0.893 0.893 0.898 0.893
n60
D 1.441 1.445 1.440 1.443
Saponification value 251 – 257 237 – 242 ca. 257 240 – 250
Melting point, ◦ C 18 – 24 32 – 34 18 – 21 30 – 36
Iodine value 10 – 14 11 – 12 14 – 16 10 – 14
Nonsaponifiable matter, % 0.4 0.3 0.3 0.3

West Africa. None of these fats is involved in The dilatation curve (plot of solids content at dif-
international trade. ferent temperatures) is very steep (see Fig. 2).
Cuphea is a herbaceous, annual plant, native The glycerides of cocoa butter consist
to Mexico and also found in Northern Brazil roughly of 2 % trisaturated compounds, 14 %
and Nicaragua. The seed oil contains various 2-oleodipalmitin, 40 % 1-palmito-3-stearo-2-
medium-chain fatty acids which, depending on olein, 27 % 2-oleodistearin, 8 % palmitodiolein,
the species, account for 40 – 80 % of the total and 8 % stearodiolein.
fatty acids. Cuphea oil could be a substitute for
coconut and palm kernel oil and serve as a natu- Production. Cocoa butter is isolated from
ral source of capric acid; agronomic research is cocoa beans by fermentation, roasting, de-
directed toward adaptation and yield improve- hulling, grinding, and expelling (→ Chocolate,
ment of Cuphea [78]. Chap. 6.1.). The fat content of dehulled cocoa
beans is about 54 – 58 % in dry matter. In some
countries the fat obtained from nondehulled co-
13.2.2. Palmitic – Stearic Acid Oils coa beans by expelling or solvent extraction may
also be called cocoa butter.
13.2.2.1. Cocoa Butter
Use. Cocoa butter is used extensively in the
Cocoa butter is the seed fat of Theobroma cacao production of chocolate and other confectionery
L., a tree reaching a height of 9 m, which is culti- products, and to a lesser extent in the pharma-
vated in many tropical countries (→ Chocolate, ceutical and cosmetics industries.
Chap. 6.1.). The cocoa tree is grown mainly in
West Africa (Ivory Coast, Nigeria) and South Test for Adulteration. Because of its high
Africa (Brazil). The world production of cocoa price, cocoa butter is sometimes admixed with
beans is in the order of 1.3×106 t/a. press or extraction fat from damaged cocoa
Saponification value 190 – 200 beans or byproducts, animal fats, coconut oil and
Iodine value 35 – 40 stearin, palm oil and palm oil fractions, or hy-
Nonsaponifiable matter 0.2 – 0.5 % drogenated vegetable or marine oils.
mp 28 – 36 ◦ C
n40 1.453 – 1.458
Extraction cocoa butter can be identified by
D
its relatively dark color, by its strong fluores-
cence under ultraviolet light, by various color
For fatty acid composition see Tables 1 and 2 reactions, and by its behavior in simple tests such
Cocoa butter has a pleasant aromatic flavor as the “smear test” (extraction fat tends to smear
and keeps well. The cocoa butter glycerides are while authentic cocoa butter tends to disintegrate
hard and brittle up to about 28 ◦ C and melt in a into small, hard pieces). In addition, extraction
range of 4 – 5 ◦ C with a pronounced oral cool- fat has a higher content of nonsaponifiable mat-
ing effect. The melting point of cocoa butter de- ter (cocoa butter contains 0.2 – 0.5 %, extraction
pends on the type and length of tempering. After fat 1.9 – 2.8 %, fat from cocoa bean hulls about
rapidly cooling to 0 – 5 ◦ C, cocoa butter melts at 7.5 % nonsaponifiable matter) and a higher con-
26 – 30 ◦ C, whereas the melting point increases tent of linoleic acid (10 – 29 % compared to 2 –
to 32 – 35 ◦ C after tempering for 40 h at 28 ◦ C. 4 % in authentic cocoa butter).
54 Fats and Fatty Oils

Animal fats such as tallow and hydrogenated S. palembassica, and S. seminis. The propor-
fish oils can be detected by gas chromatographic tions of component fatty acids in these species
analysis of the fatty acid composition and by are very similar. The size of nut varies consid-
their cholesterol content. Hydrogenated veg- erably from one variety to another, and only
etable oils can be recognized by their content a few are worth harvesting. Borneo tallow re-
of trans fatty acids. Coconut oil and similar oils sembles cocoa butter chemically and physically
can be detected by their concentrations of C8 , more closely than any other fat. For this reason
C10 , C12 , and C14 fatty acid groups. Addition of it is used in preparing cocoa butter equivalents
cocoa butter-like fats such as fractions of Bor- or extenders.
neo tallow, illipé fat, shea butter, and palm oil Sal butter is derived from Shorea robusta,
can sometimes be detected by their concentra- commonly known as the sal tree, found exten-
tion of terpene alcohols. Gas chromatographic sively in parts of Northern and Central India.
analysis of chocolate fat triglycerides can de- Illipé fat is derived from the group of Madhuca
tect so-called cocoa butter equivalents in cocoa seed fats (also known as Bassia seed fat) and
butter and certain types of chocolate; this tech- is itself produced from the Indian plant Mad-
nique can be augmented by analyzing the fatty huca longifolia. Another Indian plant, Madhuca
acid composition at the 2-position [79]. latifolia, is the source of mowrah fat which is
very similar in composition. Illipé and mowrah
fats contain sufficient unsaturated fatty acids to
13.2.2.2. Shea Butter, Borneo Tallow, and make them resemble shea butter rather than the
Related Fats (Vegetable Butters) firmer cocoa butter and Borneo tallow. Illipé and
mowrah fats are used principally in Asia for
Shea butter, also known as Karité butter or technical purposes but also for edible purposes
Galam butter, is obtained from the seeds of a tree when fully refined. Both fats are used to pre-
growing mainly in West Africa (Butyrospermum pare cocoa butter extenders. Katiau fat is derived
parkii). Plantations tend to be uneconomic since from the plant Madhuca mottleyana, and phul-
shea nuts can be harvested only after the tree is wara butter (Indian butter) from M. butyracea.
about 15 years old. For properties of the various vegetable butters
Shea butter is similar to cocoa butter (see Ta- see Table 25 [80].
ble 25). The content of nonsaponifiable matter,
which contains rubber-like hydrocarbons such
as kariten [(C3 H8 )n , mp 63 ◦ C], can be as much 13.2.3. Palmitic Acid Oils
as 11 %.
The kernels can be readily separated from the The oils in this group have a relatively high con-
fruit and the thin hulls. In Africa they are ground, tent of palmitic acid, mostly above 10 %. Cot-
boiled, and the fat is skimmed off. The commer- tonseed oil and some cereal oils are the most
cial production of shea butter by expelling in important representatives.
continuous screw presses is difficult and requires
special processing conditions. The green-brown
crude fat can be neutralized only with consider- 13.2.3.1. Cottonseed Oil
able loss of neutral oil.
Refined shea butter can be used as an Cottonseed oil [8001-29-4] is obtained from the
edible fat. The stearin fraction, primarily 2- seeds of different varieties of cotton (Gossyp-
oleodistearin, which can be obtained by crys- ium). The most important producers are the
tallization and removal of the liquid fraction, United States, the former Soviet Union, China,
is a valuable cocoa butter substitute. The ex- Pakistan, Brazil, Egypt, and India. Gossypium
port quantities (from Nigeria, Dahomey, Upper barbadense and G. hirsutum are preferred in the
Volta) amount to ca. 50 000 t/a. United States, while G. herbaceum is native to
Borneo tallow ( tengkawang tallow) is de- the Asian countries. The United States produce
rived from Shorea stenoptera, a plant growing about one-third of the world’s cottonseed oil (see
in the East Indies and Malaysia; there are about also → Cellulose, Chap. 2.1.).
100 different species including S. gysbertsiana,
 Fats and Fatty Oils 55
Table 25. Properties and analytical data of some vegetable butters

Shea butter Borneo Sal butter Illipé butter Mowrah Katiau fat Phulwara
tallow butter butter

Myristic acid, % ca. 15

Palmitic acid, % 5–6 18 – 22 8–9 ca. 28 16 – 27 ca. 10 54 – 57
Stearic acid, % 36 – 42 39 – 44 ca. 35 ca. 14 ca. 20 ca. 19 ca. 4
Arachidic acid, % ca. 1 ca. 12
Oleic acid, % 49 – 50 38 – 42 ca. 42 ca. 50 41 – 66 ca. 69 ca. 36
Linoleic acid, % 4–5 traces ca. 3 8–9 9 – 14 2–3 3–4
Saponification value 178 – 196 189 – 200 186 – 200 187 – 195 189 – 192 188 – 200
Iodine value 55 – 67 29 – 38 50 – 60 58 – 63 53 – 67 40 – 51
mp, ◦ C 32 – 42 34 – 39 25 – 29 23 – 31 30 38 – 43
n40
D 1.4635 – 1.4561 – 1.459 – 1.458 – 1.461 – 1.455 –
1.4668 1.4573 1.462 1.461 1.462 1.458
Nonsaponifiable matter, % 2 – 11 <2 1.4 – 2.3 1.2 – 2.1 0.4 – 0.5 2 – 2.8
Fat content in seed 45 – 55 20 50 50 60 – 65
kernel, %

Saponification value 190 – 198

because of dissolved resins and pigments, and
Iodine value 100 – 117 must therefore be refined before further use. The
Nonsaponifiable matter 0.5 – 1.5 % crude oil is first clarified by settling or centrifug-
mp ca. 0 ◦ C ing and then neutralized with lye, mostly in con-
n40
D 1.464 – 1.468
tinuous centrifuge lines. The neutralized oil is
free of gossypol, light yellow, stable during stor-
For fatty acid composition see Tables 1 and 2 age, and is usually traded in this form. A very
The oil contains 0.4 – 0.6 % of malvalic acid, stable oil can be obtained by postneutralization,
which presumably is the basis of the Halphen bleaching, and deodorization. Stearin separates
color reaction. The glycerides of cottonseed out at temperatures between 0 and 8 ◦ C. An oil
oil consist of approximately 12 – 14 % dis- with a low cloud point is obtained by removing
aturated – monounsaturated, 52 – 58 % mono- these solid glycerides by cooling and filtration
saturated – diunsaturated, and 25 – 30 % triun- (winterization).
saturated compounds.
Use. Winterized cottonseed oil is a very sta-
Production. Egyptian cottonseed (not de- ble salad oil. Cottonseed oil is also used in mar-
hulled) contains 22 – 24 % oil, the American garine blends without being winterized. Lard-
varieties on average 19.5 %. About 50 cotton- like fats for use in margarine blends and shorten-
seeds are contained in a pod, which opens ings are obtained by hydrogenation under iomer-
when it is ripe. After removal of the cotton, the izing conditions. Such fats have a melting point
seeds are still covered with fine hairs ( linters), between 30 and 35 ◦ C and an iodine value of 60 –
which are removed with delintering machines 80. Cottonseed oil hardened to a melting point of
that essentially consist of rotating sawtooth discs 36 – 37 ◦ C is suitable as a couverture fat for con-
[81]. The seeds are then dehulled by passage fectionery products. The characteristic Halphen
through “dehullers” (essentially rotating knives) color reaction disappears on hydrogenating the
and screens – air classifiers. The dehulled seeds oil.
(30 – 40 % oil content) are expelled in contin-
uous screw presses and the expeller residue is
extracted with solvent. 13.2.3.2. Kapok and Related Oils
Gossypol is present in the seed in concen-
trations of 0.4 – 2.0 %. However, only traces are Kapok oil is derived from the fruit of a tree be-
detectable in the crude oil, because gossypol is longing to the Bombaceae family that grows in
partially deactivated (presumably by interaction Indonesia, Sri Lanka, the Philippines, and South
with protein) during conditioning and expelling America.
the seed. Crude cottonseed oil has a dark color
56 Fats and Fatty Oils

The seeds in the fruit pods are covered with Properties. Winterized corn oil becomes
fine hairs (kapok), which are used in upholster- cloudy at about −10 ◦ C.
ing and contain ca. 25 % oil. Crude kapok oil,
Saponification value 187 – 196
produced by preexpelling and solvent extraction, Iodine value 109 – 133
has a reddish-brown color and is similar to cot- Nonsaponifiable matter 1.3 – 2.0 %
tonseed oil in composition and further process- n40
D 1.465 – 1.466
ing. It contains little or no gossypol. Kapok oil
contains ca. 15 % of a C18 cyclopropenoic acid For fatty acid composition see Tables 1 and 2
and therefore responds strongly to the Halphen Corn oil glycerides consist of ca. 2 % disatu-
reaction. rated – monounsaturated, 40 % monosaturated –
Okra oil is obtained from the seeds of Hi- diunsaturated, and 58 % triunsaturated com-
biscus esculentis, a family related to Gossyp- pounds.
ium and found in the United States and some
Mediterranean countries. Kenafseed oil is con- Production. Corn contains 3.5 – 5 % oil,
tained in the seeds of Hibiscus canabinus, a plant about 80 % of which is in the germ and about
native to India where it is grown for its fibers. 20 % in the endosperm. The corn germ itself
The properties of kapok, okra, and kenafseed contains about 36 % oil. The germs can be sep-
oils are listed in Table 26. arated by wet or dry processing. Wet processing
tends to be preferred because it gives a higher
oil yield. The cleaned corn is first conditioned
13.2.3.3. Pumpkin Seed Oil by soaking in warm water and is then milled
and slurried with water. The germs are collected
Pumpkin seed oil is popular as a high- by flotation, washed, and dried. In dry process-
quality, edible oil in Southeast Europe. It is ing, the ground corn is separated into germ and
obtained from carefully decorticated pumpkin endosperm fractions by screening and air clas-
seeds by grinding, conditioning the moistened sification; suitable moistening and conditioning
ground seeds, expelling in hydraulic presses, facilitate this fractionation. The oil is isolated
and clarification by settling in special tanks, from the germs by preexpelling followed by ex-
mostly on smaller locations. It has a reddish- traction with hexane.
brown color and a nutty taste. Refining yields an The golden yellow, crude corn oil contains
oil with properties similar to those of sunflower up to 3 % free fatty acids. After lye neutral-
oil. ization, bleaching, and deodorization it yields
Saponifaction value 185 – 198 a light, highly stable oil. The content of toco-
Iodine value 117 – 130 pherols, predominantly γ-tocopherol, is nearly
Nonsaponifiable matter 0.6 – 1.5 % 1000 ppm. Salad oils that remain clear at refrig-
Solidification point ca. −15 ◦ C
n40
D 1.466 – 1.469 erator temperatures are obtained by winteriza-
tion, during which about 500 ppm wax is re-
moved.
For fatty acid composition see Tables 1 and 2
Melon seed oil is very similar in composi-
Use. Corn oil is a universal oil; it is used es-
tion to pumpkin seed oil [82], the major fatty
pecially as a salad oil and in salad dressings.
acids being palmitic (ca. 12 %), stearic (ca.
11 %), oleic (ca. 11 %), and linoleic (ca. 65 %).
13.2.3.5. Cereal Oils
13.2.3.4. Corn (Maize) Oil
Oils are generally not extracted from cereal
grains except rice and wheat. The cereal oils
Corn oil (maize oil) [8001-30-7] is obtained
are, however, very important as constituents of
from the germ removed during the processing
bread, other bakery products, and animal feeds.
of corn (Zea mays L.) into starch.
Wheat germ oil is extracted from the wheat
germ (8 – 11 % oil) obtained as a byproduct of
 Fats and Fatty Oils 57
Table 26. Properties of kapok, okra, and kenafseed oils

Kapok oil Okra oil Kenafseed oil

Myristic acid, % ca. 0.5 0–4

Palmitic acid, % 10 – 16 23 – 33 ca. 14
Stearic acid, % 3–8 0.5 ca. 6
Arachidic acid, % ca. 1 traces
Oleic acid, % ca. 50∗ 26 – 42 ca. 45
Linoleic acid, % ca. 30 30 – 40 ca. 23
n40
D 1.464 – 1.468 1.462 – 1.467 1.465 – 1.466
Saponification value 189 – 197 192 – 199 189 – 195
Iodine value 86 – 110 90 – 100 93 – 105
Nonsaponifiable matter, % 0.5 – 1.8 0.7 – 1.4 0.4 – 3.4

∗ Including 15 % malvalic acid.

milling wheat. It has a very high tocopherol con- Some of these oils, such as hazelnut oil, poppy-
tent and is therefore popular as a dietetic oil. seed oil, walnut oil, and teaseed oil, only have re-
gional significance, while sunflower oil, sesame
Saponification value 180 – 189
Iodine value 115 – 126
oil, linseed oil, and safflower oil have consider-
Nonsaponifiable matter 3.5 – 6.0 % able commercial importance.
mp ca. 0 ◦ C
n40
D 1.468 – 1.478

13.2.4.1. Sunflower Oil

For fatty acid composition see Tables 1 and 2
Rice bran oil [68553-81-1] is an important Sunflower oil [8001-21-6] is the seed oil of the
byproduct of rice processing. It is obtained by sunflower, Helianthus annuus, that originated
hexane extraction of the bran (brown outer coat- in America and is now grown extensively in
ing) and the germ (8 – 16 % oil content) removed East, West, and South Europe, the United States,
during grinding, dehulling, and polishing rice. Canada, South America, China, India, South
The bran fraction must be extracted immedi- Africa, and Australia. The annual plant reaches
ately, preferably after heat-sterilization, to de- a height of 1 – 3 m, the short-stem varieties be-
stroy the very active lipases. Refined rice bran oil ing preferred for ease of harvesting. The air-dry
has a light yellow color and is a relatively stable seeds contain about 45 % oil.
edible oil. Rice bran oil hardened to 30 – 35 ◦ C
is often used in margarines and shortenings. In Properties. Sunflower oil begins to solidify
Japan and India ca. 100 000 t of rice bran oil are at −16 ◦ C; the cloud point is 0 – 5 ◦ C.
produced annually.
Saponification value 188 – 194
Saponification value 183 – 194 Iodine value 125 – 144
Iodine value 92 – 109 Nonsaponifiable matter 0.4 – 1.4 %
Nonsaponifiable matter 3.5 – 5.0 % n40
D 1.466 – 1.468
(including ca. 330 mg squalene per 100 g oil)
mp ca. −10 ◦ C
40
nD 1.466 – 1.469 For fatty acid composition see Tables 1 and 2
The linoleic acid content of sunflower oil is
50 – 70 % and tends to increase with decreas-
For fatty acid composition see Tables 1 and 2
ing temperatures during growing [83]. The glyc-
erides contain 35 – 45 % diunsaturated and 56 –
13.2.4. Oleic – Linoleic Acid Oils 63 % triunsaturated compounds. Linolenic acid
is present to the extent of <0.4 %.
This group encompasses a large number of dry-
ing and semidrying oils derived from plants Production and Use. Sunflower oil is ob-
growing in temperate and colder regions (see tained by preexpelling followed by extraction of
also → Drying Oils and Related Products). the expeller cake with hexane. Decortication is
58 Fats and Fatty Oils

practiced to a lesser degree; the hulls have to be Crude sesame oil is yellowish and contains up
burnt. The crude oil can be readily refined into a to 3 % free fatty acids. The glycerides contain
light, stable oil by lye neutralization, bleaching, about 66 % dioleolinolein and oleodilinolein.
and deodorization. Refined oil has a high stability due in part to
Cold-pressed sunflower oil is produced by the content of sesamol, a natural antioxidant
expelling at ≤ 80 ◦ C; posttreatment is limited formed by hydrolysis of sesamolin. The com-
to filtration and clarification. Such a “natural” bined concentration of sesamol and sesamolin
oil is often recommended for dietetic purposes is 0.1 – 0.2 %. Sesamol gives a red color with an
because of its relatively high concentration of ethanolic solution of furfural in the presence of
phosphatides. Trace contaminants such as met- hydrochloric acid (color reaction of Baudouin
als and pesticide residues, however, remain in and Villavechia); it also responds positively in
the oil. Refined sunflower oil is used extensively color tests with an acidic solution of stannous
in salad oils and margarine blends because of chloride (Soltsien test), and with 3 % hydrogen
its oxidative stability. Winterization (removal of peroxide – 75 % sulfuric acid (Kreis test).
500 – 2000 ppm of wax) of the deodorized or
the neutralized and bleached oil at 10 – 15 ◦ C Use. Sesame oil is widely used as an edible
yields an oil which does not cloud at refriger- oil in the countries of origin. A small amount is
ator temperatures. Sunflower oil that is hydro- exported for use in salad oils, salad dressings,
genated to a melting point of 32 – 35 ◦ C (iodine and margarines. The addition of sesame oil to
value 70 – 75), under isomerizing conditions, is margarine is mandatory in some countries to pro-
widely used in “one-oil” margarine blends. vide a rapid means of identifying margarine by
Smaller quantities of a new sunflower variety the above color reactions; for this application the
are being grown in California; these plants yield oil may only be lightly bleached and deodorized
an oil with an oleic acid content of about 80 % at 150 ◦ C.
and hence a very high oxidative stability. This oil
is recommended especially for salad and frying
13.2.4.3. Linseed Oil
oils [84].
Linseed oil [8001-26-1] is obtained from linseed
or flax (Linum usitatissimum), which grows best
13.2.4.2. Sesame Oil in the temperate regions of Europe, Asia, and
America. The flax fiber plant is a different va-
Sesame oil [8008-74-0] is contained in the seeds riety of the same species. There is considerable
of Sesamum indicum, a plant resembling linseed variation in the iodine value of linseed oil from
and grown mainly in China, India, Africa, and different regions. The iodine value of the oil
Mexico. The flat seeds are 2 – 3 mm long and tends to increase with severity of climate, but ge-
vary in color from white to brown-black; the netic and seasonal (e.g., rainfall) variations also
oil content is 45 – 55 %. Harvesting is relatively have an influence [85]. While 180 – 185 is a typ-
difficult because of varying rates of ripening and ical iodine value range for individual lots, it may
the ripe seed pods shattering the seed. More uni- vary from 140 to 205.
form varieties with improved harvesting proper- The main producer countries are Canada, the
ties are being developed. United States, and Argentina. The brown, flat
seeds contain ca. 40 % oil and 6 – 8 % water.
Properties. Sesame oil solidifies at −6 to
−3 ◦ C. Properties. Fatty acid composition and other
properties of linseed oil are given in Table 27
Saponification value 187 – 193
Iodine value 136 – 138
(see also Tables 1 and 2). Most applications re-
Nonsaponifiable matter 0.9 – 2.3 % quire a linseed oil with a linolenic acid con-
n40
D 1.4665 – 1.4675 tent of about 50 % and an iodine value of 170 –
190 [86], [87]. Linseed oil glycerides consist of
For fatty acid composition see Tables 1 and about 5 % disaturated – monounsaturated, 43 %
2. monosaturated – diunsaturated, and 52 % triun-
saturated glycerides, which begin to solidify at
 Fats and Fatty Oils 59
Table 27. Fatty acid composition and analytical data of vegetable oils of the oleic – linoleic group

Linseed oil Perilla oil Hempseed oil

Myristic acid, % ca. 0.5

Palmitic acid, % 5–7 7–8 ca. 6
Stearic acid, % 3–5 traces ca. 2
Arachidic acid, % ca. 6 ca. 2
Lignoceric acid, % traces
Oleic acid, % 16 – 26 ca. 8 6 – 20
Linoleic acid, % 14 – 24 ca. 38 46 – 70
Linolenic acid, % 50 – 65 44 – 50 14 – 28
Saponification value 188 – 196 188 – 196 190 – 194
Iodine value 170 – 204 170 – 204 140 – 170
Solidification point, ◦ C 10 – 21 12 – 17 15 – 17
n25
D 1.4786 – 1.4815 1.4800 – 1.4820
Nonsaponifiable matter, % ca. 1.5 <1.5 <1.5

−18 to −27 ◦ C. Most of the glycerides contain oil to 260 – 285 ◦ C increases its viscosity and
an average of seven double bonds per molecule, gives a so-called “boiled” linseed oil, which is
which is the reason for the excellent drying prop- used in special paints and coatings.
erties of linseed oil (→ Drying Oils and Re-
lated Products). The use of linseed oil for ed-
ible purposes is limited to smaller quantities 13.2.4.4. Perilla Oil
of cold-pressed oil (for dietetic purposes) and
to hydrogenated linseed oil, which can be used The seeds of Perilla ocymoides, an Asian plant,
in low concentrations in shortenings, and mar- yield perilla oil (30 – 50 %), which resembles
garine blends. linseed oil in appearance and application. For
Some wild linseed varieties (e.g., Linum capi- properties see Table 27. World production is
tatum and L. flavum) have linolenic acid contents about 25 000 t/a. Perilla oil is sometimes blended
as low as 11 %. Modern biotechnological tech- with linseed oil; in Asia it is also used as an ed-
niques are being used in Australia and Canada in ible oil .
an attempt to transfer this property to L. usitatis- Lallemantia oil (Asia) and Chia seed oil
sium. An alternative approach is γ-ray induced (Mexico) are further Labiatae seed oils with sim-
mutation of L. usitatissimum. ilar compositions.

Production. Linseed oil is obtained from the

13.2.4.5. Hempseed Oil
seed by preexpelling followed by hexane extrac-
tion of the press cake. After refining it is used The seeds of hemp (Cannabis sativa L.) con-
predominantly in the technical sector for paints tain 30 – 35 % oil. Hempseed is grown in the
and coatings. A small amount is used in East Eu- Soviet Union, India, China, Japan, and Chile,
ropean countries as edible oil. Linseed oil has a and yields fibers in addition to the oil. Hashish
characteristic odor and flavor which cannot be can also be obtained from Indian hempseed va-
removed entirely by refining. The crude oil is rieties. Hempseed itself can be used as a food-
rich in phosphatides and gums which sediment stuff. The oil is normally produced by pressing
on storage. The crude oil is often pre-deslimed the seed. For properties see Table 27. Hempseed
by treatment with hot water followed by cen- oil has been largely replaced by linseed oil for
trifugation. Oils virtually free of phosphatides technical purposes.
and gums are made by post-desliming with sul-
furic or phosphoric acid. Very light drying oils
can be made by a further posttreatment consist- 13.2.4.6. Teaseed Oil
ing of lye neutralization and earth bleaching. To
obtain virtually odorless oils, deodorization is Teaseed oils are obtained in China, Japan, In-
required as a final step. Heating refined linseed dia, and Turkey from the hazelnut-like seeds of
60 Fats and Fatty Oils

tea shrub varieties, which contain about 60 % oil. and 15 % respectively (“high oleic” varieties)
Tea shrubs grown for oil are generally not suited were developed and recommended as especially
for tea-leaf harvesting. Teaseed oil is produced stable frying oils. World production amounts to
primarily from the seeds of Thea sasanqua n. about 200 000 t/a.
(sasanqua oil) and Thea japonica n. (tsubaki oil) Niger seed oil, closely resembling safflower
by drying, grinding, conditioning, and pressing oil in its composition, is derived from the seed
or solvent extraction. After refining the oil is of the gingli plant, which is grown fairly exten-
used for edible purposes, as a special lubricant, sively in Ethiopia, Togo, and India.
and for toiletries.
The principal acids of teaseed oils [88] are
palmitic (ca. 16 %), oleic (ca. 60 %), and linoleic 13.2.4.8. Grape-Seed Oil
acid (ca. 22 %). Teaseed oils can be detected in
concentrations above 10 % in olive oil by the Fi- Grape-seed oil [60-33-3] is a valuable oil ob-
telson color reaction. The expeller cake and ex- tained from the grapeseed left in winery pomace
traction meal cannot be used as such in animal [89]. The oil content averages 15 % (dry weight
feeds because of their high saponin contents. To- basis).
tal world production is ca. 30 000 t, half of which
is exported. Properties. The flavor of grape-seed oil re-
sembles that of olive oil; however, its fatty acid
composition is similar to that of sunflower oil
13.2.4.7. Safflower and Niger Seed Oils (see Tables 1, 2).

Safflower oil [8001-23-8] is the seed oil of Saponification value 180 – 196
Iodine value 124 – 143
the thistle-like safflower plant (Carthamus tinc- Nonsaponifiable matter 0.3 – 1.6 %
torius), thriving in the West of the United States Solidification point −10 to −20 ◦ C
and in Mexico, North Africa, and India. The n40
D 1.464 – 1.471
plant can be grown under fairly arid conditions,
the oil yield increasing with available moisture
in the soil. The seeds resemble small sunflow- Use. After suitable refining (removal of
erseed kernels and can be harvested mechani- chlorophyll can be difficult), grape-seed oil
cally. The oil content of the seed is 25 – 37 %. keeps relatively well and is used as a salad and
Saponification value 180 – 194
cooking oil and in special margarine blends. In
Iodine value 136 – 152 France and Italy, 5000 t and 20 000 t, respec-
Nonsaponifiable matter 0.3 – 2.0 % tively, of grape-seed oil are produced annually.
Solidification point −13 to −25 ◦ C It has been estimated that the world production
n40
of grape seed is 1.4×106 t, with a potential oil
D 1.467 – 1.469

yield of about 190 000 t [82].

The fatty acid composition is similar to that 13.2.4.9. Poppyseed Oil

of sunflower oil (see Tables 1 and 2).
Poppyseed oil is obtained from the seeds of
Production. Modern processing involves different varieties of Papaver somniferum. The
grinding the seed followed by conditioning, ex- oil content of air-dry seeds is 44 – 50 %. Cold-
pelling, and hexane extraction of the expeller pressed oil is suitable for edible purposes, as
cake. is preexpelled and extracted oil after refining.
Poppyseed oil is also used in smaller quantities
Use. Safflower oil has a high oxidative stabil- for superior oil paints. The major fatty acids are
ity and is being used increasingly in salad oils stearic (ca. 10 %), oleic (ca. 16 %), and linoleic
and dietetic margarines because of its high con- acid (70 – 75 %).
tent of linoleic acid. Some years ago special vari-
eties with oleic and linoleic acid contents of 80 %
 Fats and Fatty Oils 61

Saponification value ca. 193

For fatty acid composition see Tables 1 and2.
Iodine value ca. 140 The oil contains 40 – 60 % triunsaturated,
n40
D ca. 1.468 30 – 35 % diunsaturated, and up to 5 % monoun-
saturated glycerides. In spite of the high toco-
pherol content (up to 1200 ppm) the stability of
The world production of poppy seed amounts the refined oil is limited, primarily because of
to about 25 000 t/a. the content of linolenic acid. Autoxidation leads
to “green”, “seedy” off-flavors. Soybean oil can
be detected in other oils by its fatty acid, toco-
13.2.5. Leguminous Oils pherol, and sterol contents.

The commercially most important repre- Production. Soybeans are normally cracked
sentatives of this group are peanut oil and soy- and flaked prior to extraction with hexane. Pre-
bean oil. Soybean oil [8001-22-7] holds first expelling is not normally performed. Soybean
place in the worldwide production of vegetable meal is a valuable animal feed. Crude soybean
oils. oil contains 0.5 – 1.0 % free fatty acids as well
as up to 2.5 % phosphatides, which are removed
by hydration with 2 – 3 % water at 70 – 80 ◦ C
13.2.5.1. Soybean Oil followed by centrifuging. Drying of the result-
ing lecithin sludge yields lecithin. Soybean oil
The cultivation of the soybean (Glycine max- is often postdegummed with phosphoric or cit-
ima) in the United States and South America ric acid prior to neutralization with lye, earth
has steadily increased. The soybean has been bleaching, and deodorization.
known in China for 5000 years. Main produc- The yield of lecithin can be increased by
ing countries today are the United States, Brazil, steam-heating the flakes prior to extraction [39].
and Argentina. Cultivation in the temperate re- With the aid of special degumming techniques
gions of Europe is possible but the hectare re- [44], the phosphorus content of the crude oil
turns are generally not sufficiently attractive. can be reduced to 20 ppm, which facilitates sub-
New, higher-yielding varieties are constantly be- sequent physical refining (i.e., direct treatment
ing developed; in the United States they thrive with acids and earth followed by combined strip-
best in the “corn-belt,” i.e., Illinois, Minnesota, ping of free fatty acids and deodorization).
Iowa, Indiana, Ohio, and Missouri.
The soy pods contain up to four soybeans (5 – Use. Soybean oil is used in almost all fatty
10 mm in length). The oil content varies between products, from salad oils to margarines. Hydro-
17 and 22 % and the protein content reaches 40 – genation with fresh catalyst at ca. 100 ◦ C yields
45 % in dry matter. Climatic conditions have a liquid oil with significantly improved stability
a considerable influence on the oil and protein due to hydrogenation of linolenic acid. Hydro-
content; late sowing and a cool, wet climate tend genation under isomerizing conditions to melt-
to lower the oil content and to increase the pro- ing points ranging from 36 to 43 ◦ C yields prod-
tein content. Development of low linolenic soy- ucts for use in shortenings and margarines. Liq-
beans in the United States has been hindered by uid soybean oil is a so-called semidrying oil; it
lower seed productivity. is used in combination with tung oil and as a
component of alkyd resins for coatings.
Properties. Refined soybean oil has a light
yellow color and a bland flavor.
13.2.5.2. Peanut Oil
Saponification value 188 – 195
Iodine value 120 – 136
Nonsaponifiable matter 0.5 – 1.5 % Peanut oil ( groundnut oil) [8002-03-7] is ob-
Solidification point −15 to −8 ◦ C tained from the seed kernels of the peanut plant
n40
D 1.465 – 1.469 (Arachis hypogaea), native to South America.
The peanut is now being grown in China, In-
dia, South Africa, West Africa, Argentina, and
62 Fats and Fatty Oils

the United States. Senegal and Nigeria are the erides containing C20 – C24 fatty acid groups.
main African export countries. The annual plant The glycerides can be removed by filtration but
thrives best on light, sandy soils and reaches only with a low yield of clarified oil.
maturity in 4 – 5 months. Peanuts for further Peanut butter is made by grinding specially
processing are mostly shipped after shelling, roasted peanuts and homogenizing the mash
whereas peanuts for direct consumption are nor- with addition of liquid and possibly also hydro-
mally exported in the pods. Peanuts are often genated peanut oil.
designated according to their shipping ports,
e.g., Bombay, Casamance, Rufisque, Bissao
nuts. 13.2.5.3. Lupine Oil

Properties. The iodine value of peanut oil is Lupins are attracting attention worldwide as an
84 – 105; Rufisque oil has an iodine value of 84 – arable crop for possible use in foods and feeds.
90 and Argentinian oil a value of 100 – 105 in Lupinus albus, L. angustifolius, L. luteus, and
line with the higher content of linoleic acid. The L. mutabilis are potential sources of edible oil.
saponification value is 185 – 196, n40 D 1.461 – Whereas the first three species (sweet varieties)
1.465. Tocopherols and other antioxidants as contain only 4 – 9 % oil in the dried seed, the
well as hydrocarbons and sterols are found in seed oil content of L. mutabilis approaches that
the nonsaponifiable matter (0.5 – 1.0 %). The oil of soybeans. The main fatty acid components
solidifies below 0 ◦ C. For fatty acid composition are palmitic (7 – 13 %), stearic (2 – 7 %), oleic
see Tables 1 and 2. The oil contains 36 – 46 % (27 –53 %), linoleic (18 – 47 %), linolenic (2 –
triunsaturated, 47 – 52 % diunsaturated, and 7 – 9 %); lower concentrations of C20 – C22 fatty
11 % monounsaturated glycerides. acids are found [90]. The meal of L. mutabilis
(bitter lupins) cannot be used as an animal feed
Production. The peanut pods contain up to without prior extraction of the alkaloids.
four hazelnut-sized kernels which are covered
with a thin, reddish-brown skin and contain 5 –
12 % water, 45 – 50 % oil, and 23 – 35 % pro- 13.2.6. Cruciferous Oils
tein. The pods are first removed by passage
through cracking rolls or disk mills and over The seed oils of the traditional cruciferous plants
screens. This step also loosens the skins, which are mainly characterized by their content of glu-
are removed by aspiration. The kernels are cosinolates (sulfur-containing glycosides) and
then screened, cracked, and expelled in screw erucic acid. Rapeseed oil is the most important
presses. The residual oil in the expelled cake cruciferous oil.
is extracted with hexane. Crude peanut oil con-
tains low concentrations of phosphatides and
up to 1.5 % free fatty acids. Lye neutralization, 13.2.6.1. Rapeseed Oil [91]
earth bleaching, and deodorization yield a light,
slightly yellowish oil with a very good oxida- Rapeseed oil [8002-13-9] is the seed oil of
tive and flavor stability. Peanut kernels to be different varieties of Brassica napus and B.
processed into oil and meal can contain up to campestris. The air-dry seed contains about
0.5 ppm of aflatoxins. The bulk of the aflatoxins 40 % oil and 7 – 9 % water. The production of
remain in the meal where they can be deactivated rapeseed, one of the oldest oil crops known, has
by treatment with, for example, ammonia; traces increased dramatically over the past 10 years.
of aflatoxin that might enter the oil are removed The introduction of so-called single-zero rape-
during neutralization with lye. seed varieties, i.e., varieties with an erucic acid
content of less than 5 % of the total fatty acids,
Use. Peanut oil is used as a superior salad and has made rapeseed oil universally applicable as
cooking oil, less so in margarines. In shortenings an edible oil. Generally, it can be used to re-
it is used as such or after hardening (mp 31 – place soybean oil. Whereas single-zero, spring-
38 ◦ C). On cooling to 6 – 8 ◦ C, peanut oil be- sown rapeseed varieties are grown in Canada, the
comes cloudy due to the crystallization of glyc- EEC countries (with the exception of Denmark)
 Fats and Fatty Oils 63

generally prefer winterhardy single-zero vari- and impair the nutritional properties of the meal
eties because of the higher crop yields. Within [92]. The enzyme responsible for glucosinolate
the European Community the traditional rape- degradation, myrosinase, is destroyed by ade-
seed varieties with up to 50 % erucic acid in quate cooking of the seed prior to expelling. Sul-
the oil are now Within the European Commu- fur compounds are removed from the oil during
nity only single-zero varieties are eligible for refining; residual traces can affect the course of
subsidy, and the United States has recently per- hardening since they act as catalyst poisons. The
mitted the use of rapeseed oil with max. 2 % residual sulfur compounds in the extracted meal
erucic acid. Whereas single-zero, spring-sown can be deactivated by treatment with alkali and
rapeseed varieties are grown in Canada, the EEC heating.
countries (with the exception of Denmark) gen-
erally prefer winterhardy single-zero varieties Use. Traditional rapeseed oil containing up
because of the higher crop yielused only for tech- to 50 % erucic acid can be hardened into steep-
nical and specialty purposes. melting products, mp 32 – 34 ◦ C, suitable as par-
The increase in planted acreage has led to tial coconut oil substitutes in shortenings and
greater availability and to processing through- couvertures. Modern single-zero varieties are
out the year; a significant improvement of the used as such, after mild hardening (which elimi-
quality of the meal and the oil has been achieved nates the linolenic acid), and after hardening un-
[92]. Canada, the European Community, Poland, der isomerizing conditions to raise the melting
Sweden, China, India, and Pakistan are the point to 30 – 43 ◦ C. The reduced complexity in
main producing countries. To facilitate the mar- fatty acid composition of the hardened oil leads
ketability of meal, double-low varieties, i.e., low to a different crystallization behavior, which can
in erucic acid and glucosinolates, are grown in be overcome by interesterification. Treatment of
Canada (spring-type) and are being introduced rapeseed oil with sulfur or sulfur compounds is
in the EEC (winter-type). The winter-sown va- the basis of mastic production.
rieties are larger in size and generally easier to
process than the smaller spring-sown varieties.
13.2.6.2. Mustard Seed Oil
Properties [92]. For fatty acid compositions
see Tables 1 and 2. Analytical data such as iodine Mustard seed oil [8007-40-7] is derived from
value and saponification value are functions of the seeds of black mustard (Brassica nigra
the erucic acid content. The high level of erucic or Sinapis nigra), brown mustard (Brassica
acid in traditional rapeseed oil has been associ- juncea), and white mustard (Brassica alba or
ated with irreversible organ changes in animal Sinapis alba). The seeds contain 30–35 % oil and
tests [92]. high levels of glucosinolates. The erucic acid
content of the oil is 40 – 50 %; it is therefore of
Production. Modern rapeseed processing interest primarily for technical applications.
entails flaking and cooking the seed prior to pre-
expelling in continuous screw presses; the press
cake is extracted with hexane. Crude rapeseed 13.2.7. Conjugated Acid Oils
oil contains up to 2 % free fatty acids and ca.
2.5 % phosphatides; it is degummed with water 13.2.7.1. Tung Oil and Related Oils
or acids, lye-neutralized, bleached with earth,
and deodorized, analogously to soybean oil. The Tung oil [8001-20-5] is obtained from the ker-
stability is also comparable. The phosphatide nels (oil content about 50 %) of the fruit of the
content of the crude oil can be reduced to 0.1 % tung tree, Aleuritis fordii (Chinese tung oil) or
(i.e., 20 ppm phosphorus) by special degumming Aleuritis cordata, syn. vernica and verrucosa
techniques [44], which enable physical refining (Japanese tung oil). The oil from Aleuritis mon-
to be carried out. tana is almost identical in composition. Oils sim-
The enzymatic degradation products of ilar to Chinese tung oil are obtained from the nuts
sulfur-containing glycosides (glucosinolates) in of Aleuritis trisperma (kekuna oil) and A. moluc-
rapeseed can influence the taste of the crude oil cana or A. triloba (lumbang oil). Tung trees
64 Fats and Fatty Oils

are cultivated in Southern China, Southern Rus- Properties. The fatty acids of castor oil con-
sia, the Southern United States, and Argentina. sist of 87 – 91 % ricinoleic acid, 2 % stearic and
Tung oil contains about 80 % α-eleostearic, 4 % palmitic acid, 4 – 5 % oleic acid, 4 – 5 % linoleic
linoleic, 3 % linolenic, 8 % oleic, 1 % stearic, acid, and 1 % dihydroxystearic acid. Pure cas-
and 4 % palmitic acid. For properties, produc- tor oil can be readily identified by its hydroxyl
tion, and use, see → Drying Oils and Related value, viscosity, and specific gravity. The oil is
Products. soluble in ethanol at room temperature and in
boiling hexane.
d25
25 0.945 – 0.965
13.2.7.2. Oiticica Oil and Related Oils n40 1.466 – 1.473
D
Solidification point −12 to −18 ◦ C
Oiticica oil [8016-35-1] is obtained mainly from Viscosity at 20 ◦ C 935 – 1033 mPa s
the nuts of the Brazilian oiticica tree, Licania [α] D +7.5 to +9.7 ◦
Saponification value 177 – 187
rigida. This evergreen tree reaches a height of Iodine value (Wijs) 82 – 90
20 m and produces 150 – 900 kg of nuts per year. Hydroxyl value 161 – 169
The kernels contain 55 – 63 % oil, which is gen- Acetyl value 144 – 150
Nonsaponifiable matter 0.2 – 0.3 %
erally obtained by pressing. Fresh oiticica oil
is yellowish and of lardlike appearance. Oiti-
cica oil for export is heated for 30 min at 210 –
220 ◦ C, after which it remains liquid. Licanic
acid, 4-oxo-9,11,13-octadecatrienoic acid, is the Production. Cold pressing of the spotted,
principal fatty acid. The oil yields varnishes sim- oblong seeds yields a light, viscous oil which is
ilar to those made from tung oil (→ Drying Oils used primarily in pharmaceutical products. Sub-
and Related Products). sequent expelling at elevated temperatures and
Boleko or isano oil ( ongoke oil) is obtained extraction with hexane yields a yellowish-brown
from the nuts of Ongokea gore Engler, a tree oil which is used primarily in technical applica-
growing in the Congo regions. It contains isanic tions. The extracted meal contains ricin, a toxic
and isanolic acids, which are fatty acids with protein, and hence cannot be used as an animal
conjugated triple bonds. feed.
Parinarium oils are contained in the kernels of
various tropical trees of the family Rosaceae and Use. A drying oil can be made by dehydrat-
have little commercial significance. Parinarium ing castor oil (dehydrated castor oil, → Drying
laurinum, a tree growing in Japan and Oceania, Oils and Related Products, Chap. 4.). Pyrolytic
yields a seed oil which contains parinaric acid, cleavage at 300 ◦ C gives undecylenic acid and
an acid with 4 conjugated double bonds. heptaldehyde, raw materials for polymers and
Néou oil, obtained from P. macrophyllum, perfumes. Alkali fusion of castor oil yields 2-
contains about 30 % eleostearic acid. Eleostearic octanol and sebacic acid.
acid, in addition to licanic acid, has been found Hydrogenation yields a fat with a melting
in po-yoak oil (obtained from P. sherbroense). point of 84 – 86 ◦ C and waxlike properties, find-
ing application as a special lubricant. Air-blown
castor oil is used as plasticizer for varnishes and
13.2.8. Substituted Fatty Acid Oils polymers. The oil is also used in the production
of transparent soap, textile processing aids, spe-
13.2.8.1. Castor Oil cial lubricants, and toiletries.

The seeds of the castor tree, Ricinus communis,

contain 45 – 50 % castor oil [8001-79-4]. The ev- 13.2.8.2. Chaulmoogra, Hydnocarpus, and
ergreen castor tree belongs to the family Euphor- Gorli Oils
biaceae and grows in tropical and subtropical
countries. It can reach a height of 10 m. The seed kernels of Taractogenos kurzii, a
tree native to Southeast Asia, contain 48 – 55 %
 Fats and Fatty Oils 65
Table 28. Properties of some “leprosy oils”

Chaulmoogra oil Hydnocarpus oil Gorli oil

(Taractogenos kurzii) (Hydnocarpus whigtiana) (Oncoba echinate)

Palmitic acid, % ca. 4 1–2 7–8

Oleic acid, % 13 – 15 5–7 2–3
Lower homologues of
hydnocarpic acid, % ca. 0.5 3–4
Hydnocarpic acid, % ca. 35 ca. 50
Chaulmoogric acid, % ca. 23 27 ca. 75
Gorlic acid, % ca. 23 12 – 13 ca. 14
n40
D 1.471 – 1.473 1.472 – 1.473
[α] 25
D ,
◦
+49.8 +55 +51.7
mp, ◦ C 22 – 30 22 – 24 42 – 44
Saponification value 198 – 208 200 – 208 190 – 194
Iodine value 98 – 105 93 – 101 94 – 100
Nonsaponifiable matter, % <0.5 <0.5 1 – 1.5

chaulmoogra oil, the chief fatty acid compo- 14.1. Land-Animal Fats [94]
nents of which are chaulmoogric acid, hydno-
carpic acid, gorlic acid, and lower homologues 14.1.1. Lard
of hydnocarpic, palmitic, and oleic acid. Chaul- Lard [61789-99-9] is the fat rendered from fresh,
moogra oil and related oils such as hydnocarpus clean, sound fatty tissues from pigs in good
oils, obtained from Southeast Asian Hydnocar- health at the time of slaughter. The tissues do
pus varieties, and the African gorli oil have been not include bones, ears and tails, internal or-
used in the treatment of leprosy; for properties gans, windpipes, or large blood vessels. Ren-
see Table 28. dered pork fat is obtained from the tissues and
bones of pigs in good health at the time of slaugh-
ter; it may contain fat from bones, skin, ears and
13.2.8.3. Vernonia Oil [93] tails, and other tissues fit for human consump-
tion. A range of different quality grades is avail-
The seeds of Vernonia anthelmintica (of the able.
Compositae family) contain an oil with a high
percentage of vernolic acid (cis-12,13-epoxy- Properties. European lard (iodine value ca.
cis-9-octadecenoic acid). This epoxy acid is 60) is often harder than America lard (iodine
used in protective coatings, plastics, and other value ca. 70).
industrial products. Efforts have been made to
grow Vernonia varieties as new industrial crops mp 30 – 40 ◦ C
Solidification point 22 – 32 ◦ C
in the United States and Asia. Saponification value 193 – 202
Nonsaponifiable matter 0.1 – 1.0 %

14. Individual Animal Fats

Lard consists of 4 – 8 % trisaturated, 32 –
Animal fats are obtained from the milk or the 40 % disaturated – monounsaturated, 45 – 50 %
fatty tissue of certain groups of animals (see also monosaturated – diunsaturated, and 3 – 10 % tri-
→ Milk and Dairy Products). The content of de- unsaturated triglycerides. The main fatty acid
pot fat varies from 0 to 60 %. The concentration components are shown in Tables 1 and 2. Lard
and composition of the fat depend on type of contains low concentrations of arachidonic acid
animal, age, sex, and diet. (0.4 – 0.9 %), trans fatty acids, as well as traces
of branched and odd-numbered fatty acids such
as saturated C15 , C17 , and C19 fatty acids and
monounsaturated C17 and C19 fatty acids. Tri-
unsaturated C18 , C20 , and C22 fatty acids are
66 Fats and Fatty Oils

also present. These typical fatty acids, together yellow because of carotenes taken up with fresh
with the cholesterol that occurs in relatively high roughage. Table 29 shows analytical data for
concentrations in animal fats, are the basis for various beef tallow products. Beef tallow con-
detecting lard and other animal fats in vegetable tains 14 – 26 % trisaturated, 22 – 34 % disatu-
oils and fats. rated – monounsaturated, and 40 – 64 % mono-
saturated – diunsaturated glycerides.
Production. Lard is obtained by dry or wet The stability of beef tallow and its products
rendering. The best quality lard (acid value is relatively poor in the absence of an added an-
<0.8; moisture <0.1 %) is made from selected tioxidant. Primary quality criteria are odor and
tissue which has been washed and cooled im- taste, concentration of free fatty acids, and ab-
mediately after slaughter. After comminution, sence of impurities and of refined low-quality
the fatty tissue is wet-rendered by steam heat- tallow (white grease).
ing at 50 – 60 ◦ C (for continuous wet-rendering
plants see Section 5.2). Prime steam lard and leaf Production. The choice of fatty tissue deter-
lard are obtained similarly from nonselected or mines the quality of beef tallow. Fat rendered
partially selected tissue. Packer’s lard retains a from the carcasses of cattle is generally not quite
typical flavor; refiner’s lard has to be refined. as hard as that obtained from sheep and goats.
Inferior varieties, made in part from inedible of- The softest, most unsaturated fat is found under
fal, include so-called white, yellow, and brown the skin, and the firmer fat is located near the
greases, which are used primarily in technical middle of the animal. The consistency of indi-
applications. vidual lots of tallow is therefore influenced by
Lard can be fractionated into a higher- and the procedure used in trimming the carcass prior
lower-melting fraction. In order to prevent the to fat rendering.
use of inferior raw materials, some European Edible tallow (dripping, max. 1 % ffa) is ob-
countries do not permit the refining of lard. The tained from clean, sound, fatty tissues of beef
addition of antioxidants significantly improves cattle in good health at the time of slaughter.
the organoleptic and oxidative stability. Lard can Premier jus (max. 0.5 % ffa) is obtained by ren-
be refined either by neutralization with lye, fol- dering the fresh fat (killing fat) of heart, caul,
lowed by bleaching with ca. 1 % earth and de- kidney, and mesentery, excluding cutting fats at
odorization at 180 – 240 ◦ C, or by simple pre- low temperature (50 – 60 ◦ C). Tallow to be in-
treatment with phosphoric acid – bleaching earth corporated into margarine blends must be re-
and subsequent distillative stripping. Interester- fined. Fractionation at 26 ◦ C yields a lower-
ification improves the performance of lard as melting fraction (olein) and a higher-melting
a shortening in terms of creaming and cake- fraction (stearin). Tallow olein is an important
making [95]. component of some margarines and shorten-
ings. Stearin is used in shortenings and in spe-
Use. Lard is used extensively as an edible fat cialty margarines. Bone grease is obtained by
(shortening, margarines) and as an energy source expelling and extracting of comminuted bones ;
in animal feeds. it is used primarily in the technical sector and
for animal feeds. Neatsfoot oil [8037-20-5] is a
low-melting, inedible fat rendered from the feet
14.1.2. Beef Tallow of cattle; it is used as a special lubricant and
leather dressing aid.
Properties. The main fatty acids of beef tal-
low [61789-97-7] are shown in Tables 1 and 2. Use. Only a small part of the annually pro-
In addition, it contains up to 4 % of characteristic duced beef tallow is used as edible fat. The con-
branched and odd-numbered fatty acids. These, centration in margarine is limited because of its
together with cholesterol, identify tallow in veg- poor stability but it is used more widely in short-
etable oils and fats. Tallow also contains 6 – 10 % enings. The technical grades are important raw
of trans fatty acids, resulting from bacterial hy- materials for soap and fatty acid derivatives and
drogenation in the rumen. Top-grade tallow is for use in animal feeds. Specifications for tech-
white to greyish-white; in summer it is slightly
 Fats and Fatty Oils 67
Table 29. Properties and analytical data of beef tallow and derived products

Beef tallow Stearin Olein Bone grease Neatsfoot oil

3
Density, g/cm 0.898 – 0.908 0.914 – 0.924
(40 ◦ C) (15 ◦ C)
n60
D 1.451 – 1.454 ca. 1.449 1.451 – 1.452 1.461 – 1.463
mp, ◦ C 40 – 50 50 – 55 23 – 35 44 – 45
Saponification value 193 – 200 190 – 198 193 – 198 190 – 200 188 – 198
Iodine value 32 – 47 14 – 25 40 – 53 49 – 53 67 – 80
Nonsaponifiable matter, % 0.3 – 0.8 0.3 – 0.8 0.1 – 0.5 0.5 – 0.6 0.1 – 0.6

Table 30. The Society of British Soap Makers specifications for tallows and greases (based on testing methods specified in B.S.3919 : 1976)

Grade ffa ∗, % Bleached oil Moisture Nonsaponifiable Titer, ◦ C Iodine value

colour (red) and dirt, % matter, %

Tallow 1 max. 3.0 max. 0.5, max. 0.5 max. 0.5 min. 40.0 max. 57
5 1/4 inch cell
Tallow 2 max. 5.0 max. 1.0, max. 1.0 max. 1.0 min. 40.0 max. 57
5 1/4 inch cell
Tallow 3 max. 8.0 max. 3.0, max. 1.0 max. 1.0 min. 40.0 max. 57
5 1/4 inch cell
Tallow 4 max. 12.0 max. 4.0, 1 inch cell max. 1.0 max. 1.5 min. 40.0 max. 60
Tallow 5 max. 15.0 max. 12.0, 1 inch cell max. 1.0 max. 1.5 min. 40.0 max. 60
Tallow 6 max. 20.0 no limit max. 1.0 max. 2.0 min. 40.0 max. 60
Grease max. 20.0 – max. 2.0 max. 2.0 36.0 – 40.0 max. 63

∗ ffa = free fatty acids.

Table 31. Analytical data for various fish oils [99]

Herring oil Sardine oil Pilchard oil Menhaden oil South American oil

n40
D 1.470 – 1.475 1.473 – 1.475 1.473 – 1.476 1.473 – 1.474 1.474 – 1.478
Saponification value 183 – 192 187 – 190 188 – 194 188 – 194 189 – 194
Iodine value 120 – 160 165 – 185 180 – 190 150 – 180 185 – 206
Nonsaponifiable matter, % 0.8 – 1.3 1.0 – 1.6 0.8 – 1.5 0.8 – 1.5 0.8 – 1.5

nical tallows used for soapmaking are shown in of branched and odd-numbered fatty acids and
Table 30. traces of trans fatty acids are also present.

14.1.3. Mutton Tallow 14.1.4. Horse, Goose, and Chicken Fat

Mutton tallow finds applications primarily in the Horse fat is softer than lard or rendered pork
technical sector. Superior grades are similar to fat. The fatty acid composition (Tables 1, 2) is
corresponding beef tallows. strongly influenced by diet. Branched and odd-
numbered fatty acids occur up to about 2 %. The
Saponification value
Iodine value
192 – 198
31 – 47
nonsaponifiable matter is <0.5 %, the melting
Nonsaponifiable matter 0.1 – 0.6 % point 29 – 40 ◦ C. Horse fat is occasionally used
Density (40 ◦ C) 0.896 – 0.898 g/cm3 in meat and sausage products in some countries.
n40
D 1.455 – 1.458 Goose fat has a relatively low melting point,
44 – 55 ◦ C
25 – 35 ◦ C; its consistency is often improved by
mp

addition of lard.
Chicken fat is also low-melting, mp 23 –
The main fatty acids are palmitic, stearic, 40 ◦ C. The fatty acid composition (see Tables 1
and oleic acids (Tables 1 and 2). Up to 4 % and 2) is strongly influenced by diet.
68 Fats and Fatty Oils
Table 32. World production of oil fruits, oilseeds, oils, and fats according to countries (annual average, expressed as oil/fat in 1000 t)

1934/38 1960 1970/71 1973/74 1980/81 1981/82 1982/83 1983/84 1984/85 a

Europe 3328 b 4790 c

EEC 2300 4220 5615 5550 6065 6215 6080
EFTA 1135 710 855 850 930 910 930
Other West European 990 805 1015 835 650 1180 750 1285 d
countries
Soviet Union 2000 3090 5335 6030 no data 4870 5340 5315 5105
Other East European 1231 1595 1975 2430 2920 2950 2975 3040 3290
countries
Africa 3015 e
West Africa 1132 2010 1845 1685 1380 2970 2800 2790
Other African countries 379 985 1420 1540
America
Argentina/Brazil 995 1525 2270 3080 5155 5100 5465 5935 6750
USA 3543 7470 11185 11945 14415 15620 16515 13535 14940
Other American countries 565 1480 3165 2605 3345 3210 3180 3340 3675
Asia
Sri Lanka/Burma 216 240 320 215 265 290 330 365 375
India/Pakistan 2274 2725 3615 3620 3890 4750 4290 4875 4825
Indonesia/Malaysia 931 780 1425 1815 4510 5380 5355 5530 6800
Philippines 452 840 965 800 1585 1500 1345 1090 1140
Chinese Republic 3341 2905 3100 3070 4250 5685 6325 6160 6650
Other Asian countries 628 960 1460 1645 1105 1045 1045 1090 1120
Australia/Oceania 575 755 955 890 1100 1140 1115 1240 1270
World production 21590 31785 44630 46320 58880 62505 65485 63145 68155
a
Preliminary data.
b

EEC, EFTA, and other West European countries.
c

EEC, EFTA.
d
Including Spain.
e

West Africa and other African countries.

14.2. Marine Oils [96] it was discovered that the oil can be converted
into a stable edible fat by hydrogenation, many
Marine oils are the oils obtained from whales thousands of tons of hardened whale oil have
and fish. Fish oils have a high content of highly been produced for margarine, cooking fats, and
unsaturated (4 – 6 double bonds) C20 , C22 , and soapmaking.
C24 fatty acids ( cf. Tables 1 and 2). The oils
from freshwater fish contain less C20 and C22 Saponification value 185 – 205
Iodine value 110 – 135
fatty acids and more oleic and linoleic acid than Nonsaponifiable <2 %
those from sea fish. These differences are caused matter
primarily by differences in the composition of Slip point 22 ◦ C
n65 1.4554 – 1.4579
the feed. Only oils obtained from sea fish are D

commercially important.
Whale oil has been graded according to free
14.2.1. Whale Oil fatty acid content and color (apart from moisture
and dirt):
The whale population has been depleted to such
an extent that whale oil is now completely over- Grade 0: pale yellow, max. 0.5 % ffa
shadowed in commercial importance by the var- Grade 1: pale yellow, max. 2.0 % ffa
ious fish oils. The Antarctic has long been the Grade 2: amber yellow, max. 6.0 % ffa
catching area. Whales are processed in modern Grade 3: pale brown, max. 15.0 % ffa
factory ships (see also Section 5.3). The color of
Grade 0 – 2 whale oils are hydrogenated for
the oil can be very light, and the concentration
edible purposes. Prior to hydrogenation the oil
of free fatty acids very low. Since 1913, when
 Fats and Fatty Oils 69
Table 33. World production of oil fruits, oilseeds, oils, and fats (annual average, expressed as oil/fat in 1000 t)

1934/1938 1960 1970/71 1973/74 1980/81 1981/82 1982/83 1983/84 1984/85a

Vegetable oils
Cottonseed 1453 2315 2450 2825 3035 3280 3025 3040 3770
Peanutb 1755 2760 3230 3965 2605 3455 2900 3190 3195
Cornc 95 185 325 390 665 695 745 785 805
Olive 950 1285 1605 1550 1980 1495 2025 1575 1785
Rapeseed 1273 1105 2220 2170 3675 4040 4905 4700 5500
d d
Safflower 170 220 265 260 245 260 265
Sesame 563 485 755 720 615 730 620 700 695
Soybean 1263 3780 7700 9670 13275 13885 15255 13540 14675
Sunflower 435 1170 3335 4250 4695 5250 6000 5530 6165
Babassu 27 50 105 125
Coconut 1633 2060 2375 2015 3150 2990 2860 2435 2640
Palm kernel 355 450 490 430 585 700 730 760 870
Palm 644 1100 1745 2260 4550 5410 5410 5645 6720
Linseed 1040 1025 1255 795 660 670 815 670 700
Castor 178 230 340 465 325 350 350 375 420
Tung 121 115 120 95 105 95 100 95 95
Otherse 220 450 65 75 25 25 25 25 25
Animal fats
Butterfat f 4160 4435 4950 5225 5450 5705 6200 6255 6135
Lard 2913 4370 4365 4180 4760 5050 5130 5185 5210
Tallow 1679 3455 5270 5320 6360 6200 6100 6110 6210
Fish oil 325 470 1170 970
1100 g 1300 g 1090 g 1265 g 1280 g
Whale oil and sperm oil 507 490 190 140
a
Preliminary data.
b
Until 1960 including 10 000 – 15 000 t teaseed.
c
Including technical olive oil.
d
Included under “others”.
e
Including oiticica, mowrah, niger, hempseed, perilla, and other commercially important oils.
f
Including ghee fat.
g

Fish oil, whale oil, and sperm oil.

is lye-neutralized and bleached. Whale oil can It is being replaced by jojoba oil, a seed oil from
be hydrogenated into soft and hard fats. Soft a shrub (Simmondsia chinensis) indigenous to
fats with a melting point between 33 and 38 ◦ C the Sonoran desert and being cultivated in arid
are produced by hydrogenation under isomeriz- zones around the world. Its seeds contain 50 –
ing conditions with a partially inactivated nickel 60 % of a liquid wax composed of esters of fatty
catalyst. Fats with a melting point between 40 acids and fatty alcohols [97].
and 45 ◦ C are produced with relatively fresh
catalyst. The crude hydrogenated fats are fil-
tered to remove catalyst, treated with weak lye, 14.2.2. Fish Oil [98]
bleached, and deodorized. In some cases, post- The bulk of fish oils is produced in modern plants
treatment can be restricted to treatment with cit- by cooking comminuted fish or fish offal, ex-
ric acid – bleaching earth followed by distillative pelling in screw presses, and centrifugation; or
stripping. Hydrogenated whale oil is stable for by extraction of dried fish meal with hexane (see
about 6 months. The softer fats are used primar- Section 5.3). Refining and hydrogenation yields
ily for shortenings, the higher melting ones for fats of edible quality which are used in margarine
preserves, dry soups, and special margarines. and shortening blends. For historical reasons fish
The main components of sperm oil oils are not permitted as edible oils in the United
[8002-24-2] are esters of fatty acids and fatty States. The main crude oil origins are Japanese
alcohols (waxes). Sperm oil is a valuable raw (iodine value ca. 180), U.S. (menhaden: iodine
material for high-quality cosmetic preparations. value 150 – 160), South American (iodine value
70 Fats and Fatty Oils
Table 34. World exports of oil fruits, oilseeds, oils, and fats according to countries (annual average, expressed as oil/fat in 1000 t)

1934/38 1965 1970 1974 1980 1981 1982 1983

Europe
Western Europe and Iceland 738 1020 1335 1693 1820 1658 2022
Eastern Europe and Soviet Union 315 783 740 532 458 548 466
Africa
Former French Equatorial/West 298 409 395 341 312 194 313 325
Africa
Nigeria 455∗ 737 392 182 107 75 55 65
Former Portuguese Africa 62 93 111 96
Sudan 115 100 105 85 91 93 52
Zaire 97 115 173 104 29 25 19 15
Other African countries 212 259 315 335 211 273 209 137
America
Argentina/Uruguay 577 416 469 224 1426 1079 1243 1548
Canada 320 556 520 1071 1215 1012 1024
United States 100 3356 4479 5319 8246 7976 8534 7603
Other American countries 133 377 579 926 234 213 334 213
Asia
India/Sri Lanka 589 142 105 123 75 138 166 163
Indonesia 529 260 317 304 610 201 323 449
Malaysia 132 164 435 883 2517 2827 3187 3346
Philippines 348 797 608 631 1002 1126 1080 1035
China 742 195 153 134 139 246 190 310
Other Asian countries 122 137 263 455 508 593 649
Australia/Oceania 363 540 640 530 755 749 790 804
Antarctic/Arctic 507 350 209 138 18 14 14 11
World exports 5829 8301 9820 13233 20819 20957 21589 21618

∗ Including Ghana, Gambia, Sierra Leone.

ca. 200), and Scandinavian (iodine value 130 – oil are valued for pharmaceutical purposes be-
140). cause of their high content of vitamin A (1500 –
The oil content of fish is subject to sea- 50 000 i.u./g) and vitamin D (40 – 200 i.u./g).
sonal variations and generally lies between 8 and Typical properties of cod-liver oil are as follows:
20 %. Typical properties of various fish oils are
Saturated fatty acids, %
shown in Table 31 (for fatty acid composition C14 6
see Tables 1 and 2). All fish oils contain small C16 6
concentrations of branched and odd-numbered C18 8
fatty acids. Unsaturated fatty acids, %
C14 traces
C16 20
Use. Fish oils are processed into hydro- C18 29
genated fats analogously to whale oil [100]. C20 26
C22 10
However, due to their content of polyunsaturated Saponification value 180 – 197
fatty acids and sulfur compounds, hydrogen- Iodine value 150 – 175
ation requires more hydrogen and more catalyst. Nonsaponifiable matter, % ca. 1
The melting points of hardened fish oils range n25
D 1.481

from 31 to 45 ◦ C. Organoleptic stability gener-

ally improves with decreasing iodine value of
the starting oil and with increasing melting point
of the hardened product. Hardened fish oils are 15. Economic Aspects
used in shortenings and margarine blends. They
have good creaming and cake-making properties Figures for the world production and exports of
but do not perform as well in frying. important fats and oils are shown in Tables 32,
Much of the oil of cod, halibut, and shark is 33, 34, 35.
stored in the liver. Cod-liver oil and halibut-liver
 Fats and Fatty Oils 71
Table 35. World exports of oil fruits, oilseeds, oils, and fats (annual average, expressed as oil/fat in 1000 t)

1934/38 1965 1970 1974 1980 1981 1982 1983

Vegetable oils
Cottonseed 189 395 307 369 495 473 522 320
Peanut 826 967 817 677 678 519 641 669
Olive ∗ 136 113 237 262 219 205 162 278
Rapeseed 51 272 481 670 1149 1364 1224 1274
Safflower 70 50
Sesame 69 70 104
Soybean 432 1802 2962 3903 6665 6757 7162 6770
Sunflower 26 263 700 629 1431 1535 1558 1832
Babassu 12 12 14
Coconut 1057 1283 1087 923 1365 1455 1411 1376
Palm kernel 320 371 327 383 431 419 462 479
Palm 447 551 744 1327 2961 2818 3336 3567
Linseed 572 473 421 271 423 420 352 402
Castor 81 206 236 227 203 202 180 184
Tung 80 42 36
Others 68 121 185 358 680 714 755 759
Animal fats
Butterfat 500 499 641 704 775 740 671 608
Lard 173 290 347 372 432 439 389 366
Tallow 162 1225 1517 1575 2193 2181 2068 2025
Fish oil 121 445 554 500 701 702 682 698
Whale oil and sperm oil 507 350 209 138 18 14 14 11

∗ Including olive oil for industrial uses.

16. Toxicology and Occupational 7. W. Wachs: öle und Fette, Part II, Paul Parey,
Health Berlin – Hamburg 1964.
8. “Fette und Lipoide,” Handbuch der
With the exception of technical oils and fats such Lebensmittelchemie, vol. IV, Springer Verlag,
as castor and tung oil, oils and fats are classed Berlin – Heidelberg –New York 1965.
9. L. V. Cocks, C. V. van Rede: Laboratory
as foods or food additives and do not entail tox-
Handbook for Oil and Fat Analysis, Academic
icological or occupational health hazards.
Press, London –New York 1966.
10. F. D. Gunstone: An Introduction to the
Chemistry and Biochemistry of Fatty Acids
17. References and their Glycerides, Chapman and Hall,
London 1967.
General References 11. H. A. Boekenoogen: Analysis and
1. E. W. Eckey: Vegetable Fats and Oils, Characterisation of Oils, Fats and Fat
Reinhold Publ. Co., New York 1954. Products, Interscience, New York 1968.
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Fettprodukte, vols. I and II, Springer Verlag, Human Nutrition, Academic Press, London
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Oils, The Garrard Press, Champaign, Ill., Parey, Hamburg 1976.
1960. 14. D. Swern (ed.): Bailey’s Industrial Oil and Fat
4. J. Devine, P. N. Williams: The Chemistry and Products, 4th ed., Wiley & Sons, New York
Technology of Edible Oils and Fats, Pergamon 1979.
Press, Oxford 1961. 15. Kirk-Othmer, 9, 795; 21, 417; 23, 717.
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ölen, 2nd ed., Th. Steinkopff, Leipzig 1962. in Human Nutrition, VCH
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for Edible Purposes, 2nd ed., Pergamon Press,
London 1962.
72 Fats and Fatty Oils

17. R. J. Hamilton, J. B. Rossell (eds.); Analysis of 37. P. König, Fette Seifen Anstrichm. 64 (1962)
Oils and Fats, Elsevier Applied Science Publ., 23.
Barking,England 1986. 38. J. Furman et al., J. Am. Oil Chem. Soc. 36
(1959) 454.
Specific References 39. G. Penk, Proc. A.S.A. Symp. Soybean Process.
18. J. Baltes: “Gewinnung und Verarbeitung von 2nd 1981.
Nahrungsfetten,” Grundlagen und Fortschritte 40. W. H. Prokop, JAOCS J. Am. Oil Chem. Soc.
der Lebensmitteluntersuchung, vol. 17, Paul 62 (1985) 805.
Parey, Berlin, Hamburg 1975, p. 42. 41. S. M. Barlow, M. L. Windsor: Techn. Bulletin
19. J. B. M. Rattray, JAOCS J. Am. Oil Chem. Soc. no. 19, Int. Ass. of Fish Meal Manufacturers,
61 (1984) 1701. UK, Sept. 1984.
20. F. D. Gunstone: An Introduction to the 42. Th. Wieske, H.-U. Menz, Fette Seifen
Chemistry and Biochemistry of Fatty Acids Anstrichm. 74 (1972) 133. V. K. Babayan, J.
and their Glycerides, Chapman & Hall, Am. Oil Chem. Soc. 51 (1974) 260.
43. O. L. Brekke in: Handbook of Soy Oil
London 1967.
Processing and Utilisation, Amer. Soybean
21. M. Szuhaj, G. List: Lecithins, AOCS
Ass., 1980.
monograph, 1985.
44. H. J. Ringers, J. C. Segers, US 4 049 686, 1977.
22. A. J. Speek et al., J. Food Sci. 50 (1985) 121. 45. A. K. Sen Gupta, US 4 062 882, 1977.
23. M. L. Meara: Leatherhead Food RA, Scientific 46. F. V. K. Young, Proc. A.S.A. Symp. Soybean
and Technical Survey no. 110, July 1978. Process. 2nd 1981.
24. K. van Putte, J. v. d. Enden, Fette Seifen 47. A. N. Sagredos, K. Remse, Fette Seifen
Anstrichm. 76 (1974) 316. Anstrichm. 85 (1983) 185. P. Röttgermann,
25. E. S. Lutton, J. Am. Oil Chem. Soc. 49 (1972) Fette Seifen Anstrichm. 85 (1983) 190.
1. 48. Y. Hoffmann, J. Am. Oil Chem. Soc. 50 (1973)
26. B. G. Linsen, Fette Seifen Anstrichm. 73 260.
(1971) 411, 753; 70 (1968) 8. 49. H. Pardun, Fette Seifen Anstrichm. 81 (1979)
27. J. W. E. Coenen in I. Morton, D. N. Rhodes 297.
(eds.): The Contribution of Chemistry to Food 50. D. C. Tandy, W. J. Macpherson, JAOCS J. Am.
Supplies, Butterworths, London 1974. Oil Chem. Soc. 61 (1984) 1253. A. Forster,
28. H. Wissebach, Tenside 3 (1966) 285. A. J. Harper, J. Food Sci. 49 (1984) 23.
29. A. K. Sen Gupta, H. Scharmann, Fette Seifen 51. H. P. Kaufmann, D. Schmidt, Fette Seifen 47
Anstrichm. 71 (1969) 873. (1940) 294.
30. H. W. G Heynen et al., Fette Seifen Anstrichm. 52. M. Kock, Proc. A.S.A. Symp. Soybean Process.
74 (1972) 677. 2nd 1981.
31. E. W. Trautschold: Die Lagerung von 53. G. Biernoth, H. E. Rost, Chem. Ind. 1967,
Sojabohnen unter Qualitätsaspekten, 2002. G. Biernoth, Fette Seifen Anstrichm. 70
DGF-paper, München 1970. (1968) 217. A. N. Sagredos, D. Sinha-Roy,
32. H. P. Kaufmann et al.: Neuzeitliche Dtsch. Lebensm. Rundsch. 75 (1979) 350.
Technologie der Fette und Fettprodukte, 54. D. B. Erskine, W. G. Schuliger, Chem. Eng.
Aschendorffsche Verlagsbuchhandlung, Prog. 67 (1971) 41.
Münster 1956 – 1965. 55. A. Thomas, Fette Seifen Anstrichm. 84 (1982)
33. I. E. Liener: Toxic Constituents of Plant 133.
Foodstuffs, Academic Press, New 56. J. B. Rossell et al., Proc. A.S.A. Symp. Soybean
York – London 1969. Process. 2nd 1981.
34. “Oilseed Processing Symposium 1976,” J. Am. 57. H. Stage: Proc. A.S.A. Symp. Soybean Process.
Oil Chem. Soc. 54 (1977) 473A. 2nd 1981.
58. A. E. Rheineck, R. T. Holman et al.: Progress
35. Deutsche Gesellschaft für Fettwissenschaft:
in the Chemistry of Fats and Other Lipids,
Gewinnung von Fetten und ölen aus
vol. 5, Pergamon Press, New York1958.
pflanzlichen Rohstoffen durch Extraktion,
59. H. J. Passino, Ind. Eng. Chem. 41 (1948) 280.
Industrieverlag von Hernhaussen KG, 60. S. W. Gloyer, J. Am. Oil Chem. Soc. 26 (1949)
Hamburg 1978 162.
36. S. Skipin, Chem. Abstr. 29 (1935) 7682. A. 61. Deutsche Gesellschaft für Fettwissenschaft:
Carter et al., J. Am. Oil Chem. Soc. 51 (1974) Die Hydrierung von Fetten, Industrieverlag
137. von Herrnhaussen KG, Hamburg 1979.
 Fats and Fatty Oils 73

62. H. B. W. Patterson: Hydrogenation of Fats and 81. A. E. Bailey: Cottonseed and Cottonseed
Oils, Elsevier Applied Science Publ., Barking, Products, Interscience, New York 1948.
England, 1983. 82. B. S. Kamel et al., JAOCS J. Am. Oil Chem.
63. F. A. Kummerow, J. Am. Oil Chem. Soc. 51 Soc. 62 (1985) 881.
(1974) 255. 83. W. Schuster, Fette Seifen Anstrichm. 74
64. E. le Breton, P. le Marchal: Riv. Ital. Sostanze (1972) 150.
Grasse 47 (1970) 231. F. Camurati et al., Riv. 84. R. Purdy, JAOCS J. Am. Oil Chem. Soc. 62
Ital. Sostanze Grasse 47 (1970) 241. (1985) 523.
65. P. v. d. Plank, Fette Seifen Anstrichm. 76 85. R. Marquard et al., Fette Seifen Anstrichm. 80
(1974) 337. (1978) 213.
66. R. C. Hastert, JAOCS J. Am. Oil Chem. Soc. 86. W. Schuster, R. Marquard, Fette Seifen
58 (1981) 169. Anstrichm. 76 (1974) 207.
67. B. Screenivasan, J. Am. Oil Chem. Soc. 55 87. J. D. v. Mikusch, Farbe + Lack 7 (1952) 303.
(1978) 803. 88. T. Yaziciovglu et al., Fette Seifen Anstrichm.
68. G. Bradshaw, Soap Sanit. Chem. 18 (1941) 79 (1977) 115.
no. 5, 23, 69. 89. G. W. Rohne, Fette Seifen Anstrichm. 86
69. A. J. Haighton, L. Vermaas, Fette Seifen (1984) 172.
Anstrichm. 74 (1972) 615. 90. B. J. F. Hudson et al., J. Plant Foods 5 (1983)
70. J. R. Rossell: “Measurement of Rancidity in 15.
Oils and Fats,” Leatherhead Food RA, 91. L.-A. Appelquist, R. Ohlson: Rapeseed,
Scientific and Technical Survey no. 140, Sept. Elsevier, Amsterdam 1972.
1983. 92. A. Thomas, JAOCS J. Am. Oil Chem. Soc. 59
71. M. Arens, E. Kroll, Fette Seifen Anstrichm. 85 (1982) 1.
(1983) 307. 93. M. Y. Raie et al., Fette Seifen Anstrichm. 87
72. G. Guhr et al., Fette Seifen Anstrichm. 83 (1985) 325.
(1981) 373. 94. O. Dahl: Schlachtfette, Fleischforschung und
73. H. Karstens, Fette Seifen Anstrichm. 70 Praxis no. 10, Verlag der Rheinhessischen
(1968) 400. Druckwerkstätte, Alzey 1973.
74. M. Unbehend et al., Fette Seifen Anstrichm. 95. E. S. Lutton et al., J. Am. Oil Chem. Soc. 39
75 (1973) 689. (1962) 233.
75. K. G. Berger: Recommended Practices for 96. “Fish Oils and Animal Fats,” Proc.
Storage and Transport of Edible Oils and Fats, Leatherhead Food RA, Feb. 1986.
Palm Oil Research Institute of Malaysia, 1986. 97. T. K. Miwa, JAOCS J. Am. Oil Chem. Soc. 62
76. “Proceedings of the World Conference, Kuala (1985) 377.
Lumpur, 1984, on Palm, Palm Kernel and 98. M. E. Stansby: Fish Oils, Their Chemistry,
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(1985) 377. 99. F. V. K. Young: The Chemical and Physical
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Fatty Acids : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
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David J. Anneken1, Sabine Both2, Ralf Christoph3, Georg Fieg4, Udo Steinberner5, Alfred Westfechtel6
1Cognis Corporation, Cincinnati OH, United States of America, retired
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2Cognis Deutschland GmbH, Düsseldorf, Federal Republic of Germany
3Cognis Deutschland GmbH, Düsseldorf, Federal Republic of Germany
4Technische Universität Hamburg-Harburg, Hamburg, Federal Republic of Germany Advanced Product Search
5Cognis Deutschland GmbH, Düsseldorf, Federal Republic of Germany, retired
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6Cognis Deutschland GmbH, Düsseldorf, Federal Republic of Germany
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Copyright © 2006 by Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.
DOI: 10.1002/14356007.a10_245.pub2
Article Online Posting Date: December 15, 2006

Abstract | Full Text: HTML

Abstract
The article contains sections titled:

1. Introduction
2. Properties
2.1. Physical Properties
2.2. Chemical Properties
3. Production of Natural Fatty Acids
3.1. Resources and Raw Materials
3.2. Fat Splitting
3.2.1. Hydrolysis – Principles
3.2.2. Hydrolysis – Industrial Procedure
3.2.3. Hydrolysis – Enzymatic Processes
3.3. Separation of Fatty Acids
3.3.1. Distillation
3.3.2. Crystallization
3.4. Modification of Fatty Acids
3.4.1. Hydrogenation
3.4.2. Double Bond Isomerization
3.4.3. Dehydration
3.4.4. Dimerization
3.4.5. Ozonolysis
3.4.6. Thermal Decomposition
3.4.7. Bio-Oxidation of Fatty Acids
3.4.8. Enzymatic Esterification
4. Production of Synthetic Fatty Acids
4.1. Hydroformylation
4.2. Hydrocarboxylation
4.3. Other Commercial and Noncommercial Processes
5. Analysis
6. Storage and Transportation
7. Environmental Protection, Toxicology and Occupational Health
8. Uses
9. References

[Top of Page]

1. Introduction
Originally the term “fatty acids” was applied only to carboxylic acids separated from animal and vegetable fats. Today it includes all saturated and unsaturated
aliphatic carboxylic acids with carbon chain lengths in the range of C6 – C24. Fatty acids obtained by splitting natural fats and oils are quantitatively far more
important than synthetic fatty acids. Different processes for modification of natural fatty acids have been developed and are used to achieve special properties in
the different fields of application. The principle production flow sheet in the oleochemistry chain is shown in Figure 1 [1].

Figure 1. Oleochemical processes and products

The world production of oils and fats has grown from 60 × 106 t in 1980 to 124 × 106 t in 2003. Vegetable oils rose to a share of about 80 %, whereas animal fats
decreased to 20 %. The majority of natural oils and fats is used for human nutrition (ca. 80 %) and animal feed (ca. 6 %). The remainder of ca. 14 % or 17 × 106
t is consumed by the chemical industry [2-5].

page 1 of 29
Fatty Acids : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
For technical applications, fatty acids play an important role since many years. World production capacity of fatty acids in 2000, not including tall oil fatty acids,
was about 5.4 × 106 t and is estimated to grow to ca. 6.5 × 106 – 8.1 × 106 t in 2005/2006. Expansion mainly took place and is planned in the Asian region.
Based on the data for 2000 the contribution of Asia was about 50 %, Europe 30 %, and America 20 % [6], [7].

Although many fatty acids — often with unusual structures — occur naturally, with few exceptions (see Dimerization) only the straight-chain C6 – C22 carboxylic
acids are of commercial importance. Moreover, in many fields of application, more or less broad cuts are employed, rather than chemically pure individual fatty
acids.

[Top of Page]

2. Properties
2.1. Physical Properties
The face of chemical manufacturing is changing rapidly, shaped by such powerful forces as intensified global competition, increased stringency of safety and
environmental regulations, and increased customer demand for consistent attainment of high product quality. In this context computer-aided process engineering
(CAPE) plays a dominant role in the fast development of new or in revamping of existing processes. All process simulators use properties as intermediate
variables. Their values are obtained from experiments or property models chosen to mimic the behavior of the process components and the operating
conditions. For the process engineer, thermodynamic data form an essential basis for process development, design, and optimization. The thermodynamic data
include thermal, transport, and caloric properties of components, such as density, heat capacity, and especially phase-equilibrium properties such as vapor –
liquid phase equilibria. These data are necessary for the simulation of heat and mass transfer, design of thermal separation processes, and chemical reactors [8-
10].

Especially important are physical data associated with a phase change from the solid to the liquid state or vice versa. The behavior on melting is highly specific
for each fatty acid. For this reason, determination of the melting point is often used for identification and quality control. The melting point of a fatty acid depends
on the number of carbon atoms, the degree of saturation, and the structure of the hydrocarbon chain.

With straight-chain fatty acids, the melting point increases alternatingly with increasing chain length, so that the melting points of fatty acids with an odd number
of carbon atoms are somewhat lower than those of the adjacent even-numbered fatty acids. The behavior of fatty acids with chain lengths C6 – C22 is illustrated
in Figure 2.

Figure 2. Melting point alternation of straight-chain saturated fatty acids

For unsaturated fatty acids, the relationship is more complex. In general, a decrease in the melting point is observed with increasing number of double bonds.
However, naturally occurring cis isomers melt or solidify at lower temperatures than the corresponding trans isomers, as shown in Figure 3 for the C18 fatty
acids. Other interesting parameters are the position of the double bond and, for polyunsaturated acids, the location of double bonds relative to each other. Fatty
acids in which a conjugated arrangement ( CH CH CH CH ) occurs have considerably higher melting points than nonconjugated acids. An
example is given for eleostearic acid (Fig. 3).

Figure 3. Effects of number of double bonds, cis – trans isomerism, and conjugation on melting points of C18 acids

A comprehensive survey of physical and chemical properties of straight-chain fatty acids is presented in Tables 1 and 2 [11-32].

Table 1. Physical properties of straight-chain saturated C6–C30 fatty acids

Molar
heat
capacity Molar
Density kJ heat Molar heat
Systematic CAS bp°C Refractive kmol–1 of of
name (trivial registry Formula, M Neutralization mp (p, kg/m3 index nD K–1 (t, ° fusion vaporization
name) no. CnH2nO2 kg/kmol value °C kPa)a (t, °C) (t, °C) C) kJ/mol kJ/mol(t, °C)

Hexanoic [142-62-1] C6H12O2 116.16 483 –3 205.7 875.2 1.4170 261.41 15.20 63.01 (120)
(caproic) (101.3) (80) (20) (80)
Heptanoic [111-14-8] C7H14O2 130.19 431 -7.5 223 867.0 1.4230 260.45 14.99 71.08 (120)
(enanthic) (101.3) (80) (20) (15)
Octanoic [124-07-2] C8H16O2 144.22 389 16.5 239.7 861.2 1.4280 332.72 21.39 71.19 (120)
(caprylic) (101.3) (80) (20) (80)
Nonanoic [112-05-0] C9H18O2 158.24 354 12.4 255.6 855.6 1.4322 364.91 20.30 73.51 (120)
(pelargonic) (101.3) (80) (20) (80)
Decanoic [334-48-5] C10H 172.27 325 31.6 195.9 851.8 1.4269 390.09 28.05 74.78 (150)
(capric) (10.13) (80) (70) (80)
20O2
Undecanoic [112-37-8] C11H 186.28 301 28.5 208.3 850.8 1.4202 404.56 25.07 78.72 (150)
(10.13) (80) (70) (40)
22O2
Dodecanoic [143-07-7] C12H 200.32 280 43.8 218.9 845.4 1.4230 454.66 36.03 85.52 (150)
(lauric) (10.13) (80) (70) (80)
24O2
Tridecanoic [638-53-9] C13H 214.35 261 41.4 230.9 845.8 1.4252 489.32 33.58 79.17 (200)
(10.13) (80) (70) (50)
26O2

page 2 of 29
Fatty Acids : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
Tetradecanoic [544-63-8] C14H 228.38 245 54.2 241.5 844 1.4273 522.43 45.05 83.21 (200)
(myristic) (10.13) (80) (70) (80)
28O2
Pentadecanoic [ C15H 242.41 231 52.1 251.4 842.3 1.4292 539.15 43.12 89.6 (200)
1002-84-2] O (10.13) (80) (70) (60)
30 2
Hexadecanoic [57-10-3] C16H 256.43 218 62.8 261.7 839.7 1.4309 592.19 54.34 96.28 (200)
(palmitic) (10.13) (80) (70) (80)
32O2
Heptadecanoic [506-12-7] C17H 270.46 207 61.3 219.7 839.6 1.4324 634.13 51.16 91.53 (220)
(margaric) (1.33) (80) (70) (64)
34O2
Octadecanoic [57-11-4] C18H 284.49 197 69.6 282.4 837.4 1.4337 660.60 62.51 93.13 (220)
(stearic) (10.13) (80) (70) (80)
36O2
Nonadecanoic [646-30-0] C19H 298.51 187 68.7 237.4 877.1 1.4512 686 (72) 57.80
(1.33) (24) (25)
38O2
Eicosanoic [506-30-9] C20H 312.54 179 75.3 300.1 836.7 1.4250 717.78 70.92 61.76 (240)
(arachidic) (10.13) (100) (100) (80)
40O2
Docosanoic [112-85-6] C22H 340.60 164 80.0 263 822.1 1.4270 792.24 78.59
(behenic) (1.33) (100) (100) (80)
44O2
Tetracosanoic [557-59-5] C24H 368.65 152 84.2 257 820.7 1.4287 902.23 78.59
(lignoceric) (0.533) (100) (100) (98)
48O2
Hexacosanoic [506-46-7] C26H 396.70 141 87.7 271 819.8 1.4301 947.17
(cerotic) (0.533) (100) (100) (94)
52O2
Octacosanoic [506-48-9] C28H 424.76 132 90.9 285 819.1 1.4313
(montanic) (0.533) (100) (100)
56O2
Triacontanoic [506-50-3] C30H 452.81 123 93.6 299 1.4323
(melissic) (0.533) (100)
60O2

akPa = 10 mbar

Table 2. Physical properties of straight-chain unsaturated C11 C22 fatty acids

Density Refractive
Systematic name (trivial CAS M Neutralization Iodine mp, ° bp, °C ks/m3 index nD (t,
name) registry no. Formula kg/kmol value value C (p, kPa) (t, °C) °C)

Unsaturated fatty acids with a single double bond

10-Undecenoic [544-64-9] C11H 184.28 304 138 24.5 275 907.2 1.4486 (24)
(101.3) (24)
20O2
cis-9-Tetradecenoic [373-49-9] C14H 226.36 248 112 –4.0 183– 903.2 1.4558 (20)
(myristoleic) 186 (20)
26O2 (1.87)
cis-9-Hexadecenoic [593-39-5] C16H 254.42 221 100 28– 218– 900.3 1.4586 (20)
(palmitoleic) 30 220 (15)
30O2 (2.0)
cis-6-Octadecenoic [593-40-8] C18H 282.47 199 90 28– 237– 879.4 1.4528 (40)
(petroselinic) 30.1 238 (40)
34O2 (2.4)
trans-6-Octadecenoic [112-80-1] C18H 282.47 199 90 54
(petroselaidic)
34O2
cis-9-Octadecenoic (oleic) [112-79-8] C18H 282.47 199 90 13.4 ( 223 890.5 1.4582 (20)
) (1.33) (20)
34O2 16.3 (
)
trans-9-Octadecenoic [29204-02-2] C18H 282.47 199 90 45 225 873.4 1.4488 (50)
(elaidic) (1.33) (45)
34O2
cis-9-Eicosenoic (gadoleic) [112-86-7] C20H 310.53 181 82 24– 888.2 1.4597 (25)
24.5 (25)
38O2
cis-13-Docosenoic (erucic) [112-38-9] C22H 338.58 166 75 34.7 254.5 869.9 1.446 (57)
(1.33) (55)
42O2
trans-13-Docosenoic [506-33-2] C22H 338.58 166 75 61.9 285 858.5 1.4472 (64)
(brassidic) (4.0) (57)
42O2

Unsaturated fatty acids with two double bonds

cis,cis-9,12-Octadecadienoic [60-33-3] C18H 280.45 200 181 –5.2 224 902.5 1.4699 (20)
(linoleic) (1.33) (20)
32O2
trans,trans-9,12- [506-21-8] C18H 280.45 200 181 28– 179–
Octadecadienoic 29 183
(linolelaidic) 32O2 (0.11)

Unsaturated fatty acids with three double bonds

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cis,cis,cis-9,12,15- [463-40-1] C18H 278.44 202 274 –11 224.5 915.7 1.4800 (20)
Octadecatrienoic (1.33) (20)
30O2
trans,trans,trans- [28290-79-1] C18H 278.44 202 274 30 358.9 915.9 1.4678 (50)
9,12,15,Octadecatrienoic (101.3) (20)
(linolenic) 30O2

cis,trans,trans-9,11,13- [4337-71-7] C18H 278.44 202 274 49 235 898.0 1.5112 (50)
Octadecatrienoic (a- (1.6) (56)
eleostearic) 30O2

trans,trans,trans-9,11,13- [544-73-0] C18H 278.44 202 274 71– 883.9 1.5002 (75)
Octadecatrienoic (b- 72 (80)
eleostearic) 30O2

Highly unsaturated fatty acids

5,8,11,14-Eicosatetraenoic [7771-44-0] C20H 304.48 184 334 –49.5 169– 922 (20) 1.4870 (20)
(arachidonic) 171
32O2 (0.02)
4,8,12,15,19- [2548-85-8] C22H 330.52 170 384 –78 236 935.6 1.5014 (20)
Docosapentaenoic (0.67) (20)
(clupanodonic) 34O2

The behavior of fatty acid mixtures is characterized by a considerable lowering of the individual melting or solidification points. Most binary mixtures have phase
diagrams with a eutectic point. Depending on the types of acids combined, three groups can be distinguished: mixtures of saturated fatty acids, mixtures of
saturated and unsaturated fatty acids, and mixtures of unsaturated fatty acids. In Figures 4 and 5, typical solidification and melting point curves are illustrated.
The values are plotted as a function of the concentration of the higher melting component [28], [33-35].

Figure 4. Freezing points of binary systems of saturated C8 – C22 fatty acids

Figure 5. Freezing or melting points of binary systems of unsaturated fatty acids

The liquid densities of fatty acids are shown in Figure 6. The densities of C6 – C20 fatty acids are all less than 1000 kg/m3. The lower the molecular mass and
the higher the degree of unsaturation of fatty acids, the higher is their density.

Figure 6. Densities of liquid straight-chain fatty acids as a function of temperature

Optical properties such as light refraction have long been used to identify liquids and establish their purity. The refractive index of pure fatty acids increases with
increasing molecular mass, number of double bonds, and conjugation [30]. However, today measurement of the refractive index of fatty acids plays only a minor
role in quality control. Modern gas chromatographs are the standard equipment for the determination of mixture compositions.

The heat of fusion is the energy consumption for phase transition from the solid crystal to the liquid state. Measured values of molar heat of fusion for straight-
chain saturated fatty acids are listed in Table 1. Heats of fusion increase alternatingly with the length of the carbon chain. Fatty acids with an even number of
carbon atoms have a higher heat of fusion than adjacent odd-numbered acids. Above a chain length of ten carbon atoms the heat of fusion can be determined
by the following equations:

for even-numbered fatty acids (Table 1):

for odd-numbered fatty acids (Table 1):

where Hf is the heat of fusion (kJ/mol), and n the number of carbon atoms.

Table 3 lists heats of fusion for some C18 unsaturated fatty acids. They were derived from experimental data or calculated with the aid of theoretical relationships
[28], [29], [36]. As expected, the values are lower than those for saturated fatty acids.

Table 3. Heat of fusion of some unsaturated C18 fatty acids

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Component Heat of fusion, kJ/mol

Oleic (9 c) 30.14
Elaidic (9 t) 38.94
Linoleic (9 c, 12 c) 51.50
Linolenic (9 c, 12 c, 15c) 39.36
-Eleostearic (9 c, 11 t, 13 t) 43.96
-Eleostearic (9 t, 11 t, 13 t) 55.27

The heat of vaporization and the related properties boiling point and vapor pressure are very important for the design and optimization of distillation columns by
using simulation tools.

The boiling point and the molar latent heat of vaporization rise with increasing molecular mass (see Tables 1 and 2). The influence of the degree of saturation is
of minor importance. As expected, fatty acids show an almost ideal equilibrium behavior, that means, fulfillment of Dalton's and Raoult's laws (especially under
vacuum).

The molar latent heat of vaporization can be estimated by use of the integrated form of the Clausius – Clapeyron equation:

where hv is the molar latent heat of vaporization (J/kmol), R the universal gas constant (8314 J kmol–1·K1), T1, T2 are temperatures (K), and p1, p2 pressures
(Pa).

The vapor pressure curves for fatty acids of chain lengths C6 to C20 are presented in Figure 7 [18], [22], [23].

Figure 7. Vapour pressure of straight chain saturated fatty acids as a function of temperature

The following correlation relates vapor pressure and temperature of saturated, straight-chain fatty acids:

where t is the temperature (°C), p the vapor pressure (mbar), and M the molecular mass (kg/kmol).

The heat of combustion is of great practical and theoretical importance. It can be used to calculate the heat of formation, by means of which the enthalpy change
in chemical reactions can be established. Heat of combustion and heat of formation increase with increasing number of carbon atoms. The data for unsaturated
fatty acids, as far as they are known, are almost identical with those for the corresponding saturated fatty acids. For straight-chain saturated fatty acids the
following linear correlations can be used (Tables 4 and 5):

where n is the number of carbon atoms (C6 – C20), Hcomb the heat of combustion (kJ/mol), and Hform the heat of formation, kJ/mol

Table 4. Heat of combustion of straight-chain fatty acids (experimental values)[31, 33, 40]

Component – Hcomb, kJ/mol

C6 3 474
C8 4 792
C10 6 103
C12 7 416
C14 8 731
C16 10 039
C18 11 351
C20 12 648
C22 13 954
C18 : 1 c 11 168
C18 : 1 t 11 152
C22 : 1 c 13 799
C22 : 1 t 13 772

Table 5. Heat of formation of straight-chain fatty acids

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Component Hform, kJ/mol

C6 584.0
C8 635.2
C10 685.2
C12 775.6
C14 835.9
C16 892.9
C18 949.4
C20 1064.0
C18 : 1 c 710.2
C18 : 2 c 603.1
C18 : 3 c 485.9
C20 : 1 c 763.9
C22 : 1 c 807.5

For straight-chain saturated fatty acids in the liquid phase, the molar heat capacity is shown in Figure 8. For solid fatty acids, the values are presented in Figure
9 [19]. The molar heat capacity is particularly important when considering heat-transfer problems (e.g., design of heat exchangers).

Figure 8. Molar heat capacity of straight-chain saturated fatty acids (liquid phase)

Figure 9. Molar heat capacity of straight-chain saturated fatty acids (solid phase)

Thermal conductivity and dynamic viscosity are important properties in the assessment of heat transfer and fluid dynamics. The thermal conductivity and
dynamic viscosity of straight-chain saturated fatty acids as a function of temperature are shown in Figures 10 and 11, respectively.

Figure 10. Thermal conductivity of straight-chain saturated fatty acids

Figure 11. Dynamic viscosity of straight-chain saturated fatty acids as a function of temperature

At temperatures up to 100 °C, fatty acids and water have only low mutual solubilities, and the solubility of fatty acids in water is considerably lower than that of
water in fatty acids. Both solubilities increase with increasing temperature and decrease with increasing chain length. Some data on the mutual solubilities of the
binary water – saturated fatty acid system are given in Table 6. At high temperature and pressure, however, the solubility of water in fatty acids and in fatty acid
– fat mixtures is considerable. At 250 °C and 5 MPa, for example, approximately 12 % of water dissolves in the fatty acid phase of a mixture of tallow fatty acids
and water, while the value is 24 % for a mixture of coconut fatty acids. Complete miscibility with water is obtained at 320 and 290°C, respectively [37]. This fact
must be considered in the high-pressure splitting of fats and oils (see Section Hydrolysis — Industrial Procedure).

Table 6. Mutual solubilities of saturated fatty acids with water

Component Solubility of water in fatty acids, Solubility of fatty acid in water,

g water per 100 g acid (t, °C) g acid per 100 g water (t, °C)

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C6 4.96 (12.3) 0.968 (20)

10.74 (46.3) 1.171 (60)
C8 4.04 (14.4) 0.068 (20)
0.113 (60)
C10 3.22 (29.4) 0.015 (20)
0.027 (60)
C12 2.41 (42.7) 0.006 (20)
2.93 (90.5) 0.009 (60)
C14 1.73 (53.2) 0.002 (20)
0.003 (60)
C16 1.27 (61.8) 0.0007 (20)
0.001 (60)
C18 0.93 (68.7) 0.0003 (20)
1.03 (92.4) 0.0005 (60)

Above their melting points, fatty acids are miscible in all proportions with many organic solvents such as hydrocarbons, ketones, esters, alcohols, and chlorinated
or aromatic solvents. In the solid state, the solubility of saturated fatty acids depends on chain length and increases with increasing temperature. Unsaturated
fatty acids, however, are completely miscible at room temperature and display only limited solubility at lower temperature [28], [33], [38], [39].

In Tables 7 and 8, the solubilities of saturated and unsaturated fatty acids in methanol are given as examples.

Table 7. Solubility of saturated fatty acids in methanol

Component Solubility, g acid per 100 g methanol

0 °C 10 °C 20 °C 40 °C 60 °C

C8 330 1300 ∞ ∞ ∞
C10 80 180 510 ∞ ∞
C12 12.7 41.1 120 2250 ∞
C14 2.8 5.8 17.3 350 ∞
C16 0.8 1.3 3.7 77 4650
C18 0.1 11.7 520

Table 8. Solubility of unsaturated fatty acids in methanol

Component Solubility, g acid per 100 g methanol

–50 °C –30 °C –20 °C –10 °C 0 °C + 10 °C

C18 : 1 c 0.1 0.86 4.02 31.6 250 1820

C18 : 1 t 0.01 0.06 0.18 0.48
C18 : 2 c 3.3 48.1 233 1850
C22 : 1 c 0.007 0.068 0.19 0.49

The surface tension at the liquid – vapor interface and the interfacial tension in liquid – liquid systems are important properties for estimating the wetting behavior
at solid surfaces and the coalescence behavior in liquid – liquid extraction. The surface tension of liquid fatty acids decreases with decreasing chain length and
with increasing temperature. In Figure 12 and Table 9, some data are presented or listed for saturated fatty acids.

Figure 12. Surface tension of saturated fatty acids at 75 °C

Table 9. Interfacial tension of saturated fatty acids at 75 °C

Component Interfacial tension*, mN/m

C6 2.1
C8 5.8
C10 8.0
C12 8.7
C14 9.2

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C16 9.2
C18 9.5

*System: Fatty acid - water

Dry fatty acids are poor conductors of electricity. The specific electrical conductivity is a function of chain length and temperature. Values vary from 0.6 × 10–9 to
83 × 10–9 –1 m–1. The relative dielectric constants vary between 2 and 3, depending on the number of double bonds and the temperature [29].

The flash point and the autoignition temperatures of fatty acids are listed in Table 10 [41]. They rise significantly with increasing chain length.

Table 10. Average values for flash points and autoignition temperature of saturated and unsaturated fatty acids

Component Flash point, °C Autoignition temperature, °C

C6 103 308
C8 130 440
C10 147,150 -
C12 >160 -
C14 >160 -
C16 206 -
C18 196 395
C22(85%) 220 -
C18:1(80%) 180 -
C22:1(90%) 190 -

2.2. Chemical Properties

Fatty acids undergo the typical reactions of the carboxyl group ( Carboxylic Acids, Aliphatic). Commercially important derivatives such as esters, amides,
nitriles, and alkali or other metal salts are obtained by conventional methods (see also Uses). Hydrogenation of the carboxyl group to form fatty alcohols usually
involves esterification and is discussed in detail under Fatty Alcohols.

Unsaturated fatty acids are sensitive to atmospheric oxygen (see Storage and Transportation).

For industrially important reactions involving the double bond of unsaturated fatty acids (e.g., hardening, cis – trans isomerization, and dimerization) see
Modification of Fatty Acids. Scientific approaches for the functionalization of fatty acids have been reviewed [42], [43]. Focus here is on the reaction of the double
bonds of the fatty acids in order to achieve other or special properties.

[Top of Page]

3. Production of Natural Fatty Acids

3.1. Resources and Raw Materials
Fatty acids are widely distributed in nature as components of lipids such as oils and fats (esters of fatty acids with glycerol), waxes (esters of fatty acids with fatty
alcohols), sterol esters, and other minor compounds.

Vegetable oils are obtained mainly from seeds and only to a small extent from fruit pulp; animal fats are obtained from fat deposits and from organs ( Fats
and Fatty Oils). Oils and fats are one of the most important renewable resources suitable to develop sustainable concepts. The term fats normally means
materials of solid consistency, whereas liquid materials are referred to as oils. The definitions are indistinct, since the solid – liquid state of fats depends on
temperature and many fats show a semisolid consistency at ambient temperature.

For the manufacturing of fatty acids on a commercial scale, only oils and fats which are regularly available in large quantities are used as raw materials. Much
research in plant breeding has been done in the last few decades to adjust the fatty acid composition of vegetable oils to the needs of the food industry. The
main commercial results were achieved with low erucic acid rapeseed oil (LEAR, Canola) and high oleic sunflower oil (HOSO) [44], [45]. By the use of transgenic
approaches the fatty acid profile of soybean and rapeseed oil has been modified [46]. Though these developments have not been commercially used until now,
they show that in future fatty acid compositions of vegetable oils may vary over broader ranges.

Fats and oils have characteristic fatty acid profiles [47], [48]. Tables 11 and 12 list the fatty acid composition of important fats and oils for fatty acid production.

Table 11. Fatty acid composition of important oils and fats (weight percent)* [continued in Tab. 12

Fatty acid(trivial
name) Carbon No. of Cotton Peanut Coconut Linseed Palm Olive Rape-seed Palm
no. double seed oil oil oil oil kernel oil oil oil
(C22-low, LEAR,
bonds oil Canola)

Caproic acid C6 0 0–1 tr

Caprylic acid C8 0 5 – 10 3–6
Capric acid C10 0 5 – 10 3–5
Lauric acid C12 0 45 – 53 40 – 52
Myristic acid C14 0 0–2 0–1 15 – 21 tr 14 – 18 0 – 1 0–2 0–2
Palmitic acid C16 0 17 – 29 6 – 16 7 – 11 5–8 6 – 10 7 – 16 1–5 38 – 48
Stearic acid C18 0 1–4 1–7 2–4 2–4 1–4 1–3 1–3 3–6
Arachidic acid C20 0 0–1 1–3 tr 0–1 0–1 0–1
Behenic acid C22 0 tr 2–5 0–1

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Palmitoleic acid C16 1 0–2 0–1
Oleic acid C18 1 13 – 44 36 – 72 6–8 15 – 25 9 – 16 65 – 85 50 – 66 38 – 44
Gadoleic acid C20 1 tr 0–2 1–3
Erucic acid C22 1 0–5
Linoleic acid C18 2 33 – 58 13 – 45 1–3 12 – 16 1–3 4 – 15 15 – 30 9 – 12
Linolenic acid C18 3 0–1 50 – 60 0–1 6 – 13
Iodine value of oil 96 – 112 85 – 102 8 – 12 160 – 14 – 23 80 – 88 105 – 120 44 – 54
200
Saponification value 190 – 188 – 250 – 188 – 245 – 188 – 185 – 198 194 –
of oil 198 195 264 195 255 196 206
Fatty acid titer, °C 30 – 36 26 – 32 20 – 24 19 – 21 20 – 28 17 – 26 5 – 15 40 – 47

*tr = traces; no value = no data in the literature or below precision of measurement.

Table 12. Fatty acid composition of important oils and fats, continued (weight percent)*

Fatty acid (trivial

name) Carbon No. of Castor Rapeseed Soybean Sunflower Sunflower Sardine Beef
no. double oil oil oil oil oil oil tallow
(C18:2- HOSO(C18:1-
bonds (C22-rich) rich) rich)

Caproic acid C6 0
Caprylic acid C8 0
Capric acid C10 0
Lauric acid C12 0
Myristic acid C14 0 0–1 tr tr 4–6 1–6
Palmitic acid C16 0 2–3 2–5 7 – 12 3 – 10 3–5 9 – 11 20 – 37
Stearic acid C18 0 2–3 0–3 2–3 1 – 10 3–5 1–3 15 – 30
Arachidic acid C20 0 0–2 0–3 0–1 tr
Behenic acid C22 0 0–1 tr 0–1 1–2
Palmitoleic acid C16 1 tr tr 0–1 0–1 10 – 15 1–9
Oleic acid C18 1 4–9 11 – 24 20 – 30 18 – 28 82 – 86 15 – 25 20 – 50
Gadoleic acid C20 1 5 – 12 0–1 tr tr
Erucic acid C22 1 40 – 55 tr
Ricinoleic acid C18 1 80 – 87
Linoleic acid C18 2 2–7 11 – 29 45 – 58 60 – 68 4–7 3–8 0–5
Linolenic acid C18 3 6 – 13 4 – 10 0–1 0–1 1–3 0–3
Polyunsaturated fatty C20 2–6 15 – 30 tr
acid
Polyunsaturated fatty C22 3–6 15 – 20
acid
Iodine value of oil 81 – 91 95 – 108 120 – 120 – 140 85 – 90 170 – 35 – 55
140 193
Saponification value of 174 – 170 – 180 190 – 186 – 194 185 – 194 189 – 190 –
oil 186 195 193 200
Fatty acid titer, °C 13 – 16 20 – 24 16 – 20 8 – 20 39 – 43

*tr = traces; no value = no data in the literature, below precision of measurement.

Soap-stock fatty acids are byproducts in the processing of crude fats for human nutrition. The pulping of wood in the sulfate pulp process results in the digestion
of the lipids composed of esters of triterpene alcohols that are present in the resin. The free fatty acids found as constituents of tall oil ( Drying Oils and
Related Products) represent another starting material for the commercial production of fatty acids.

Natural waxes, such as sperm oil or jojoba oil, are not significant sources of fatty acids.

3.2. Fat Splitting

Fats are fatty acid esters of glycerol and are also known as triglycerides. By splitting the glycerides, fatty acids and glycerol can be recovered (Fig. 13).

Figure 13. Formation and splitting of glycerides

The most important splitting agents are water (hydrolysis), methanol (methanolysis), caustic soda (saponification), and amines (aminolysis) (Fig. 14). Because of
drawbacks in the subsequent purification of glycerol, saponification and aminolysis are of less commercial interest when full recovery of glycerol is important.
Today, most soaps and fatty acid amides are manufactured via fatty acids or fatty acid methyl esters. Exceptions are ricinoleic acid and hydroxystearic acid,
which are produced commercially by saponification of castor oil and hardened castor oil, respectively. In this way, the esterification reactions that occur with the
hydroxyl groups of ricinoleic and hydroxystearic acids during hydrolysis are avoided.

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Figure 14. Agents used to split triglycerides

3.2.1. Hydrolysis — Principles

The reactants in the hydrolysis of fats form a heterogeneous system made up of two liquid phases. The disperse aqueous phase consists of water and glycerol;
the homogeneous lipid phase contains glycerides and fatty acids. The hydrolysis of fat to form glycerol and fatty acids occurs essentially as a homogeneous
reaction by dissolved water in the lipid phase. The water – fat interfacial reaction is of minor significance [49]. The reaction takes place in several stages, via
partial glycerides (diglycerides and monoglycerides), as shown in Figure 15.

Figure 15. Typical course of hydrolysis reaction at 235 °C and 3.5 MPa using 1 part oil and 2 parts water

The total reaction can be summarized as follows (cf. Fig. 13):

The reaction proceeds to a state of equilibrium. At higher temperature, the endothermic nature of fat hydrolysis results in displacement of the equilibrium in favor
of the split products. The rate at which equilibrium is reached corresponds approximately to a first-order reaction [50]:

where

k = rate constant
t = reaction time
c = concentration of triglyceride

However, at the beginning and the end, the reaction does not proceed according to this equation. This is because the necessary excess of water is present only
after an induction period. Toward the end of the reaction, the glycerol concentration (which is not considered in the equation) has an increasing influence
because of the reverse reaction.

Values of the rate constant k are highly dependent on temperature because of the increased solubility of water in the lipid phase [49], which leads to:

where

k0 = statistical probability of reaction

E = energy of activation
T = absolute temperature
R = universal gas constant

An increase in temperature of 10 °C, for example, approximately doubles the value of k. Catalysts influence the rate constant k by changing the energy of
activation, whereas k0 is affected only slightly by temperature.

In the liquid two-phase system prevailing during hydrolysis of fats, the concentrations of the reactants depend primarily on the diffusion between the lipid and
aqueous phases. Mass transfer can be influenced favorably by large, turbulent interfaces. During the entire reaction two mass transfer effects, which proceed in
opposite directions, are of special importance for a high degree of conversion: (1) diffusion of water into the lipid phase and (2) removal of glycerol from the lipid
phase into the aqueous phase by water extraction.

The overall hydrolysis reaction is a very slow process mainly controlled by temperature and duration. In comparison, mass transfer of glycerol and water across
the phases is relatively fast [51]. LASCARAY [50]. summarized the complex reaction conditions in an empirical formula. He described the degree of splitting
(hydrolysis) in the lipid phase as a function of the glycerol concentration in the aqueous phase:

where

H = degree of splitting (% ffa = acid value/saponification. value × 100%)

cG = glycerol concentration (wt % in the water phase)

Optimization of this process by chemical engineering largely determines the yields of fatty acid and glycerol. Temperature, duration, heat transfer, and
hydrodynamic conditions, as well as the choice of catalyst, are the important parameters for approaching near-equilibrium conditions under the most favorable
economic conditions, i.e., in the shortest time possible.

3.2.2. Hydrolysis — Industrial Procedure

Pretreatment. Crude commercial fats are sometimes purified to remove troublesome impurities, such as minerals, gums, soaps, and proteins, before they are
subjected to splitting and following steps such as distillation or crystallization. The normal procedure is to heat the crude fat and then filter it or treat it with a small
quantity of 0.3 – 1.0 % sulfuric acid. Animal fats from slaughterhouses contain varying amounts of dissolved packaging materials that consist mainly of
polyhydrocarbons with differing rheological properties. These can best be separated from fats by filtration or centrifugation at ca. 70 °C with the use of filter aids.
Also, settling of the fats over several days before splitting can be helpful for removing most of the impurities, which form deposits at the bottom of the tank. In this
connection, one of the indicators for the quality of the fats and later yield of fatty acids is the share of total fatty material, which is defined as 100–M.I.U. (%
moisture + % insolubles (dirt) + % unsaponifiables, e.g., polyethylene). Typical values for traded animal fats are a saponifiability of 97 % (0.5 % moisture, 0.5 %

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dirt, 2 % unsaponifiables).

To suppress oxidation, degassing to remove atmospheric oxygen is recommended. All hydrolytic processes employ demineralized water as the splitting agent.
The hardness of water reduces catalyst efficiency and increases the salt content of the glycerol obtained.

Catalysts. Up to 100 °C, fat hydrolysis is very slow. For palm oil with an initial content of 5 % free fatty acids (ffa), a degree of splitting of ca. 20 % is reached
after 10 d at 100 °C [52]. TWITCHELL achieved a technical breakthrough in 1898 with an effective catalyst consisting of aromatic hydrocarbons, oleic acid, and
concentrated sulfuric acid (Twitchell reagent). The original Twitchell batch process operates under atmospheric pressure at almost 100 °C in wooden tubs. The
batch time is 12 – 24 h, and the degree of splitting without a change of water is about 80 – 85 % [53].

Lipases are specific biocatalysts for ester hydrolysis and exhibit optimum efficiency at temperature below 50 °C. Enzymatic splitting of fats is therefore of great
interest today as a low-energy process combined with the advantage of low thermal stress to the heat-sensitive fats. Furthermore, enzymatic splitting can be
applied to special fats which can be normally hydrolized only by saponification and neutralization (see Enzymatic Hydrolysis Processes). An improved fat-
splitting process using lipase presplitting prior to pressure splitting is described by Henkel Corporation [54]. The partial hydrolysis achieved by the presplitting
step mainly eliminates the induction period encountered during pressure splitting and leads to time savings or higher capacity of about 20 % compared to similar
nonpresplit fats.

Acid catalysts are generally very effective for accelerating hydrolysis reactions. At higher temperature, however, material corrosion occurs. This problem does
not arise when basic oxides are used as catalysts. Dibasic metal oxides have a higher activity than the more strongly alkaline monobasic metal oxides. In the
literature, zinc oxide in its active form as zinc soap is described as the most effective accelerator for hydrolysis. The Zn2+ ion functions not so much as a Lewis
acid, but rather as a phase-transfer catalyst which carries water in the form of hydrate into the lipid phase [55], [56].

Temperature. Without catalysts, the rate of fat hydrolysis is economical only above 210 °C (Table 13). The development of high-pressure techniques was the
decisive step in making hydrolysis of fats a large-scale manufacturing process. Initially, batch operation in autoclaves at medium pressures of 0.6 – 1.2 MPa was
employed.

Table 13. Influence of temperature on splitting time [57], [58]

t, °C Time to reach equilibrium, min *

Beef tallow Coconut oil Peanut oil

225 156 (62) 158 (58) 156 (50)

240 82 (34) 85 (33) 85 (25)
260 47 (18) 46 (23) 53 (16)
280 34 (8) 33 (10) 33 (10)

* In parentheses: halftime of splitting.

Modern continuous splitting units operate at 210 – 260 °C and 1.9 – 6.0 MPa. The rate of splitting in high-pressure plants is sufficiently fast without any catalysts.
With rising temperature and pressure, the mutual solubility of the two phases increases to a point where a homogeneous phase is formed. When coconut fat is
used, this occurs at 293 °C and 8.0 MPa. For tallow, the values are 321 °C and 12.0 MPa [59].

Equipment. High pressure splitting can be carried out in autoclaves, which are employed mainly in batch operation. With a battery of autoclaves in parallel, a
one-stage process can be carried out in cycles (Fig. 16). Autoclaves in series enable multistage processes to be operated batchwise or continuously with co- or
countercurrent streams [60].

Figure 16. Batch fat splitting in two parallel autoclaves with direct heating

a) Splitting autoclaves; b) Flash tank; c) Separation tank; d) Condenser

For high throughput rates, spray columns operating countercurrently are used [60], [61-63]. The main feature of this system is the countercurrent movement of
the two liquid phases as a result of their difference in density. Efficient mutual extraction is essential for fast hydrolysis of fat. This process, first described by H.
MILLS [59], has been modified by several companies. Commercial countercurrent splitting towers with varying features (e.g., internal heat transfer between lipid
and aqueous phases for energy conservation) were designed years ago, for example, by Colgate-Emery [64], Foster-Wheeler, Feld & Hahn [60], Crown Iron
Works [65] (formerly Wurster & Sanger) and Lurgi [66]. An overview on plant and equipment suppliers is given in [67]. Based on the Crown Iron Works process
[65] the main elements are shown in Figure 17.

Figure 17. Continuous fat splitting (Foster – Wheeler)

a) Splitting column (250 – 260 °C, 5 – 6 MPa); b) Flash tank; c) Level control; d) Pressure control; e) Condenser

Fat and process water (mainly condensate from the concentration of glycerol water) are pumped into a splitting column by high-pressure metering pumps. Fat is
fed in near the bottom of the column ca. 0.5 m below the interface; water is fed in at the top. The reaction zone, which lies between the upper and lower heat-
exchange zones, is heated to 250 °C by direct feeding of high-pressure steam. The upper heat-exchange zone (water – fatty acid) is provided with baffles,
whereas the lower heat-exchange zone (oil – glycerol/water) includes the interphase. In case of difficult fats (emulsion formation), feeding of the fat above the
interface is recommended. A pressure regulator controls the discharge of fatty acids at the top, and an interface regulator automatically adjusts the flow of the
glycerol-water mixture (12 – 18 % glycerol) from the bottom of the column.

Mass transfer between the lipid and aqueous phases, as described by LASCARAY [50], has a decisive influence on the final degree of fat splitting. Degrees of
splitting >98 % are achieved today by applying principles of liquid – liquid extraction, especially at the top of the splitting tower (water against fatty acid).

Steam from expansion of the glycerol – water can be used as an energy source for the following evaporation of the glycerol – water, which comes out of the
splitter with 15 – 20 % glycerol and which is generally concentrated to 88 % crude glycerol.

Continuous splitters have a consumption of high-pressure steam of about 200 kg steam per tonne of oil or lower. The ratio of the feeding rates of oil to water is
normally about 2:1. In addition, the condensate of the direct-heating steam must be added to the water phase. The oil feeding rate per unit splitter volume (empty
column) can be specified at about 200 kg h–1 m–3, which corresponds to a residence time of the lipid phase of about 4 h.

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Within the normal working range, the splitting degree (see Hydrolysis — Principles) shows a nearly linear dependence on the input flow rate of the oils. For the
same column at constant splitting temperature, the plots for different oils and fats have different positions (see Figure 18). The splitting degree decreases with
increasing input rate.

Figure 18. Splitting degrees of continuous splitting columns. Typical dependence from input rate.

The hydrolysis of fatty acid methyl esters into fatty acids and methanol is of special interest for generating short-chain fatty acids (C6 – C10) if the demand is
higher than normally generated via oil splitting and fatty acid fractionation. The equipment and the conditions of normal direct steam splitting are not applicable.
Therefore, formerly two-step processes were used, such as saponification and subsequent neutralization or transesterification with glycerol (glycerinolysis) and
then normal splitting. Both are not very economical. Recent developments describe more efficient ways by direct splitting with the help of organic catalysts such
as sulfonic acids [68] or metal soaps of organic acids [69]. The last process has been successfully used for some years on a industrial scale. Furthermore,
enzymatic splitting of fatty acid methyl esters has been developed and can be recommended as suitable process (see Enzymatic Hydrolysis Processes).

3.2.3. Enzymatic Hydrolysis Processes

The high temperatures employed for steam splitting makes this process unsuitable for sensitive triglycerides, conjugated systems, hydroxylated fats and oils,
and polyunsaturated oils with high iodine numbers (Table 14). There are also difficulties associated with alkaline hydrolysis, namely, high energy costs and the
need to acidify the formed soaps in a second step to obtain the fatty acid products.

Table 14. Disadvantageous effects of chemical hydrolysis with sensitive triglycerides

Component Disadvantage of chemical hydrolysis

Conjugated thermal degradation, isomerization
Hydroxylated dehydration, polymerization
Polyunsaturated polymerization, coloration

A goal of technology in the 21st century is to become more environmentally friendly. For this reason, industrial enzyme catalysis technology based on green
chemistry concepts is indispensable.

The enzymatic process is an alternative way to produce fatty acids, in which enzyme-catalyzed hydrolysis Enzymes – Fat Splitting is carried out under milder
conditions that restrict secondary reactions to a very low level; for example, coloration and the trans isomer content of the processed fatty acids are reduced due
to the high enzyme selectivity.

Modification of starch and proteins by enzymatic processes is well established on an industrial scale. However, the use of enzymes to modify lipids, despite the
significant research effort made in this field, is mostly still in the development stage.

The hydrolysis of oils and fats is catalyzed by lipase (EC 3.1.1.3), which breaks the ester bonds of acylglycerides. Lipases are produced by plants, animals, and
microbes. However, plant and animal enzymes are not used commercially, while microbial enzymes (fungal, yeasts, molds and bacteria) are used extensively
[70], [71].

Lipases have the particular characteristic of catalyzing the reaction only at the water/lipid interface. Thus, the surface area available for reaction is a crucial
process efficiency factor, and an excess of water is essential. Both free enzymes in emulsion systems and immobilized enzymes have been extensively studied
for performing the hydrolysis of fats and oils [72-77].

Lipases can be nonspecific enzymes that remove any fatty acid from the glycerol, e.g., lipases from Candida cylindracea [78]. Alternatively, they can be specific
for positions in the triglyceride, e.g., 1,3-specific lipases from Candida antarctica preferentially release fatty acids from postions 1 and 3 of glycerol to give fatty
acids and monoglycerides [79]. A lipase from Geotrichum candidum is specific for fatty acids with a cis-9 double bond [80].

Most microbial lipases for hydrolysis have a pH optimum of between 5 and 9 at the emulsion interface. The optimum temperature is 30 – 50 °C. Depending on
enzyme concentration, stirring, water content, number of hydrolysis steps, and oil source, nearly complete hydrolysis can be performed in 8 – 72 h.

Prolonged reaction times can eventually yield complete hydrolysis of triacylglycerides to fatty acid and glycerol when a 1,3-specific lipase is used. To circumvent
this issue, enzyme mixtures can be used in the process, as described in the enzymatic splitting process of castor oil to obtain high-quality ricinoleic acid [81]. The
enzymatic hydrolysis can be conducted as a presplitting process that is combined with subsequent chemical hydrolysis to enhance the capacity of the overall fat
splitting process [82].

As mentioned in Section Hydrolysis — Industrial Procedure methyl esters can be used instead of glycerides as further components to produce fatty acids. Most
enzymes are inactivated in the presence of small amounts of methanol or they catalyze the esterification reaction to produce methyl esters. Therefore, the
methanol content should be reduced by continuously removing methanol from the system, and water should be present in excess. There are two processes
possible to obtain short-chain fatty acids in high quality: continuous removal of a methanol – water distillate and splitting and phase separation in several steps
[83].

Lipase not only catalyzes the hydrolysis of glycerides, but can also catalyze the synthesis of esters or interesterification reactions by a reverse reaction (see
Enzymatic Esterification and Enzymes – Interesterification).

3.3. Separation of Fatty Acids

3.3.1. Distillation
Crude fatty acid mixtures from splitting contain a number of high-boiling impurities (e.g. partial glycerides, soaps, glycerol, sterols, phosphatides, pitch, color
bodies) as well as low-boiling components (water, low molecular mass hydrocarbons, aldehydes, methyl ketones, odor bodies). These impurities must be
removed by distillation to ensure the high quality of fatty acids demanded by customers. Processed crude fatty acids such as oleic acids obtained from
crystallization (see Crystallization) and modified fatty acids (see Modification of Fatty Acids), as well as fatty acid bottom products of fractionation columns are
also subjected to distillation.

On the other hand fatty acids are very reactive chemical components that can be damaged by oxidation, thermal decomposition, dehydration, polymerization,
polycondensation, and other chemical reactions taking place in manufacturing plants. Typically, the reaction rate increases exponentially with increasing process
temperature. The byproducts formed lead to a deterioration in color, color stability, odor, and other quality-control criteria. And from an economical point of view,
byproducts lead to reduced product yields, which increase manufacturing costs.

Both mentioned points have a decisive influence on the engineering design of fatty acid manufacturing plants. The equipment development since ca. 1985 has
concentrated on the chemical properties to produce fatty acids of high quality together with appropriate economic efficiency. The major requirement in the field of
fatty acid distillation is to avoid product damage. This requires the liquid to be exposed to the lowest possible boiling temperature for the shortest period of time.

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In the following two principle technologies for products of different quality and composition are considered in more detail: distillation and fractionation. Currently,
both processes are only conducted continuously. Therefore, batch processes, which were often applied in the past, are not considered.

Due to their limited thermostability, fatty acids must be distilled or fractionated at low temperature under high vacuum. However, in conventional vacuum
distillation systems the hydrostatic pressure of the liquid phase above the heating surfaces of the evaporator system partly destroys the effect of the vacuum
system. As a solution, modern falling-film evaporators are widely used. Since ca. 1985 falling-film evaporators have practically replaced the forced-recirculation
evaporators used until then. In most falling-film evaporators the heating medium is steam or heat-transfer fluids (e.g. Marlotherm, Dowtherm).

The falling-film evaporator is especially desirable from a product point of view, as it offers a short residence time. In falling-film evaporators, liquid and vapors
flow downwards in parallel. The liquid to be partially evaporated is preheated to boiling temperature. An even thin film enters the heating tubes via a distribution
device at the top of the evaporator, flows downward at boiling temperature, and is partially evaporated. This gravity-induced downward movement is increasingly
augmented by the cocurrent vapor flow.

Falling-film evaporators can be operated with very low temperature differences between the heating media and the boiling liquid, and they also have very short
product contact times, typically just a few seconds per pass. These characteristics make the falling-film evaporator particularly suitable for the partial evaporation
of fatty acids as heat-sensitive products, and it is today the most frequently used type of evaporator in the field of fatty acid distillation. Falling-film evaporators
must be designed very carefully for each operating condition; sufficient wetting of the heating surface by liquid is extremely important for trouble-free operation of
the production plant. The proper design of the liquid-distribution system is critical to achieve full and even product wetting of the tubes. If the heating surfaces are
not wetted sufficiently dry patches will occur; at worst, the heating tubes will be completely clogged. Thermal decomposition of fatty acids could occur.

Another advantage of falling-film evaporators is the low liquid holdup in this type of unit. As a result, the plant can be started up quickly.

The most important development in distillation and fractionation of fatty acid mixtures surely is the substitution of conventional trays and dumped packings by
structured packings. The main advantage is that the pressure drop of a packed bed relative to the corresponding number of theoretical stages is much less than
that of conventional trays. This pressure drop is less than 0.5 mbar per theoretical stage with a typical F factor of about 2 – 2.5 Pa0.5. This is smaller by factor of
12 – 15 than that of conventional trays.

Another advantage of structured packing is the high separation efficiency. Typical established and experimentally investigated values for distillation of fatty acids
in industrial plants are in the range 2 – 2.2 theoretical stages per meter packing (e.g., Mellapak 250, Sulzer AG) [84]). Latest developments in this field (Mellapak
Plus, Sulzer AG; Montz-Pak Type M, Montz GmbH [85-88]) ensure higher F factors without simultaneous deterioration of the separation efficiency. This leads to
distillation plants and fractionation columns that can be operated at lower pressure drop. The result is less thermal stress on the fatty acids. Therefore, the
quantity of byproducts produced by thermal decomposition is reduced. This leads to better product quality and higher product yields.

Another benefit of structured packings is the extremely small liquid holdup in comparison to conventional trays. For this reason the residence time is lower than
in the case of conventional trays. A typical holdup value of a structural packing is in the range of 2.5-3 % relative to the packing volume.

Additionally, structured packings permit a very wide range of liquid loads in the operating point of the production unit. For example, the minimum liquid load for
Mellapak 250 (Sulzer AG) is in the range of 0.2 – 0.3 m3 m–2h–1, and the upper limit ranges up to 200 m3 m–2h–1.

Another gain of structured packings is the increased safety in scale-up in comparison to conventional trays. At present there is no longer need for experimental
tests for the purpose of plant design. Modern flow-sheeting tools [89-91] guarantee a safe design.

To reduce the pressure drop in the distillation columns new types of condensers were developed and applied successfully in industrial practice. For example,
special plate-type heat exchangers [92], [93] show extremely low pressure drop. This feature reduces the top pressure of a distillation plant and ensures the
manufacture of high-quality fatty acids.

Distillation. Crude fatty acids from splitting contain a series of high-boiling impurities and lower boiling components. These impurities must be removed by
distillation. In the following some industrial examples are presented and analyzed.

In a plant offered by Lurgi [94], the crude fatty acid is predried in the drier and degasser under vacuum (Fig. 19). It is then drawn into the distillation still, which is
equipped with two sections of structured packing and internal chambers for separation of heavy ends. The chamber incorporates one or more heating elements
and baffles. Propelling steam, which expands into a large volume in the vacuum space, circulates the liquid between heating elements and baffles by the
principle of an air lift pump. The fatty acid is sprayed into a fine maze as it impinges on the baffles and heavy ends evaporate on the large liquid surface. The
nonvaporized portion accumulates at the bottom and is circulated again, while the remaining undistilled residue is continuously discharged. A falling-film
evaporator is used to reduce thermal stress on the product. An optional heat-recovery system can be applied in the top condenser.

Figure 19. Fatty acid distillation plant (Lurgi AG)

At the top of the column fatty acid vapors are condensed in surface condensers. To remove low-volatility light-end components causing odor and color, the main
distillate is taken out as a middle fraction, and the light ends as the top fraction. Heavy ends, primarily color carriers, can either be withdrawn separately or
recycled directly for complete or partial redistillation.

The above-mentioned positive features of falling-film evaporators for the distillation of fatty acid mixtures are exploited in a manufacturing process of Cognis (Fig.
20). Crude fatty acid mixture is degassed and dried, preheated, and then evaporated in a falling-film evaporator. The vapors pass through the distillation column
equipped with modern structured packings and condense stepwise in the upper part of the column in two condensers connected in series. The lower boiling
components are removed from the second total condenser. The condensate from the first (partial) condenser is returned as undercooled reflux to the rectifying
part of the distillation column. The main fraction is withdrawn above the stripping part of the distillation column. A second falling-film evaporator concentrates the
residues in a side chamber of the still. With this arrangement, a strong fractionating effect is achieved, by which low-boiling odorous substances and high-boiling
colored materials are removed.

Figure 20. Continuous fatty acid distillation (Cognis Deutschland GmbH)

a) Dryer and degasser; b) Feed preheater; c) Falling-film evaporator; d) Distillation column; e) Internal condensation section; f) Falling-film evaporator (pitch
stage); g) Residue cooler; h) Reflux cooler; i) Reflux condenser; j) Light-ends condenser; k) Cooler for main distillate reflux; l) Distillate cooler

Fractional Distillation. Fractional distillation is applied to obtain products of high purity. Typical raw materials are fatty acid mixtures with chain lengths of C6 –
C18 from the splitting of coconut or palm-kernel oil and unsaturated C18 – C22 fatty acids from the splitting of rapeseed oil. The purity required for the products

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(referred to as fatty acid fractions in this section) is up to 99 %. Separation of fatty acids from resin acids in tall oil [95] is also accomplished by fractional
distillation, while the fractionation of tallow, soybean, cottonseed, and linseed fatty acids is of lesser importance.

Separation usually takes place in vacuum distillation columns, column systems, or complex distillation arrangements with sophisticated internals (new generation
of modern structured packings) to intensify mass and energy transport between the vapor and liquid phases and to minimize pressure drop in the columns.
Before fractionation begins, the crude fatty acid must be degassed and dried. The final step is overhead distillation of the bottom product of the last column to
improve the color.

In the bottom of the column, heat is supplied by means of falling-film evaporators. In the top of the column heat is removed by surface condensers. The vacuum
system includes a multistage jet pump which permits a pressure of less than 2 – 3 mbar at the top of the column. Sealing the plant is particularly important
because the presence of atmospheric oxygen results in rapid oxidation of fatty acids.

Column systems are being increasingly applied for the fractionation of fatty acid mixtures. The simplest case is a production plant with a system of several
distillation columns connected in series (Fig. 21) [96]. The multicomponent mixture from splitting is first degassed and dried in a dryer. Then the mixture is fed to
a system of distillation columns. Separation takes place in all columns in two product streams: top and bottom product streams.

Figure 21. Sequence of fatty acid fractionation columns (Sulzer AG)

Figure 22 illustrates an improved alternative for the separation of crude coconut or palm kernel fatty acid [97]. Here, three products are simultaneously
manufactured in a distillation column with a sidestream. The precut (C6 – C10) forms the top product. The bottom product contains the C16 – C18 components.
The fraction C12 – C14 is produced as a sidestream. This sidestream is separated in two further columns to produce the C12 products and C14 products. The
precut is specially treated and is used in a column system for the production of C6, C8, and C10 fatty acid fractions. For the separation of the C16 – C18 bottom
product of the first column a sidestream column can be used again to obtain, e.g., a 16/70 % fraction as top, 18/92-94 % as sidestream, and a bottom fraction of
C18 and higher.

Figure 22. Fractionation of fatty acid mixture in a sequence of distillation columns with sidestreams

For all considered separation processes one distillation column can also be used several times, but this approach is not economical. The reason is repeated
cooling and heating of the product streams, which raises energy costs and deteriorates the quality of the end products due to longer residence time.
Furthermore, this technical solution demands many additional tanks for intermediate products.

A further application of a column with sidestream (Figure 23) permits production of the three products (C16 – C18, C18 – C20, and C22) in one run [97]. The aim
of the separation procedure is the production of erucic and behenic acid from the raw material after the splitting of erucic-rich rapeseed oil. In this case low top
pressure, low pressure drop, and short residence time of the products in a distillation column due to the high temperature (ca. 270 °C) are important.

Figure 23. Manufacturing of erucic and behenic acids

The above-mentioned systems cover two or three product streams in distillation columns connected in series. Figure 24 shows two conventional arrangements
for the separation of a typical four-component mixture (usually known as direct and indirect sequences). Process integration has proven to be very successful in
reducing the energy costs for conventional distillation arrangements. One of the most significant nonconventional arrangements involves “thermal coupling”.
Figure 25 shows a short survey of nonconventional arrangements which use thermal coupling. In thermal coupling part of the heat transfer necessary for
separation is provided by direct contact via the product flows. Typically, the arrangement consists of a main distillation column surrounded by additional devices
such as prefractionator, side stripper, and side rectifier.

Figure 24. Conventional structures for the separation of a ternary system

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Figure 25. Complex distillation arrangements

The key advantage of the complex column over a sequence of simple columns is more compact equipment and substantial reduction of investment and
manufacturing costs, instrumentation, man power, and maintenance. The application of these arrangements in industrial practice is changing rapidly because of
recent advances in simulation, dynamics and control.

An interesting solution in the field of multicomponent distillation of oleochemical mixtures is a column with a vertical partition, proposed by Sulzer Chemtech for
the separation of fatty acids [96]. This configuration is shown in Figure 26 and is often referred to as a dividing-wall column [98]. The advantage of this
partitioned column is that a ternary mixture can be distilled into pure product streams with only one column, one reboiler, and one condenser. This reduces the
cost of separation in comparison to sidestream columns or column systems [99-102]. It is expected that all above-mentioned complex arrangements will expand
into the fractionation of fatty acid mixtures increasingly in the future because of clear economic advantages.

Figure 26. Dividing-wall column

Process Control. The increasing role of product quality control of distillation columns for manufacturing of fatty acids is significant. Driven not only by meeting
fatty acid specifications and economic goals, distillation columns must also satisfy new customer demands. In many distillation columns product quality has been
directly controlled by means of temperatures inside the column. However, since the feed to the distillation columns consists of multicomponent mixtures and they
are often changed by operating conditions of the upstream units, rigid relations do not always exist between column temperatures and product qualities. In this
context, it is difficult to control product quality by using column temperatures. In the modern oleochemical industry, there is a strong emphasis on the use of
process analyzers to provide real-time process quality data for the purpose of maximum operating efficiency.

Fatty acids manufactured by using distillation columns with liquid or vapor sidestreams instead of two or more columns mostly require higher utility usage.
Therefore, the application of these columns provides significant economic incentives of reduced capital and operating expenses. On the other hand, they also
pose a more challenging control problem than standard distillation columns. Columns with a liquid or vapor sidestream have an additional degree of freedom and
therefore an additional dimension of coupling. Therefore, these columns are generally more difficult to control than typical distillation units.

A newer process control concept for fatty acid qualities in distillation columns with a liquid sidestream has been presented [103]. The fatty acid composition is
determined by an on-line gas chromatograph (Fig. 27). The determined product composition is then checked for consistency by an expert system embedded in
the distributed control system (DCS). An additional supervision level is a fundamental element of the control system, implemented in the DCS and consisting of
two basic parts: a diagnostic and an information level. The basic function guarantees an error-free operational sequence of the composition control by
interception of all uncertain information due to the plant operator (errors in setpoints, product specifications) or the measurement procedure (errors of analyzing
system). The next step of the control system covers composition control (Fig. 27). It was realized by using decentralized, time-discrete PI controllers [104]. A
special user interface in the DCS for the plant operator was developed as a diagnosis, information and warning platform.

Figure 27. Process control system with on-line gas chromatograph

In summary, only the successful integration of all mentioned elements of the developed composition control system guarantees a stable operating point of the
fatty acid fractionation plant.

3.3.2. Crystallization
Separation by crystallization means the separation of a fatty acid mixture into a higher melting fraction, consisting mainly of saturated acids, and a lower melting
fraction, consisting mostly of unsaturated acids.

The prototype of this process is the separation of tallow fatty acids into stearic acid (stearin) and oleic acid (olein). The stearin obtained from this separation has
an iodine value of less than 20 and is normally hardened subsequently to an iodine value of 1. The crude olein obtained has a cloud point below 3 °C. Apart from
tallow fatty acid, distilled or crude fatty acids from the splitting of, bonefat, soybean, sunflower, palm, rapeseed oil or the C16 – C18 fraction of palm kernel fatty
acid can be employed.

When molten fatty acids such as tallow fatty acid are cooled, the higher melting, saturated constituents crystallize first, while the appreciably lower melting,
unsaturated constituents remain liquid over a defined temperature range. Because of the formation of mixed crystals, the solid phase still contains residual
unsaturated fatty acids. Conversely, residual saturated fatty acids are found in the liquid phase because of their solubility in unsaturated fatty acids. Since
various chain lengths and degrees of saturation are present in natural fatty acid mixtures, a theoretical discussion of this solid – liquid equilibrium is extremely
difficult. From the experimentally determined phase diagram for tallow fatty acid, the composition and quantitative ratio of the two phases “stearin” and “olein”
can be seen in relationship to temperature and to the composition of the starting material (Fig. 28).

Figure 28. Phase diagram of tallow fatty acids

A = saturated fatty acids; B = unsaturated fatty acids [105]

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Olein must be removed at a temperature corresponding to the desired olein content. However, because the olein content of stearin increases with decreasing
temperature, separation at higher temperature of a stearin with a low olein content may be advisable. Separation of the liquid phase can then be carried out in a
second step at a lower temperature.

Fractional Crystallization without Additives. In the “panning and pressing process, ”the molten tallow fatty acid is cooled slowly to ambient temperature in flat
aluminum pans. Fatty acid cakes are wrapped in cloths and separated from the liquid fraction in hydraulic presses. The liquid from the first pressing is cooled to
5 – 10 °C, and more stearin crystals are removed, which results in an olein with a cloud point of 5 – 10 °C. Today, the pressing process is no longer used
because it is labor-intensive and separation is poor [31].

The fractional crystallization developed by Sulzer [106] is a solvent-free batch process divided into the three principal steps of 1) crystallization, 2) partial melting
(sweating), and 3) melting. Depending on the purity of the final product the simpler process of static crystallization can be applied or, in the case of higher
qualities, falling-film crystallization. The static crystallizer uses cooling plates immersed in a stagnant melt, whereas the falling-film crystallizer is equipped with a
tube bundle that is cooled from outside, and the processed melt is pumped in a loop through the tubes. Both processes can be combined with each other or with
other processes such as distillation. Typical applications are monomer purification and isomer separation to obtain purified products such as acrylic acid or
paraffin waxes. In the case of fatty acids the static unit is used for enrichment of unsaturated acids based on rapeseed, soybean, or sunflower oil.

Fractional Crystallization with Addition of a Wetting Agent. Liquid and solid phases can be separated more easily and more completely if an aqueous
solution of a wetting agent is added to the crystal paste. The stearin crystals are wetted by the wetting agent and form an aqueous suspension which is
separated from the olein phase by centrifugation.

This principle was developed by Henkel as a continuous, two-stage hydrophilization process [107]. The mode of operation can be seen from the flow diagram
(Fig. 29). Lurgi built in the past one- and two-stage plants based on this principle [108], [109].

Figure 29. Flow diagram of two-stage hydrophilization process

a) Stirred vessel (wetting); b) Centrifuge; c) Cooler; d) Heater; Settling tank (separation of wetting solution); f) Settling tank (washing stage)

Stearin crystals form when molten tallow fatty acid is cooled to ca. 20 °C. The aqueous wetting agent solution containing a hydrophilization component such as
sodium lauryl sulfate and an electrolyte such as magnesium sulfate is added to the mixture of stearin crystals and liquid olein, and the crystals are thus wetted.
The stearin – water suspension is separated from olein in a centrifuge. Olein from the first stage is cooled in a second step to the desired cloud point, treated
again with a solution of wetting agent, and separated in a centrifuge. The cold stearin suspension from the first stage is heated to above the melting point of the
stearic acid and separated from the wetting agent solution. Before additional processing (e.g., final hardening), the stearin is washed and dried under vacuum.
The stearin suspension from the second stage is recycled by adding it to the starting material for the first stage. The solution of wetting agent and electrolyte is
also recycled; only a small amount of fresh material must be added continuously to maintain optimal concentration. Cooling is normally carried out indirectly by
passing chilled brine through the outer jacket of a scraped surface crystallizer. Otherwise, the mixture can be cooled by evaporating part of the water under
vacuum.

The hydrophilization is sometimes referred to as the Henkel [31], the Lipofrac [110], or the Lanza (Unilever) [111] process.

Fractional Crystallization from Solvents. Another method of crystallization is based upon the fact that saturated fatty acids are less soluble than their
unsaturated counterparts in organic solvents such as methanol, hexane, or acetone. The first process of this type was put into operation by Emery (Emersol
plant, Fig. 30) [31], [112].

Figure 30. Flow diagram of Emersol® crystallization plant (Cognis Corporation)

(a)economizer (b)crystallizers (c)vacuum pump (d)vent scrubber (e)seal liquid receiver (f)filter (g)cake melt tank (h)wash chiller (i)wash receiver (j)filtrate
economizer (k)filtrate receiver (l)wash economizer (m)wash alcohol receiver (n)process alcohol (o)oleic preheater (p)alcohol condenser (q)oleic evaporator (r)
stearic surge tank (s)oleic surge tank (t)oleic still (u)oleic drier (v)preheater (w)stearic still (x)stearic drier

A ca. 30 % solution of, for example, tallow fatty acid in 90 – 95 % methanol is cooled continuously to –12 °C in a tubular crystallizer equipped with scrapers.
Optionally, a crystal promoter or modifier may be added to the process to improve the separation efficiency [113]. From the resulting crystal paste, the mother
liquor containing mainly unsaturated fatty acids is sucked through a rotating vacuum filter. The filter cake, which contains saturated fatty acids, is washed free of
the mother liquor and melted. The solvent is recovered from both the filter cake and the mother liquor by distillation. The stearin obtained still contains ca. 5 –
15 % oleic acid and has an iodine value of ca. 5 – 15. Depending on the filtration temperature, the olein has a cloud point from 1 to 8 °C [114].

The corresponding Armour process applies acetone as a solvent [115], [116]. Indirect cooling can be replaced by direct cooling, e.g., by partial evaporation of
the solvent at reduced pressure [117], [118].

The Bernardini [119] and Rau [120] processes also operate on the principle of fractional crystallization from solvents.

Common to all these processes is the need for extensive safety measures (explosion prevention) and for environmental protection with respect to the emission
of solvents. Recovery of solvents requires additional equipment and energy.

Adductive Crystallization with Urea. Adductive crystallization with urea, that is, formation of urea inclusion compounds, is a well-known technique for
fractionation of fatty acids. The method is useful to separate saturated fatty acids from unsaturated and to isolate selectively a variety of polyunsaturated fatty
acids (PUFAs) from lipid mixtures, e.g., to increase the nutritional quality of the fatty acids.

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For example 97 – 99 % oleic acid containing only 0.2 % polyunsaturated material has been obtained from olive oil fatty acid [121]. The fatty acids in soybean,
fish, wheat germ, and grape-seed oils have also been separated by this method [122].

The main selectivities of this procedure are [123]:

z Enhanced selectivity against inclusion with increasing number of double bonds per fatty acid molecule
z Preferences for fatty acids of longer chain length
z Preference for trans versus cis double bonds in inclusion
z Sensitivity for double bond position

Processes for fatty acid fractionation [123], [124-127] are listed in Table 15.

Table 15. Fractionation of fatty acids by formation of urea inclusion compounds

Fatty acid source Application

Fish oil isolation of EPA* and DHA*
Linseed oil isolation of ALA*
Rapeseed oil removal of saturated fatty acid
Borage oil isolation of GLA*
CLA reaction mixture isolation of 18:2 (9c, 11 t) and 18:2 (10t, 12c)

*EPA: eicosapentenioc acid; DHA: docosahexenoic acid; ALA: -linolenic acid; GLA: -linolenic acid CLA: conjugated linoleic acid.

The formation of urea inclusion compounds is an exothermic and equilibrium reaction. The equilibrium and stability constants of urea complexes for different fatty
acids are listed in Table 16 [128].

Table 16. Equilibrium and stability constants of urea complexes for different fatty acids

Component Equilibrium constant K Stability constant 1/K

Caprylic acid 0.07 14
Caprinic acid 0.0185 54
Lauric acid 0.0063 159
Myristic acid 0.0029 345
Palmitic acid 0.0017 588
Stearic acid 0.0002 5000
Oleic acid 0.0024 476
Linoleic acid 0.019 53

The differences in the constants show that fractionation is possible under certain conditions.

A scheme of a urea complexation and crystallization process for separating saturated from unsaturated fatty acids is demonstrated in Figure 31.

Figure 31. Process scheme for separation of saturated and unsaturated fatty acids with urea complexation [128]

Other Separation Methods.

Adsorption. For the separation of oleic and linoleic acids, UOP recommends an acid-resistant, hydrophobic, non-zeolite molecular sieve (Silicalite) [129]. Oleic
acid is first selectively adsorbed and later displaced with the aid of a solvent. A nonionic, hydrophobic, spatially cross-linked styrene polymer has been used for
the same purpose [130].

Extraction. Laboratory separation of stearic and oleic acids has been achieved by high-pressure extraction with a supercritical gas at 10 MPa and ca. 130 °C
[131]. Benzene was used as solvent and ethylene as extractant.

The solubility of oleic, stearic, and behenic acids in supercritical carbon dioxide has been investigated at 40 and 60 °C and 10 – 25 MPa. A significant
enrichment of oleic acid compared to stearic acid is observed only above 20 MPa [132]. Enrichment depends on the rate of material transfer and on the relative
rates of movement of the phases, so that a separation can be expected after brief extraction [133].

High-purity oleic, linoleic, and linolenic acids have been prepared by means of liquid – liquid extraction, with solvent pairs such as furfural – hexane and ethanol
– petrol ether [134].

Separation in the Presence of Acid Soaps. In the system soap – fatty acid – water, micelles known as “acid soaps ”form at certain concentrations [135]. Acid
soaps of saturated acids crystallize from aqueous solution, whereas those of unsaturated acids remain in solution. Thus two fractions are obtained with differing
degrees of saturation [136].

3.4. Modification of Fatty Acids

3.4.1. Hydrogenation
Catalytic hydrogenation of unsaturated fatty acids can be carried out in such a way that the carboxyl group is retained and saturated fatty acids are formed [137]
by addition of hydrogen. Because of the increase in the degree of saturation, the melting point of the fatty acids increases. This process is generally known as
hardening. Hardening of fatty acids usually means complete saturation of the carbon – carbon double bonds down to an iodine value less than 1. In this way,
light-colored fatty acids are obtained which are thermally more stable and resistant to oxidation. Starting materials are, for example, split fatty acids from tallow,
the stearin fraction from the olein – stearin separation process, fatty acid fractions from rapeseed oil (erucic acid), and lauric acid, and acid oils from the refining
of edible oils. A short overview on fatty acid hydrogenation is given in [138].

Chemistry and Reaction Conditions. The hardening reaction, i.e., the addition of hydrogen to the double bonds of unsaturated fatty acids, is exothermic. Like
other types of heterogeneous catalysis, the reaction proceeds in stages [49]:

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Highly unsaturated fatty acids are hydrogenated more rapidly than monounsaturated fatty acids (k3 > k2 > k1). Hydrogenation is accompanied by isomerization
processes in which double bonds migrate (conjugation) and geometrical changes occur (cis – trans isomerism) [139]. Because fatty acid hardening is carried out
predominantly to achieve complete saturation, the selectivity of the reaction (i.e., the ratio k3: k2 (2 – 3) or k2: k1 (10 – 50) Fats and Fatty Oils) is only of
importance in some special cases [140]. It has more relevance in oil hardening, e.g., of soybean or rapeseed oil to achieve higher concentrations of
monounsaturated acids by selective hydrogenation of the linolenic and linoleic content.

To some extent, the fatty acid reacts with the nickel catalyst, particularly in the absence of hydrogen and in the presence of water, to form nickel soaps [141],
[142]:

Because nickel soaps are catalytically inactive, this reaction blocks the active surface of the catalyst. To reduce soap formation, the reaction with hydrogen is
carried out at higher pressure [143], generally 2.0 – 3.0 MPa, and the fatty acids are predried. Despite these precautions, catalyst consumption is appreciably
higher in the hardening of fatty acids than in hydrogenation of the corresponding triglycerides. The rate of hydrogenation increases initially with increasing
temperature, then passes through a maximum in the range of 180 – 210 °C depending on the fatty acid used, and finally decreases [144]. Starting temperature
of the reaction is in practice about 150 °C. Hydrogen transport through the liquid to the surface of the catalyst is dependent on the presence of large interfaces
between the phases. Hardening is therefore carried out with intensive mixing by means of stirrers or circulation pumps. Newer developments show that sound
waves also are suitable to accelerate the reaction [145]. The influence of various reaction parameters on the reaction rate of fatty acid hardening [146] is
illustrated in Figure 32.

Figure 32. Effect of operating variables on the reaction rate of fatty acid hydrogenation

The average practical reaction rate corresponds to a reduction of the iodine value by 1 – 2 units per minute. A reduction of 1 in the iodine value corresponds to
the consumption of ca. 1 m3 (STP) of hydrogen per cubic meter of fatty acid and results in a temperature increase of ca. 1.5 °C.

It was further found that formation of nickel soap in the absence of hydrogen depends on temperature and is relatively fast, especially at temperatures normally
used for hydrogenation [147]. This has an impact on the remaining nickel content of the hydrogenated fatty acid and subsequently of the distillation residue.

Catalysts. The hardening of fatty acids on a commercial scale is mostly carried out with nickel-based heterogeneous catalysts in slurry form. Dry reduced carrier
catalysts (nickel on silica) with high activity and a good resistance to poisoning are used. The active surface of this type of catalyst has been increased to over
100 m2/g. The pore diameter of the carrier must be large enough (ca. 3 nm) to allow transport of fatty acid molecules to the nickel crystallites. The nickel carrier
catalyst is pyrophoric in its activated form. For safer transport and handling, the catalyst is passivated temporarily by a coating of hydrogenated fat and normally
sold as pellets in drums. A typical catalyst has the following composition: 20 – 25 % nickel, 10 – 15 % silica, and 60 – 65 % fat. Catalyst consumption depends
on the properties of the feedstock and the intended reduction in iodine number, as well as on the hardening conditions. Therefore prior laboratory trials are
useful. A gross catalyst consumption of 0.2 – 0.4 % relative to the feedstock is the normal range. Detailed selectivity data of nickel catalysts are given in [148].

Higher selectivity is obtained when heterogeneous copper or palladium catalysts are applied [149]. Homogeneous catalysis by a liquid – liquid two-phase
technique with a solvent-stabilized palladium colloid is described in [150].

A number of other catalysts have been described [151]. Acid- and poison-resistant catalysts in pellet form have been investigated for continuous hydrogenation
of fatty acids in a fixed-bed process. Catalysts in pellet form based on noble metals are acid resistant, but they are deactivated rather quickly, especially when
crude fatty acids are used as feedstock [152].

Manufacturing Procedure. In principle, the same plants can be used for the hydrogenation of fatty acids and for the hardening of oils. Plants in which fatty
acids are processed, however, require stainless steel as construction material. The reactor is designed for pressures up to ca. 3.5 MPa. An increasing number of
hardening plants operate continuously. The economics of batch operation have been improved significantly by heat recovery systems [153]. Despite good acid
resistance of the catalyst, after filtration the hardened fatty acids still contain nickel soap. To minimize this content, the reactor should be discharged by the
hydrogen pressure and the hardened fatty acid should be cooled (heat recovery) to about 80 – 120 °C before filtration under ambient conditions. The hardening
step is usually followed by distillation to remove the nickel soap and to free the hardened fatty acids from the odor that arises during hardening.

Figure 33 shows a typical batch hardening plant. Hardening is carried out in batches of 5 – 30 t. Thorough mixing by effective agitators keeps the catalyst
suspended and the hydrogen well dispersed.

Figure 33. Batch hydrogenation plant

a) Dryer; b) Autoclave; c) Cooler; d) Filter

Particularly thorough mixing is achieved with the reaction loop designed by Lurgi or by Davy Process Technology (formerly Buss); see Fats and Fatty Oils).
This process can be carried out batchwise in a single reactor or nearly continuously by using several reactor loops in series [154], [155].The plant can also be
equipped with a heat recovery system.

In the continuous slurry hardening process developed by Lurgi, a mixture of dried fatty acid, nickel catalyst slurry, and hydrogen is fed into the bottom of the
reactor which consists of several chambers. The fatty acid passes through the reactor only once, while the excess of hydrogen is recycled ( Fats and Fatty
Oils).

Alternatively, continuous hardening can also be carried out in fixed-bed reactors in the presence of a noble metal (e.g., palladium) pellet catalyst [156]. The
feedstock, together with the hydrogen, directly enters the trickle bed at the top of the mixed-phase reactor. The process is free of any slurry handling and
eliminates metal soap formation and therefore nickel contamination and nickel residues. A process designed by Lurgi [157] is shown in Figure 34. Also fixed-bed
reactors in form of tube-bundle reactors can be used. Such equipment was also developed for the hydrogenation of fatty methyl esters to fatty alcohols [158].
The major advantage is that the tubes filled with the catalyst pellets can be cooled very effectively to remove the exothermic heat and to avoid hot spots. A
simulation program for the scale-up of trickle bed hydrogenation reactors are described by [159].

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Figure 34. Continuous hydrogenation with fixed bed reactor (Lurgi AG)

3.4.2. Double-Bond Isomerization

Isomerization can be split in two main fields of commercial interest: isomerization of monoenes (cis/trans) and isomerization of dienes (conjugation).

Monoene Isomerization. Natural fatty acids occur mostly in the higher energy cis configuration. The conversion of oleic acid (cis configuration) into elaidic acid
(trans configuration) is carried out industrially by treating oleic acid with sulfur dioxide, oxides of nitrogen, selenium, or acid-activated earths at 100 – 200 °C. The
rearrangement reaches an equilibrium at 75 – 80 % elaidic acid [160-162].

Partial hydrogenation of polyunsaturated fatty acids always increases the proportion of trans isomers. Therefore, this process can be used specifically for the
preparation of technical elaidic acid. Selective partial hardening of oils for the food industry is carried out to increase the melting point of the oil. In this case low
cis-trans isomerization is of interest. Today trans fatty acids are avoided in food applications because of negative health effects on blood cholesterol levels [163].
It was found that temperature, pressure, and catalyst type are the main parameters for formation of trans isomers. Operating at lower temperature and higher
pressure with a noble metal catalyst results in a large drop in trans formation but also reduced selectivity [164-167].

Reduced formation of trans fatty acids was also achieved by using special types of zeolites suitable for triglycerides as well as for fatty acids [168], [169].

Another way to control of the melting point of fats without any problems with trans isomers is interesterification of completely saturated triglycerides with
unhydrogenated oils (mostly cis).

Diene Isomerization. The conjugation of dienoic fatty acids has some commercial importance because of the higher reactivity of conjugated unsaturated fatty
acids in technical applications such as alkyd resins and because of effects of single isomers in human nutrition [170]. Conjugated systems for technical
applications are formed by alkali-catalyzed isomerization of nonconjugated fatty acids, e.g., fatty acids from sunflower or soybean oil:

The conjugation of diene fatty acids is carried out by saponification with an aqueous alkali solution and heating with excess alkali to 200 – 300 °C. The soap
paste is treated with mineral acid to recover the fatty acid mixture. The degree of conjugation achieved is 95 % [171], [172]. The conjugated diene fatty acids
obtained are partially isomerized, so that a mixture of the cis-cis, cis-trans, trans-cis, and trans-trans configurations is formed.

For the more selective preparation of conjugated linoleic acid isomers, a catalytic isomerization process starting from the monoester of linoleic acid has been
developed [173]. This process leads mainly to the 9-cis-11-trans and the 10-trans-12-cis isomers and avoids the formation of other species. Due to growing
scientific interest in the biological effects of the single isomers [174], a synthesis of the pure 9-cis-11-trans isomer starting from ricinoleic acid has also been
published [175], [176].

3.4.3. Dehydration
Fatty acids with a hydroxyl group in the carbon chain can be dehydrated. Ricinenic acid is obtained by dehydration of ricinoleic acid [177]. Ricinenic acid is a
mixture of ca. 30 % conjugated 9,11-linoleic acid and ca. 50 % unconjugated 9,12-linoleic acid. The double bonds are partly in the trans configuration. By
subsequent conjugation, a ricinene fatty acid with an increased content of conjugated double bonds can be prepared. A similar process is known for the
dehydration of castor oil ( Drying Oils and Related Products).

3.4.4. Dimerization
Unsaturated fatty acids can undergo self-condensation reactions to form high molecular weight dibasic and polybasic acids. Thermal condensation of
unsaturated fatty acids was reported in the early 1900s [178], [179] and patents for commercial processes were issued to Emery Industries in 1949 [180] and
1953 [181]. This thermal condensation is believed to be a Diels – Alder type reaction, and the reaction rates are reported to be proportional to the degree of
unsaturation [182], [183]. The products are known as dimer acids ( Dicarboxylic Acids, Aliphatic – Dimer Acids). The feedstocks used are generally highly
unsaturated C18 fatty acids derived from vegetable sources such as tall oil.

By the 1950s patents had been issued for catalytic condensation processes [184], [185]. The catalytic condensation reaction is believed to proceed via a
carbonium ion intermediate [186] and is much less dependent on degree of unsaturation, which allows even mono-unsaturated fatty acids (e.g., oleic acid) to
condense. The principal process flow sheet is given in Figure 35.

Figure 35. Principle process scheme for dimer production

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Dimer acids are known to be a mixture of many chemical isomers with branching in their structure; therefore, they are liquid at room temperature. It was shown
that they contain acyclic, cyclic, and aromatic structures, all of which show many isomers [187], [188].

The carbonium ion intermediate in this reaction can also undergo rearrangement to form a branched-chain monomeric acid, which is the source of commercial
grades of isostearic acid [182]. The isostearic acid is obtained by hydrogenating the monomer acid and then separating into liquid and solid components. The
liquid fraction is termed isostearic acid.

A special type of dimerization is the formation of so-called estolides, which are formed from two or more fatty acids when the carboxyl group of one fatty acid
reacts with the double bond or hydroxyl group of another. Estolides are found naturally in some oils (e.g. Euphorbiaceae), but mostly are sythetically produced
from ricinoleic acid (12-hydroxy-9-octadecenoic acid) or oleic acid [189], [190], as shown in Figure 36. Also the use of meadowfoam oil fatty acid (64 % C20:1,
cis-9-eicosenoic acid) has been reported [191]. In principal estolides can be characterized as fatty acid polymers with ester bonds and monocarboxylic acid
functionality.

Figure 36. Formation of estolides (A: ricinoleic acid, B: oleic acid)

3.4.5. Ozonolysis
Oxidative cleavage of the double bond of oleic acid has been known for many years. This process leads to a C9 dicarboxylic acid (azelaic acid, Dicarboxylic
Acids, Aliphatic – Degradative Methods) as main product and to C9 monocarboxylic acid (nonanoic or pelargonic acid). A first commercial process was
introduced in the late 1940s using chromium acid as oxidative agent [192]. Later the oxidative cleavage of oleic acid was carried out with ozone and an oxidative
treatment [193], [194]. In the first stage, ozone is added to the double bond of oleic acid. The reaction is carried out preferably at 25 – 45 °C with oxygen
containing 1 – 5 % ozone. In a second reaction stage, the ozonide is then split by oxidation with ozone-free oxygen to form crude azelaic and pelargonic acids.
This step is carried out at 75 – 120 °C. Afterwards further steps for purification of the crude azelaic acid are necessary [195]. Azelaic acid is used for the
production of specialty nylons, ester and polyester for elastomers, polyamide fibers, resins, lubricants, and also in cosmetic applications for skin care and an
active ingredient for the treatment of acne vulgaris [196].

3.4.6. Thermal Decomposition

Heptanoic acid is produced by Atochem in France by thermal decomposition of esters made from castor oil. At 500 – 600 °C, ricinoleic acid methyl ester
decomposes in the presence of water vapor to form oenanthal (heptanal) and undecenoic acid methyl ester. The oenanthal is then oxidized with oxygen to
heptanoic acid [197]. The main product, undecenoic acid, is used as starting material in the manufacture of nylon 11 (Rilsan).

The alkaline cleavage of ricinoleic acid or castor oil at higher temperature leads to sebacic acid and 2-octanol as a byproduct [198] ( Dicarboxylic Acids,
Aliphatic – Degradative Methods).

3.4.7. Biooxidation
In the biooxidation process a terminal methyl group of the fatty acid is transformed into a carboxyl group without shortening the carbon chain. This fermentation
method is useful for the production of long-chain dicarboxylic (dibasic) acids (carbon number > C12). The microorganism used in the process is a genetically
engineered yeast, Candida tropicalis [199]. The process has been developed since 1985, starting with modification of the Canidida tropicalis strain [200], [201].
The complex fermentation procedure is followed by extensive downstream processing to produce purified dicarboxylic acids (see Fig. 37) [202-204]. An overview
on existing routes for the different carbon chain lengths together with the new possibilities via biooxidation is given in Figure 38. The long-chain dicarboxylic
acids are mainly used in polymer and hot-melt adhesive applications.

Figure 37. Process scheme for production of long chain dicarboxylic acids

Figure 38. Existing routes and new route via biooxidation for production of dicarboxylic Acids [205]

DDDA: Dodecanediacid

3.4.8. Enzymatic Esterification

Lipases not only catalyze the hydrolysis of glycerides, they can also catalyze the esterification of fatty acids with alcohols to give different esters.

Most nonpolar organic liquids generally deactivate biocatalysts, though many remain active in polar solvents like acetone or water. Modification of the biocatalyst
may stabilize it against deactivation. Immobilized lipases have been found to remain active in anhydrous organic solvents [206-211]. This property enables
lipases to be widely used as biocatalysts in organic syntheses of various useful esters.

Esterification is the reaction between a fatty acid and an alcohol.

Water as a product of the reaction has dramatic effects on shifting the reaction equilibrium. It must be continuously removed from the system to enhance the
yield. On the other hand, a certain dynamic water environment should be maintained in order to have high enzyme activity. The removal rate of water from the
reaction system should be carefully controlled in order not to dry out the lipase. The most common methods to remove water from the reaction system are
vacuum and membrane evaporation, azeotropic solvent distillation, drying agents, and bubbling of dry nitrogen [212].

The development of enzyme immobilization enables the enzyme esterification process to be performed at low water contents. The immobilized enzyme is
surrounded with water on the carrier (microaqueous reaction system) while the overall water content of the system is low (see Fig. 39).

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Figure 39. Scheme for immobilized enzyme and water content in the reaction system

The immobilization technique enables enzymatic esterification to compete with chemical esterification processes both with respect to operational and capital
costs. Production rates of several thousands of kilograms of product per kilogram of immobilized catalyst and operational lifetimes of up to several months in
packed-bed reactors or slurry systems encourage use of enzymatic catalysis [213].

At the same time the enzyme process produces pure products with respect to functionality, quality, and health aspects. Due to their high catalytic activity at
ambient temperature and under mild reaction conditions it is possible to use their stereoselectivity toward a broad range of substrates and to synthesize
enantiomerically pure intermediates [214], [215].

Owing to the solvent capability of most of the alcohols, esterification can be performed in solvent-free, homogeneous systems to increase the economic
profitability of the process [216].

Meanwhile a large range of alcohols has been used for the synthesis of a variety of ester compounds. Table 17 lists some examples [212].

Table 17. Products from enzymatic esterification of C6–C26 fatty acids

OH source Products/applications
Straight-chain alcohols (C1–C18) biofuel, emollients, cosmetics
Straight chain alcohols (C19–C28) wax esters
Branched chain alcohols (C3–28) wax esters, lubricants
Glycerol and glycerides triglycerides, 1,3- or 1,2-diglycerides, 1- or 2-monoglycerides, functional foods, emulsifiers
Glucose, fructose, etc sugar and fructose esters, active cosmetics, emulsifiers
Sterols sterol esters, functional foods
Ascorbic acid ascorbyl esters, food preservative
Glycols glycol esters, cosmetics

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4. Production of Synthetic Fatty Acids

Mixtures of saturated fatty acids have been manufactured in the past by oxidation of alkanes, but have no economic relevance today. This process led to fatty
acids with odd-numbered and branched carbon chains that were inferior in quality and were therefore mainly used in technical applications [217-220], [221].

Specific fatty acids for technical applications are produced from olefins by hydroformylation and hydrocarboxylation.

At present, no economical synthesis for unsaturated, even-numbered, long-chain fatty acids (e.g., cis-9-octadecenoic acid) exists.

4.1. Hydroformylation
In the oxo reaction discovered by ROELEN, carbon monoxide and hydrogen are added to the double bond of olefins to form aldehydes ( Oxo Synthesis). This
highly exothermic reaction takes place only in the presence of catalysts at temperatures above 180 °C and pressures of 8 – 30 MPa. Oxidation of the
intermediate aldehyde yields the desired fatty acid. By starting with terminal linear olefins, both straight-chain and -branched-chain fatty acids can be obtained
[222]. The ratio of straight-chain to branched-chain fatty acids can be varied by changing the catalyst in the hydroformylation reaction. Suitable catalysts are
cobalt compounds or rhodium phosphine complexes. The latter result in a higher percentage of straight-chain compounds. Celanese employs this process [223],
[224]. Fatty acids with varying degrees of branching are produced in the range of heptanoic to nonanoic acid.

4.2. Hydrocarboxylation
In a similar reaction, the Koch – Haaf method, carbon monoxide is added to the double bond of olefins in the presence of strong acids. In a second step, the
intermediate product reacts with water to form branched-chain fatty acids [225]. Concentrated sulfuric acid, phosphoric acid, hydrogen fluoride, or boron
trifluoride can be used as catalyst. The reaction mechanism involves a carbonium ion, which reacts with carbon monoxide to form an acylium ion. This then
reacts with water to form carboxylic acid. Fatty acids with highly branched chains result from rearrangement of the carbonium ion. The process operates under
mild conditions up to 80 °C and 10 MPa. Shell manufactures Versatic acids by this method (for Koch process see Carboxylic Acids, Aliphatic – Carboxylation
of Olefins, Koch Process and for Versatic acids see Carboxylic Acids, Aliphatic – Versatic Acids and Neo Acids).

4.3. Other Commercial and Noncommercial Fatty Acid Syntheses

A method used for manufacturing special fatty acids is the caustic fusion of alcohols. Hoechst (now Clariant) converts tridecyl alcohol to isotridecanoic acid, and
the oleochemical part of Henkel (now Cognis) produces isopalmitic acid from the C16 Guerbet alcohol ( Fatty Alcohols – Guerbet Alcohols) made from
caprylic alcohol [226], [227].

Furtheron Akzo was investigating the addition of acetic anhydride to linear terminal olefins (telomerization). After hydrolysis of the intermediate product,
branched-chain fatty acids with high molecular masses and low melting points are obtained, which are especially useful in the manufacture of synthetic
lubricants and enamels [228], [229].

Many other processes for making synthetic fatty acids have been developed to the stage of technical feasibility. However, no synthesis can compete
economically with the less expensive natural fatty acids. For example, hydrocarboxylation of olefins or acetylene with carbon monoxide and water in the
presence of metal carbonyl catalysts (Reppe reaction, Carbonylation – Introduction, Carbonylation – Carbonylation of Alkynes, Carbonylation –
Carbonylation of Alkenes) has not yet been used for the commercial production of fatty acids, although this reaction has been the subject of intensive work by
several firms [31], [57], [230], [231].

Likewise, oxidation of olefins with air, ozone, chromium trioxide, potassium permanganate, or other compounds has not resulted in an economical manufacturing
process. Oxidation of fatty alcohols with air or oxygen has also not been commercially successful. Reaction of trialkylaluminum (obtained as an intermediate in
the Ziegler alcohol synthesis, Fatty Alcohols) with carbon dioxide under pressure has not led to a usable process.

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5. Analysis
A number of wet chemical and physical methods are used for quality control of commercial products and identification of individual fatty acids. The composition
of fatty acid mixtures and natural fats is best determined by gas chromatography, which allows the identification of individual fatty acids with great accuracy.
Whereas fatty acid mixtures up to a chain length of 20 carbon atoms can be analyzed directly, fatty acids having a longer carbon chain must first be converted to
their methyl esters to increase accuracy. Natural oils and fats must first be saponified and then derivatized or analyzed directly depending on the nature of the
oil. Gas chromatography also allows determination of cis/trans contents or composition of conjugated isomers. Nuclear magnetic resonance (NMR) and infrared
(IR) spectroscopy have been successfully applied to the determination of the molecular structure of fatty acids.

Many chemical data determined by wet analysis are used to characterize commercial fatty acids and to check their purity [49]. Important parameters are the acid
value, saponification value, iodine value, and content of unsaponifiable matter ( Fats and Fatty Oils – Chemical Methods). From the acid and saponification
values, the average molecular mass and thus the average chain length of the fatty acids can be calculated. If a distilled fatty acid contains no esters or
anhydrides components the saponification value is identical to the acid value. The difference between the saponification and acid values is the so-called ester
value.

The iodine value is a measure of the total unsaturation of a fatty acid but does not permit conclusions to be made about the content of saturated fatty acids.
Thus, oleic acid has the same iodine value (90) as a fatty acid consisting of a 1 : 1 mixture of stearic and linoleic acids.

Practically all technical-grade fatty acids contain small quantities of foreign substances which do not have carboxyl groups and are therefore not saponifiable.
These constituents of natural fatty acids arise from foreign material in the fats, natural byproducts of the organisms that also generated the oil or fat, or from
decomposition products. The content of nonsaponifiable material in technical-grade fatty acids is regarded as a quality criterion and is usually in the range of 0.5
– 2 %.

Based on the composition of the fatty acids determined by gas chromatography, analytical data, normally obtained by traditional wet chemical analysis as acid or
saponification value or iodine value, can also be calculated. The calculation is the more exact the lower the content of unsaponifiables is.

Important physical data for characterizing fatty acids are the solidification point, sometimes called titer, the cloud point, and the color. The solidification point is
the temperature at which a fatty acid begins to solidify and is defined as the temperature maximum resulting from the release of the heat of crystallization.

Low-melting technical fatty acids without sharp solidification temperatures (< ca. 15 °C) are characterized by the cloud point, i.e., the temperature at which a
clearly perceptible turbidity occurs.

The measurement of color is also used to specify the quality of fatty acids. Color determination can be carried out by comparison with either standard solutions
(APHA, Hazen) or colored glass standards (Lovibond, Gardner, F.A.C.). APHA/Hazen define their standards as aqueous solutions made of inorganic salts in
given concentrations. Today for all methods the determination itself is mostly no longer carried out by subjective visual comparison but by means of automatic
spectrometers. Instead of the Lovibond yellow and red colors it is also common to use the percentage transmission at defined wavelengths, e.g., at 440 and 550
nm.

Analytical methods are standardized and well documented in compendia issued by different associations. Important ones are ISO, AOCS, and DGF [232-234]
(see Table 18).

Table 18. Common analytical methods for fatty acids

Method ISO AOCS DGF

Acid value 660 Te 4a-70 C-V 2
Saponification value 3657 Tl 1a-64 C-V 3
Iodine value 3961 Tg 1a-64 C-V 11d
Unsaponifiables 3596-1 Tk 1a-64 C-III 1a
Titer 935 Tr 1a-64 C-IV 3c
Cloud point Cd 15-78 D-III 3
Color (Lovibond scale) Cc 13e-92 C-IV 4b
Gas chromatography 5508 Ce 1e-91 C-VI 10

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6. Storage and Transportation

Storage. Fatty acids are unstable in the presence of atmospheric oxygen. As with fats, autoxidation of fatty acids leads to the formation of hydroperoxides, which
decompose to oxygen-containing products such as aldehydes, ketones, and hydroxy compounds. Other secondary products, such as polymers and splitting
products, can also be found [31], [235-238].

The effect of atmospheric oxygen on fatty acids depends primarily on the temperature, the number of double bonds, and the molecular structure. Saturated fatty
acids show little tendency to undergo autoxidation, whereas unsaturated fatty acids, and especially polyunsaturated acids, are very susceptible in this respect.
Higher temperatures favor the reaction. Small quantities of other substances present either naturally or adventitiously in the fatty acids can act as pro- or
antioxidants. All vegetable oils and fats contain, for example, tocopherols as natural antioxidants. In general, vegetable oils have a higher tocopherol content
than animal fats and therefore are usually more stable than animal fats with an equivalent degree of unsaturation. On the other hand, metals such as copper and
iron (in the form of soaps) act as prooxidants [49].

Autoxidation products affect the color stability of fatty acids, produce a pungent, rancid odor, and alter characteristic analytical values. The content of
nonsaponifiable matter and the ester value increase; the acid value and the iodine value decrease. The peroxide value is a measure of the degree of oxidation
[239]. The stability of commercial fatty acids cannot be predicted reliably from the analytical data because the relationship of the raw material, manufacturing
process, and storage conditions to the autoxidation behavior is very complex.

Synthetic antioxidants are not normally used in manufacturing, but they may be necessary for special applications of technical-grade fatty acids. Thus, up to
0.5 % 2-naphthol is added to oleic acid used as a lubricant in the textile industry. This reduces the tendency to self-heating as a result of autoxidation (Mackey
test). Other widely used synthetic antioxidants for fatty acids are butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), and tert-butyl hydroquinone
(TBHQ), which are used for stabilization of oils and fats as well as for fatty acids. They are approved in many countries for food, drugs, and cosmetics [49], [238].
Concentrations in the order of 0.01 % have proved sufficient. With regard to health and safety, fatty acids can alternatively be stabilized by natural antioxidants
such as tocopherols and their esters in concentrations on the order of 0.1 % [240-242].

Fatty acids are stored in liquid or solid form. In most cases, liquid fatty acids are kept in heated tanks. Stainless steel and aluminum are the construction
materials normally used for tanks and pipelines. Storage temperature should be slightly above the solidification point.

Under these conditions, saturated fatty acids can be stored for several weeks without detrimental effects on quality; however, with some unsaturated fatty acids,
the color deteriorates after a few days. Stability can be improved by storage under a nitrogen blanket.

Transportation. Railway tank cars, tank trucks, containers, ships, and aircraft are used for transporting liquid fatty acids. Materials and temperature correspond
to those used for storage. Dispatch in steel drums lined with a protective, fatty acid-resistant coating or in plastic drums is less important.

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Fatty Acids : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
Because of their corrosiveness, short-chain C6 – C9 fatty acids are subject to international regulations for the transportation of dangerous goods. This no longer
applies to C10 or mixtures of C10 and C12 fatty acids, which must be labeled as irritant. Mixtures with main component C8 such as C8 – C10 must be labeled as
corrosive. Mixtures with main component C12 such as C8 – C14 or C12 – C18 fatty acid fractions from palm kernel must be labeled as irritant. Special labeling
and handling are not required for C14 and longer chain fatty acids. An overview on the classification for road (ADR), railroad (RID), inland water (ADNR), marine
(IMDG), and air transport (IATA) is given in Table 19.

Table 19. Transport and safety classifications of fatty acids

Tranport class Hazard Packaging Storage

Hazard symbola no. Transport UN no. ident. no. group WGKb class VCIc
Related to ADR, RID, ADNR, ADR, RID, ADNR, ADR, RID, ADNR, ADR, RID IMDG, IATA
IMDG, IATA IMDG, IATA IMDG, IATA
C6 C 8 2829 80 III 1 8A
C8 C 8 3265 80 III 1 8A
C8–C10 (main C 8 3265 80 III 1 8A
C8 )
C10 Xi 1 10
C12 Xi 1 11
C8–C14 Xi 1 10
(mainly C12)
C12–C18 Xi 1 11
(mainly C12)
≥ C14 11

aC = corrosive, Xi = irritant. WGK = Wassergefährdungsklasse (water-endangering class) according to German VwVwS of May 17, 1999, Appendix 1/2
(1 = slightly water-endangering product). VCI = Verband der chemischen Industrie (Association of the German Chemical Industry).

In compliance with EEC directives [243], members of the European Association of Fatty Acid Producing Countries (Association Européenne des Producteurs
d'Acides Gras, APAG) have worked out a uniform method of labeling for Europe [244]. All available data on the transported product (including toxicity data),
protective measures for storage and handling, and measures to be taken in case of accidents and fires are specified in the respective safety data sheets.

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7. Environmental Protection, Toxicology, and Occupational Health

Organic substances such as fats and their components (fatty acids and glycerol) are major constituents of wastewater streams from industrial plants engaged in
oleochemistry and in processing natural fats and oils or their fatty acids. In domestic wastewater streams, these substances are also ubiquitous components and
originate from soaps, kitchen waste and foodstuffs.

Whereas saturated fatty acids of a chain length of 14 or higher are not classified as being a danger to water (German water-endangering class WGK 0: generally
not water-endangering) because they have low toxicity and are easily biodegradable, saturated acids up to C12 and unsaturated fatty acids are classified as
slightly water endangering (WGK 1). However none of the fatty acids is classified as environmentally dangerous with respect to the EEC directive [243]. When
industrial plants discharge their wastewater into municipal sewage systems for joint treatment with domestic wastewater, a certain pretreatment may be required.
Simple gravitational separation is often sufficient due to the low solubility of fatty acids in water. If necessary addition of traces of sulfuric acid and/or a surfactant
greatly enhances the degree of separation. Emulsified fatty acids are separated and skimmed, whereas dissolved fatty acids remain in the wastewater. The latter
fatty acids are mostly short-chain types originating from the vacuum systems of the distillation units.

The operation of sewage treatment plants can be badly disturbed by bulking sludge and scum caused by microorganisms (Type 021N, Nocardioform
actinomycetes). It was found that native fats are primarily responsible for promoting the growth of the organisms. Therefore, the problems can be eliminated by
reducing the load of native fats [245].

The entire organic load of the wastewater is established on the basis of the chemical oxygen demand (COD). The biological oxygen demand (BODn) within a
certain number of n days at 20 °C is a measure of biodegradability achieved by the action of microorganisms [246]. The BOD5 values of some fatty acids and
related compounds are given in Table 20. Under both aerobic and anaerobic conditions, unsaturated fatty acids are degraded more rapidly than saturated acids.
The rate of degradation of saturated fatty acids increases with decreasing chain length [31]. Fatty acids fulfil the ultimate (ready) biodegradability pass criterion of
60 % BOD/COD according to EEC directive [247] (method: OECD 301).

Table 20. Values of BOD5 for fatty acids and related compounds [31]

Component BOD5, mg/g

Palmitic acid 1070

Stearic acid 786
Sodium palmitate 1020
Sodium stearate 1200
Sodium oleate 1430
Glycerol 780

In addition to the organic load, often also the heavy-metal load and concentration is limited for wastewater. In the case of fatty acid production Ni plays the main
role. Nickel in wastewater results from cleaning processes in the hydrogenation plant or from treatment of distillation residues of hydrogenated acids with mineral
acid and water. Nickel content can be reduced sufficiently by carefully handling of the spent catalyst and by final treatment of the contaminated wastewater
streams. Precipitation with alkaline agents such as calcium hydroxide can achieve Ni contents of 1 ppm and lower.

Air pollution in the fatty acid industries, which results from the venting of storage tanks, reactors, or other process units, is objectionable due to the resulting
odors mainly caused by unsaponifiables and short-chain fatty acids up to capric acid rather than toxic properties. The best way of dealing with odors is
combustion. This is performed most economically by leading the exhaust air to the boiler house to replace part of the air normally used for combustion. Solid and
liquid residues are processed to form a suspension which is then burned in the boiler house or utilized in special combustion plants for the production of low-
pressure steam [248].

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Fatty Acids : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
The toxicological properties of C6 – C12 fatty acids can be summarized. Their acute oral toxicity LD50 in rats is > 2000 mg/kg (method: OECD 401). Therefore,
they can be classified as nontoxic [243], [249-253]. Neither MAK nor TLV values have been established. However, fatty acids up to lauric acid are corrosive or
irritant, and skin or eye contact should be prevented. The acute fish toxicity (LC50) is about 100 mg/L or more (method: ISO 7346/2).

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8. Uses
Fatty acids are used in various branches of industry as the acids themselves or in the form of derivatives such as soaps, esters, alcohols, or amides [49], [31],
[254], [255], [256]. The shares of the main end-use sectors consuming fatty acids are given in Table 21 for Europe and worldwide consumption [255], [257-259].

Table 21. Main applications of fatty acids in 2003

Europe % World, %
Detergents, personal care, soaps, cosmetics 40 49
Plastics 14 10
Rubber and tire industry 7 6
Lubricants and greases 6 3
Paper chemicals 5 3
Protective coatings and resins 5 3
Others (food, feed, candles, textile, leather, adhesives, agrochemicals, construction ) 23 26
100 100

The main end-use sectors as function of applied fatty acid C chain is shown in Table 22 [256].

Table 22. Main applications of fatty acids as function of C-chain

One of the oldest applications of fatty acids is in the manufacture of candles. Stearin (saturated C16 – C18 fatty acids) has been used for over 150 years as the
basic material for this purpose. However, stearin has been replaced largely by paraffin ( Candles).

Fatty alcohols, fatty amines, and fatty acid esters represent important intermediates in many different fields of application. The syntheses of these derivatives are
analogous to those of other monocarboxylic acids, and reactivity decreases with increasing molecular mass.

The fatty acid esters include methyl esters, partial glycerides, wax esters (esters of fatty acids with long-chain fatty alcohols), and ester oils (esters of fatty acids
with polyalcohols). Fatty acid methyl esters are intermediates in the manufacture of fatty alcohols and fatty acid alkanolamides. The partial glycerides (mono-
and diglycerides) of hardened fatty acids in the palmitic – stearic acid range are used in the food industry as emulsifiers in cakes, pastries, and ice cream. Ester
oils are used as lubricants for car engines and compressors, hydraulic fluids, and biogreases [260]. Epoxidized fatty acid esters are used as softeners or
plasticizers in plastics such as poly vinyl chloride (PVC). Lead and cadmium stearates are good stabilizers for PVC. as are zinc, calcium, calcium – zinc, and
barium – zinc stearates. Cadmium has been replaced because of its toxicity. Wax esters of long-chain fatty acids and fatty alcohols are used as external
lubricants in PVC processing [261].

In detergents, soaps, and cosmetics, fatty acids are used primarily in the form of their sodium soaps. The sodium soaps used in the manufacture of soap bars
are sometimes made from fatty acids or their methyl esters but are still obtained mainly by saponification of neutral oils many of the newer synthetic detergent
(syndet) cleansing bars incorporate teh sodium salt of a fatty acid/isethionate ester. Fatty acid alkanolamides and quaternary fatty alkylammonium salts are used
in detergents and cosmetics as foam stabilizer, booster, thickening agent, and consistency factor, and as base for shampoos and body cleansing products.
Sulfonated fatty acid methyl esters are of interest as readily biodegradable detergents. Esters such as isopropyl myristate and the triglycerides of short-chain
fatty acids are employed as the oil component of cosmetics and pharmaceutical products. Metal soaps, such as aluminum, magnesium, and zinc soaps, serve
as thickening agents in cosmetic creams. These metal soaps are also used in powders, because of their lubricating properties. Sodium, lithium, and calcium
soaps are employed as additives in mineral-oil lubricants for high-performance engines.

Fatty acid amides serve as slip agents and antiblock agents in plastic formulations [261], stabilizers of emulsions and dyes, builders in synthetic detergents,
intermediates in the production of textile water repellent [49], and as components for agricultural chemicals such as pesticides.

Fatty acid amines produced from fatty acids via the nitrile route are used in the rubber industry as mold-release and accelerating agents and for reclamation.
They are employed as corrosion inhibitors in the metal industry and for flotation of minerals. After quaternization they are applied for preparing cationic softeners
in the textile industry, as antistatic agents, for producing cationic surfactants agents, and oil-well drilling auxiliaries.

Both fatty amides and amines can be transformed into nonionic surfactants by reaction with ethylene oxide, whereas processing with chloroacetates yields
amphoteric surfactants with betaine structure [257].

Large quantities of fatty acids are required in the production of alkyd resins for surface coatings (e.g., paints and varnishes) used in all areas of coating
applications. The polyunsaturated fatty acids obtained from soybean and sunflower oils are reacted with a polyhydric acid such as phthalic anhydride and
polyalcohols to form alkyd resins and are especially important for this purpose [254]. Conjugated fatty acids, saturated fatty acids, and short-chain fatty acids are
also used in making paints.

Dimer fatty acids from tall, soybean, or sunflower oil are are mainly employed as polyamides for the coatings and paint industry, as well as for hot-melt
adhesives and printing inks. Reactive polyamides of dimer fatty acids are effective hardeners for epoxy resins. Isostearic acid as byproduct of the dimerization
process is a monofunctional branched-chain fatty acid. Because of their low solidification points (titers) and high oxidative stability its esters and the conversion
product isostearic alcohol are especially used for lubricants, cosmetics, and detergents. Isopalmitic acid has the same application areas. Estolides (also one acid
function) and estolide esters have growing importance in cosmetics, coatings, and biogradable lubricants. Another special form of acid dimers that have been
used for years in the paper industry for paper sizing (surface treatment) are alkyketene dimers (AKD) based on C16 – C22 saturated fatty acids, which are
prepared by dehydrochlorination of the corresponding fatty acid chlorides ( Ketenes – Production and Uses).

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Fatty Acids : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
Dibasic fatty acids such as azelaic acid (C9 from oleic acid, see chap. Ozonolysis), sebacic acid (C10 from ricinoleic acid, see chap. Thermal Decomposition) and
brassilic acid (C13 from erucic acid, see Section Biooxidation) find important outlets in form of esters as plasticizers, modifiers, components for lubricants, and for
polymers such as PVC and Nylon.

The C22 fatty acids erucic acid (monounsaturated) and behenic acid (saturated) from high-erucic rapeseed oil have applications as surfactants, plastics additives
(erucaamide, behenamide), and lubricants [262], [263]. Fatty acid distillates of low-erucic rapeseed oil are used as vegetable-based unsaturated C18 source.
Partial hydrogenation gives a high oleic acid with improved oxidation stability for production of diverse esters or for unsaturated fatty alcohols [264].

Ricinoleic acid as main natural hydroxy acid can be used for direct esters, estolides, fatty amides, or ethoxylates employed for cosmetics, coatings, and
lubricants. Undecylenic acid (C11, pyrolysis of ricinoleic methyl ester) is used as starting material in the manufacture of nylon 11 (Rilsan). The hydrogenation of
ricinoleic acid leads to 12-hydroxy stearic acid, which is mainly used in lubricant greases [198]. The synthetic production of dihydroxy or polyhydroxy fatty acids
involves as first reaction step the epoxidation ( Epoxides) of the base fatty acid (e.g., oleic acid) or oil (e.g., rapeseed, soybean) followed by a catalytic epoxy
ring opening in the presence of water or hydrogen donors. Applications exist in polymer additives (PVC), plastics, surfactants, lubricants, and the textile industry.

In the rubber industry, various types of stearin (mixture of C16 and C18) are used as lubricants. In tire manufacture, stearic acid is also used as a separating
agent during molding. Zinc and magnesium stearates act as accelerators in the vulcanization process. Soaps of diverse fatty acids are used as emulsifiers in
emulsion polymerization for the manufacture of synthetic rubber. Stearin also serves as auxiliary for treatment of recycled paper (e.g., deinking) in the paper
industry.

Olein, i.e., technical-grade oleic acid, has been used for many years as a lubricant in the textile industry and for leather auxiliaries. Saponification of oleic acid
leads to soft soaps. Oleic acid derivatives are employed as wetting, leveling, and finishing agents in many other operations in textile manufacturing. Thus, N-
methyloleyltaurine is used in dyeing textiles, and sulfonated monoethanolamides are used in washing printed cloths. Finishing agents contain esters and amides
of longer chain fatty acids with polyglycols or polyamines. Melamine resins modified with fatty acids serve as impregnating agents. Oleic acids are used for
producing fatty alcohols with high oleic content for the cosmetic, detergent, and plastics industries, where they are employed as solvents, oily components,
super-fatting agents, defoamers, plasticizers, and emulsifiers. Esters of oleic acid with fatty alcohols such as oleic acid oleyl ester (C18 unsatd/C18 unsatd) or
oleic acid decylester (18 unsatd/C10 satd) serve as oily components for cosmetics. Esters of oleic acid with di- or polybasic alcohols such as trimethylolpropane
are used for lubricants.

Distillation and fractionation result in bottom products (residues) of 5 – 10 % in relation to the feed crude fatty acid [265]. Coproducts contain free fatty acids in
the range of about 25 – 50%. The use as ingredients in feed compounds is limited according to regional laws with respect to heavy metal content and animal
origin. APAG reports a maximum of 200 ppm Ni in the fat component and 5 – 20 ppm in the final feed [266]. Owing to mad cow disease (BSE) tallow-based
coproducts are not permitted for feeding in Germany [267]. Therefore, an economical outlet for the coproducts in Europe is today mainly thermal utilization as
fuel substitute in boiler houses and incinerators of the concrete and steel industry. The heat of combustion depends on the mix and achieves about 70 – 90 % of
the value of light crude oil (42 MJ/kg). The allowed Ni content depends on the equipment and license of the end users.

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Fatty Alcohols : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

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Klaus Noweck1 and Wolfgang Grafahrend1 Print this page
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DOI: 10.1002/14356007.a10_277.pub2 Advanced Product Search
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Abstract | Full Text: HTML

Abstract
The article contains sections titled:

1. Introduction
2. Saturated Fatty Alcohols
2.1. Physical Properties
2.2. Chemical Properties
2.3. Production from Natural Sources
2.3.1. Hydrolysis of Wax Esters
2.3.2. Reduction of Wax Esters with Sodium
2.3.3. Hydrogenation of Natural Raw Materials
2.3.3.1. Raw Materials and Pretreatment
2.3.3.2. Hydrogenation Processes
2.4. Synthesis from Petrochemical Feedstocks
2.4.1. Ziegler Alcohol Processes
2.4.2. Oxo Process
2.4.3. Hydrogenation of Fatty Acids produced by Oxidation of Paraffinic Hydrocarbons
2.4.4. Bashkirov Oxidation
2.4.5. Other Processes
2.5. Uses
3. Unsaturated Fatty Alcohols
4. Guerbet Alcohols
5. Bifunctional Fatty Alcohols
6. Quality Specifications
7. Storage and Transportation
8. Economic Aspects
9. Ecotoxicology and Toxicology
9.1. Ecotoxicology and Environmental Aspects
9.2. Toxicology

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1. Introduction
Fatty alcohols are aliphatic alcohols with chain lengths between C6 and C22:

They are predominantly linear and monohydric, and can be saturated or have one or more double bonds. Alcohols with a
carbon chain length above C22 are referred to as wax alcohols. Diols whose chain length exceeds C8 are regarded as
substituted fatty alcohols. The character of the fatty alcohols (primary or secondary, linear or branched-chain, saturated or
unsaturated) is determined by the manufacturing process and the raw materials used. Natural products, such as fats, oils,
and waxes, and the Ziegler alcohol process provide linear, primary, and even-numbered alcohols; those obtained from

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Fatty Alcohols : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
natural sources may be unsaturated. In contrast, the oxo process yields 20 – 60 % branched fatty alcohols, and also some
odd-numbered ones. Guerbet dimerization results in -branched, primary alcohols, whereas Bashkirov oxidation yields
secondary alcohols.

Depending on the raw materials used, fatty alcohols are classified as natural or synthetic. Natural fatty alcohols are based on
renewable resources such as fats, oils, and waxes of plant or animal origin, whereas synthetic fatty alcohols are produced
from petrochemicals such as olefins and paraffins. Up to 1930, when catalytic high-pressure hydrogenation was developed
ADKINS and FOLKER [7], NORMAN [8], SCHRAUTH [9], and SCHMIDT [10], the manufacture of fatty alcohols was based almost
exclusively on the splitting of sperm oil. By 1962, the world production capacity from natural raw materials had grown to
ca. 200 000 t/a. New processes utilizing petrochemical raw materials, e.g., the Ziegler alcohol process, the SHOP process,
the oxo process, and the construction of additional plants for high-pressure hydrogenation of natural raw materials, allowed a
further increase. In 2005, the world nameplate production capacity of fatty alcohols was estimated to be 2.5 × 106 t/a, being
nearly equally based on natural and petrochemical feedstocks. This ratio will change because 600 000 – 700 000 t/a of
additional production capacity based on natural feedstocks will come on stream by 2008. Production and consumption were
estimated to amount to only 80 % or less of capacity. Fatty alcohols and their derivatives are used in polymers, surfactants,
oil additives, and cosmetics and have many specialty uses.

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2. Saturated Fatty Alcohols

2.1. Physical Properties
Saturated fatty alcohols up to dodecanol are clear, colorless liquids. The next higher homologues are soft materials;
tetradecanol and higher alcohols have a waxy consistency. The saturated alcohols crystallize in a nearly orthorhombic lattice
[11] and all have a lower specific density than water. The lower members of the series have characteristic odors; the higher
fatty alcohols are odorless, except for traces of impurities such as carbonyl compounds and hydrocarbons, which are usually
present.

Physical properties of linear, primary fatty alcohols are summarized in Table 1 (for additional data on pure alcohols and
commercially important blends, see [12-15]).

Table 1. Physical and chemical properties of fatty alcohols

IUPAC name Common CAS Molecular Mr Hydroxyl mp, bp, °C Density, Refractive
name registry
number formula number °C (p, kPa) g/cm3 index
(t, °C) (t, °C)

1-Hexanol caproic [111-27-3] C6H14O 102.2 548 –52 157 0.819 1.4181
alcohol (20) (20)
1-Heptanol enanthic [111-70-6] C7H16O 116.2 482 –30 176 0.822 1.4242
alcohol (20) (20)
1-Octanol caprylic [111-87-5] C8H18O 130.2 430 –16 195 0.825 1.4296
alcohol (20) (20)
1-Nonanol pelargonic [143-08-8] C9H20O 144.3 388 – 4 213 0.828 1.4338
alcohol (20) (20)
1-Decanol capric [112-30-1] C10H22O 158.3 354 7 230 0.829 1.4371
alcohol (20) (20)
1-Undecanol [112-42-5] C11H24O 172.3 326 16 245 0.830 1.4402
(20) (20)
1-Dodecanol lauryl [112-53-8] C12H26O 186.3 300 23 260 0.822 1.4428
alcohol (40) (20)
1-Tridecanol [112-70-9] C13H28O 200.4 280 30 276
1-Tetradecanol myristyl [112-72-1] C14H30O 214.4 261 38 172 0.823 1.4358
alcohol (2.67) (40) (50)
1-Pentadecanol [629-76-5] C15H32O 228.4 245 44 1.4408
(50)
1-Hexadecanol cetyl [ C16H34O 242.5 230 49 194 0.812 1.4392
alcohol 36653-82-4] (2.67) (60) (60)
1-Heptadecanol margaryl [1454-85-9] C17H36O 256.5 218 54
alcohol
1-Octadecanol stearyl [112-92-5] C18H38O 270.5 207 58 214 0.815 1.4388
alcohol (2.67) (60) (60)
1-Nonadecanol [1454-84-8] C19H40O 284.5 196 62 1.4328
(70)
1-Eicosanol arachidyl [629-96-9] C20H42O 298.6 187 64 215 0.806
alcohol (1.33) (70)
1-Heneicosanol [ 312.6 179 68

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15594-90-8] C21H44O
1-Docosanol behenyl [661-19-8] C22H46O 326.6 171 71 241 0.807
alcohol (1.33) (80)
1-Tricosanol [3133-01-5] C23H48O 340.6 164 74
1-Tetracosanol lignoceryl [506-51-4] C24H50O 354.7 158 77
alcohol
1-Pentacosanol [ C25H52O 368.7 152 78
26040-98-2]
1-Hexacosanol ceryl [506-52-5] C26H54O 382.7 146 81
alcohol
1-Heptacosanol [2004-39-9] C27H56O 396.8 141 82
1-Octacosanol montanyl [557-61-9] C28H58O 410.8 136 84
alcohol
1-Nonacosanol [6624-76-6] C29H60O 424.8 132 85
1-Triacontanol myricyl [593-50-0] C30H62O 438.8 128 87
alcohol
1- melissyl [544-86-5] C31H64O 452.9 124 87
Hentriacontanol alcohol
1-Dotriacontanol lacceryl [6624-79-9] C32H66O 466.9 120 89
alcohol
1-Tritriacontanol [ C33H68O 480.9 116
71353-61-2]
1- geddyl [ C34H70O 494.9 113 92
Tetratriacontanol alcohol 28484-70-0]

Boiling points and melting points increase uniformly with chain length. Both are significantly higher than those of the
hydrocarbons with the same number of carbon atoms. The influence of the polarizing hydroxyl function diminishes with
increasing chain length. Thus hexanol and even octanol show some water solubility, but decanol and the higher fatty alcohols
can be considered as immiscible with water. However, a slight hygroscopicity is observed even with octadecanol and higher
fatty alcohols, which can absorb water vapor from air during storage. Common organic solvents such as petroleum ether,
lower alcohols, and diethyl ether are suitable solvents for fatty alcohols.

2.2. Chemical Properties

The industrial importance of the fatty alcohols is due to the large number of reactions that the hydroxyl group may undergo.
Figure 1 shows some typical examples (see also Alcohols, Aliphatic); many of the resulting derivatives are intermediates
of commercial importance (see section Uses). Ethoxylation with ethylene oxide yields fatty alcohol polyglycol ethers, which
are of major importance for the detergent industry ( Laundry Detergents; Surfactants):

Figure 1. Typical reactions of fatty alcohols

Under normal conditions, fatty alcohols are resistant to oxidation. However, they can be converted into aldehydes or
carboxylic acids using strong oxidants or by catalytic oxidation with air or oxygen [16-20]. This reaction is important for the
synthesis of C6 – C10 aldehydes if these are not readily available from natural sources [21] and are therefore produced from
synthetic alcohols.

2.3. Production from Natural Sources

Two groups of natural raw materials are used for the production of fatty alcohols: (1) fats and oils of plant or animal origin,
which contain fatty acids in the form of triglycerides that can be hydrogenated after suitable pretreatment ( Fats and Fatty
Oils – Refining) to yield fatty alcohols; and (2) wax esters from whale oil (sperm oil), from which the fatty alcohols are
obtained by simple hydrolysis or reduction with sodium. The commercial exploitation of sperm oil has led to depletion of
whale populations and is banned in some countries. Attention has therefore turned to the jojoba plant whose oil also consists
of wax esters. Successful attempts to cultivate this desert shrub and develop it as a source of raw material have been made.
But this wax is mainly used in cosmetic applications in a small amount.

Most fatty chemicals obtained from natural sources have chain lengths of C16 – C18. The limited availability of compounds
with 12 – 14 carbon atoms, which are important in surfactants, was one of the driving forces behind the development of

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petrochemical processes as well as the intensification of plantation and the breeding of new crops for the production of fatty
alcohols (see Section Synthesis from Petrochemical Feedstocks). Higher alcohols, such as C20 – C22 alcohols, can be
produced from rapeseed oils rich in erucic acid and fish oils. Unsaturated fatty alcohols may be manufactured in the
presence of selective catalysts. Hydroxyacids for production of diols are available from castor oil. For detailed reviews of
large-scale industrial processes for the production of fatty alcohols, see [1], [22], [23].

2.3.1. Hydrolysis of Wax Esters

The hydrolysis of wax esters is of minor importance today. It is carried out by heating sperm oil with concentrated sodium
hydroxide at ca. 300 °C and distilling the alcohol from the sodium soap.

The distillate consists of partially unsaturated C16 – C20 alcohols, which are hardened by catalytic hydrogenation to prevent
autoxidation. Since sperm oil contains only ca. 70 % wax esters, the alcohol yield is about 35 %.

2.3.2. Reduction of Wax Esters with Sodium

The reduction of esters with sodium was first described in 1902 by BOUVEAULT and BLANC (for a review, see [24]). Large-
scale application of this process was achieved in 1928 (Dehydag).

Molten sodium is dispersed in an inert solvent and the carefully dried ester and alcohol are added. When the reaction is
complete, the alkoxides are split by stirring in water, and the alcohols are washed and distilled [25].

The added alcohol R3OH, preferably a secondary alcohol, acts as a hydrogen donor. Because of side reactions, the
consumption of sodium can be as much as 20 % above the stoichiometric requirement.

The reduction proceeds selectively without production of hydrocarbons and isomerization or hydrogenation of double bonds.
Extensive safety measures are required due to the large quantity of metallic sodium used. The process was used until the
1950s to produce unsaturated fatty alcohols, especially oleyl alcohol from sperm oil. These alcohols can now be produced by
selective catalytic hydrogenation processes using cheap raw materials, and the sodium reduction process is of interest only
in special cases. A fully continuous plant with a production capacity of 3600 t/a was built in Japan in 1973 for the reduction of
sperm oil [26].

2.3.3. Hydrogenation of Natural Raw Materials

2.3.3.1. Raw Materials and Pretreatment
For the production of C12 – C14 alcohols, preferably coconut oil and palm kernel oil are used. Rape seed oil, palm oil,
soybean oil, and tallow are the main sources for C16 – C18 alcohols. Rapeseed oil rich in erucic acid yields fatty alcohols with
20 or 22 carbon atoms. Bifunctional fatty alcohols can be obtained from castor oil and other special oils (see
Chap. Bifunctional Fatty Alcohols). More than 90 % of the 125 × 106 t/a of vegetable oils are used in food applications.

Before hydrogenation, contaminants such as phosphatides, sterols, or oxidation products and impurities such as seed
particles, dirt, and water are removed in a cleaning stage, which includes refining by treatment with phosphoric acid,
centrifugation, and adsorption, e.g., on charcoal or bentonite ( Fats and Fatty Oils – Refining).

The refined triglycerides are then hydrolyzed to yield fatty acids ( Fatty Acids) or transesterified with lower alcohols to
yield fatty acid esters.

Refined free fatty acids, wax esters, and fatty acid methyl esters are used for hydrogenation. Direct hydrogenation of
triglycerides is also possible; however, under the reaction conditions, glycerol is reduced to propylene glycol and propanol
and therefore makes no commercial contribution as a byproduct. More hydrogen is needed and catalyst costs increase.
Therefore, triglyceride hydrogenation is not used industrially.

Fatty acid esters are produced either by esterification of free fatty acids or by transesterification of triglycerides (see also
Esters, Organic).

Esterification of Fatty Acids. Esterification is an equilibrium reaction:

Excess alcohol or removal of water shifts the equilibrium toward ester formation. Industrial esterification is carried out in a
column at 200 – 250 °C under slight pressure and with excess methanol. Some processes use a catalyst like an ion

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exchanger [27]. Distilled fatty acids, which no longer have the composition of the original natural product, are predominantly
used. Methanol reacts with the fatty acid in a countercurrent. The acid number (milligrams of KOH needed to neutralize one
gram of substance) is used as a quality characteristic and for process control. Batch and continuous processes give esters of
similar quality, but the continuous process uses less methanol and the residence time is reduced. The methyl ester is
subsequently distilled for purification. Another uncatalyzed process esterifies the distilled fatty acid with an excess of fatty
alcohols to wax esters at about 200 – 250 °C [28].

Transesterification of Triglycerides. This reaction is carried out continuously with alkaline catalysts. Like esterification,
transesterification is an equilibrium reaction and is shifted toward the desired ester by excess methanol or removal of
glycerol:

If the reaction is carried out under mild conditions (50 – 70 °C, atmospheric pressure, excess methanol), free fatty acids
present in the oils must first be removed or pre-esterified, e.g., with glycerol. Under more severe conditions (i.e., at 9 –
10 MPa and 220 – 250 °C), pre-esterification is unnecessary, and less pure, cheaper raw materials can be used.
Disadvantages of the latter process are the need for high-pressure equipment, a greater excess of methanol, and the energy-
intensive further processing of the aqueous methanol. The methyl esters are purified by distillation.

Figure 2 demonstrates the production tree of physical and chemical processing of fats and oils.

Figure 2. Physical and chemical processing of fats and oils

2.3.3.2. Hydrogenation Processes

Three large-scale hydrogenation processes are used commercially:

1. Gas-phase hydrogenation
2. Trickle-bed hydrogenation
3. Suspension hydrogenation

The first two processes use a fixed-bed catalyst. In contrast to gas-phase and trickle-bed hydrogenation the suspension
process uses a powdered catalyst with a specific particle size distribution. The selection of a process depends on the
integration into existing plants and the choice of raw materials. In all cases, hydrogenation is carried out with copper-
containing, mixed-oxide catalysts at 170 – 270 °C and 4 – 30 MPa. By using proprietary fixed bed catalysts methyl esters can
be hydrogenated at 170 – 250 °C and 10 – 40 MPa in a trickle bed [31], [30] or in the gas phase (Fig. 12) [27]. The wax ester
process operates at 170 – 270 °C and from less than 10 to 30 MPa (Fig. 13) [28].

Figure 12. Production of fatty alcohols by hydrogenation of fatty acid methyl esters

Figure 13. Wax ester route to fatty alcohols

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Suspension Hydrogenation. This process is applicable to fatty acid methyl esters as well as to fatty acids.

Hydrogen (ca. 50 mol per mole of ester) and the heated methyl ester are fed separately into the bottom of a narrow reactor.
The reaction is carried out at ca. 25 MPa and 250 – 300 °C in the presence of a fine powdery copper catalyst; the LHSV
(liquid hourly space velocity) is approximately 1. The excess hydrogen serves to circulate the reaction mixture. The product
mixture is separated into a gas phase, which is recycled to the reactor, and a liquid phase, from which the methanol is
stripped. The crude product, which still has a saponification number of 6 – 10 (milligrams of KOH required to saponify one
gram of substance), is distilled off after removal of the catalyst. If a stainless steel reactor is used, this process can be
applied to the direct hydrogenation of fatty acids. In this case, an acid-resistant catalyst is required, and catalyst consumption
is increased.

A variant that is particularly suitable for the hydrogenation of fatty acids has been developed by Lurgi (Fig. 3) [31], [32] [34]
and is used by several manufacturers. This process employs a large excess of fatty alcohol in the hydrogenation reactor.
Hydrogen, fatty alcohol – catalyst slurry, and fatty acids are fed separately into the reactor; the ester forms almost
instantaneously [34] and is then hydrogenated in the same reactor in a slower, second reaction step. Hydrogenolysis is
carried out at ca. 30 MPa and 260 – 300 °C. Catalyst consumption is 3 – 7 kg/t fatty acid depending on the acid and the
concentration of catalyst-poisoning impurities like sulfur, chloride, and phoshorus. The catalyst is separated by centrifugation,
and the crude fatty alcohol, which has an acid number of < 0.1 and a saponification number of 2 – 5, is purified by distillation.
The selectivity of the process is > 99 %.

Figure 3. Suspension hydrogenation of fatty acids (Lurgi process)

By continuously replacing part of the spent catalyst, the activity of the copper chromite contact can be held constant.

Gas-Phase Hydrogenation. This process requires a vaporized substrate and is therefore particularly suitable for methyl
esters, preferably with a chain length of 12 – 18 C-atoms [34]. Characteristics of the process are a large excess of recycle
gas (ca. 600 mol of H2 per mole of ester), high gas velocities and the addition of methanol to aid evaporation [35], [36].
Decomposition of methanol creates significant quantities of carbon monoxide, water, and dimethyl ether. Admixture of an
inert gas to the hydrogen is claimed to make the addition of methanol superfluous and to reduce the excess of recycle gas
[37]. Catalysts like copper–zinc or copper–chromium mixed oxides are used in a fixed bed. The conditions required are 4 –
10 MPa pressure and 170 – 230 °C, with an LHSV of about 0.3. Alcohol yields of > 99 % are achieved. Catalyst
consumption is < 0.8 kg/t feed. The product mixture is separated into a gas and a liquid phase, the hydrogen recycled and
the methanol stripped from the fatty alcohol.

Trickle-Bed Hydrogenation. In this process, the products to be reduced are used in their liquid form. The process is
therefore also suitable for methyl esters [31] and non-vaporizable substrates such as wax esters and [28]. Corrosive effects
of acids can be neutralized by hydrogenation in the presence of amines [38]. If a considerably lower excess of recycle gas
(ca. 100 mol of H2 per mole of ester) is used, a different plant design is necessary. The reaction is carried out at <10 –
30 MPa and about 170 – 230 °C, with an LHSV of 0.5 – 0.8. Normally, catalysts based on copper, chromium- or copper-zinc
mixed oxides are employed. More rarely, supported catalysts such as copper chromite on silica are used. Catalyst
consumption is < 0.8 kg/t feed. Further treatment of the product is identical to that described for gas-phase hydrogenation.

Comparison of Hydrogenation Processes. In the case of the fixed-bed processes (gas-phase and trickle-bed
hydrogenation), the catalyst need not be separated from the crude fatty alcohol. However, a gradual decrease in the
hydrogenating activity due to catalyst poisons such as sulfur, phosphorus, or chlorine is observed, whereas continuous
replacement of the catalyst in the suspension process ensures constant activity. If methyl esters are employed, separation
and further processing of the methanol is necessary.

Catalysts that contain noble metals, especially rhenium, may allow hydrogenation at lower pressures, which would reduce
capital and operating costs [39-41].

2.4. Synthesis from Petrochemical Feedstocks

2.4.1. Ziegler Alcohol Processes
Two processes for the production of synthetic fatty alcohols are based on the work of ZIEGLER on organic aluminum
compounds: the Alfol process, developed by Conoco, and Ethyl Corporation's Epal process [42], [43]. Fatty alcohols
synthesized by these processes are structurally similar to natural fatty alcohols and are thus ideal substitutes for natural
products.

Conoco started the first Alfol plant in the United States in 1962. This plant is now operated by Sasol Northe America. In 1964
Condea Chemie (now Sasol) installed a similar plant in Brunsbüttel, Federal Republic of Germany. Ethyl Corporation (today
BP/Amoco) developed its own process (Epal process) and began operations in 1964. Additional Alfol alcohol plants were
built in Ufa/ Russia in 1981 and in Jilin/ China in 1998.

Alfol process. Figure 4 shows a simplified diagram of the Alfol process [44]. A hydrocarbon is used as solvent. The process
involves five steps: hydrogenation, ethylation, growth reaction, oxidation, and hydrolysis.

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Figure 4. Alfol alcohol process

1. Hydrogenation

2. Ethylation

3. Growth Reaction

4. Oxidation

5. Hydrolysis

Two-thirds of the triethylaluminum produced in the ethylation reaction (b) are recycled to the hydrogenation stage (a), and
one-third enters the growth reaction (c). Insertion of the ethylene molecule into the aluminum – carbon bonds occurs as a
statistical process and leads to a broad distribution (Poisson distribution [45], [46]) of chain lengths, ranging from C2 to
beyond C26 [44]. An optimal yield of the C12 – C14 alcohols, which are important in the surfactant sector, requires addition of
about four molecules of ethylene per aluminum – carbon bond (see also Table 2). A small percentage of olefins are formed
as byproducts.

Table 2. Typical alcohol distributions in Alfol and Epal processes

Distribution, %

Alcohol Alfol process Epal process

Ethanol 0.5 traces

Butanol 3.4 0.1
Hexanol 9.5 1.5
Octanol 16.1 3.5
Decanol 19.5 8.0
Dodecanol 18.4 34.0
Tetradecanol 14.1 26.0
Hexadecanol 9.1 16.0
Octadecanol 5.1 8.8
Eicosanol 2.5 1.9
Docosanol 1.1 0.2

Because of the varying reactivity of partially oxidized trialkylaluminum compounds, oxidation is carried out stepwise by

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passing through carefully dried air. Cooling is necessary, especially at the start of the reaction. Alkanes and oxygen-
containing compounds are formed as byproducts [42].

Prior to hydrolysis, the solvent is removed by distillation. Hydrolysis with water gives high-purity hydrated alumina as a
coproduct, which has many industrial applications, e.g., in catalytic processes ( Aluminum Oxide – Catalytic Applications)
and in ceramics. In the 1960s, hydrolysis was carried out with hot sulfuric acid at Conoco's and Ethyl Corporation's plants.
Conoco changed to neutral hydrolysis, but the sulfuric acid method was used in the Epal process until its shutdown and leads
to high-purity aluminum sulfate as a coproduct. The crude alcohols are finally fractionated into marketable blends and single
cuts.

Epal Process (see Fig. 5). Many attempts have been made to achieve a narrower distribution of chain lengths in the growth
reaction [43]. The only process that has been used on an industrial scale is the Epal process developed by the Ethyl
Corporation (today BP/Amoco). The reaction steps resemble those of the Alfol process, but the growth reaction is not carried
as far. The product of the growth reaction is subjected to transalkylation (290 °C, 3.5 MPa) with C4 – C10 olefins. The chain
lengths of the resulting trialkylaluminum compounds are predominantly C4 – C10. Excess olefins are removed in a stripping
column and then fractionated. The trialkylaluminum compound is subjected to a second growth reaction and then
transalkylated (200 °C, 35 kPa) with C12 – C18 olefins. Again the olefins are separated in a stripper and fractionated. At this
stage, the trialkylaluminum compound consists largely of alkyl chains with 12 – 18 carbon atoms.

Figure 5. Flow diagram of the Epal process

The alcohol distributions achieved in the Epal and Alfol processes are shown in Table 2 [47]. The Epal process offers greater
flexibility than the Alfol process because both the alcohols and the -olefins that are formed as intermediates can be
marketed [48]. Disadvantages of the Epal process are the higher capital and operating costs, a considerably more
complicated process control, and an increased proportion of branched-chain olefins and alcohols.

2.4.2. Oxo Process

The oxo process (hydroformylation) consists of the reaction of olefins with an H2– CO gas mixture in the presence of suitable
catalysts. This reaction was discovered in 1938 by O. ROELEN at Ruhrchemie during work on the Fisher – Tropsch synthesis.
Although the first production plant was constructed before 1945 [49], the oxo process achieved industrial importance only in
the 1950s, with the increasing demand for plasticizers and detergents. The process is based on the following reaction (for
details on the reaction mechanism, see [50] and Oxo Synthesis):

-Olefins yield approximately equal amounts of straight-chain and branched aldehydes (see also Fig. 10). Internal and
branched alkenes can also be used in this reaction. Internal olefins give a product containing some primary aldehyde
because the catalyst effects double-bond isomerization.

For a long time paraffin-based processes were predominant as a source of olefins, especially for detergents [48], [57]. With
the development of the SHOP process (Shell's Higher Olefin Process), ethylene has become the preferred raw material [58].
The principal steps in the SHOP process are ethylene oligomerization, isomerization, and metathesis ( Hydrocarbons).
The products are C12 – C18 -olefins and C11 – C14 internal olefins, which are all important in the area of surfactants [59],
[60].

Heterogeneous hydrogenation of the oxo aldehydes at 5 – 20 MPa and 150 – 250 °C in the presence of catalysts based on
nickel, molybdenum, copper, or cobalt yields the corresponding alcohols. Alternatively, the aldehyde can be subjected to an
aldol reaction as in the production of 2-ethylhexanol ( 2-Ethylhexanol – Industrial Production). A flow sheet of the oxo
process is depicted in Figure 6. Worldwide there are three variants of the oxo process [52]: (1) the classical process using
HCo(CO)4 as catalyst; (2) the Shell process based on a cobalt carbonyl – phosphine complex [51]; and (3) a process using a
rhodium catalyst. The key parameters of these processes are compared in Table 3.

Table 3. Typical process parameters of the oxo processes

Parameter Oxo process

Classical Shell Union Carbide

Catalyst cobalt cobalt carbonyl – phosphine rhodium carbonyl – phosphine

carbonyl complex complex
complex phosphine complex

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Catalyst 0.1 – 1.0 ca. 0.5 0.01 – 0.1
concentration, %
CO : H2 ratio 1 : 1 – 1.2 1 : 2 – 2.5 excess hydrogen
Temperature, °C 150 – 180 170 – 210 100 – 120
Pressure, MPa 20 – 30 5 – 10 2–4
LHSV* 0.5 – 1.0 0.1 – 0.2 0.1 – 0.25
Primary products aldehydes alcohols aldehydes
Linearity, % 40 – 50 80 – 85 ca. 90 (n-butanol)

* Liquid hourly space velocity

The classical, cobalt-catalyzed oxo process involves the following steps: oxo reaction, catalyst separation and regeneration,
aldehyde hydrogenation, and alcohol distillation. Variants of this process differ mainly in the catalyst separation and
regeneration steps [53], [54].

In the Shell process, alcohols are obtained directly because of the greater hydrogenating activity of the catalyst; the aldehyde
hydrogenation step is unnecessary. Linearity is improved and the 2-methyl isomer is the main byproduct. A disadvantage is
the loss of olefins due to hydrogenation to alkanes.

Hydroformylation based on a rhodium catalyst has been used by Union Carbide since the 1970s for the production of n-
butanol and 2-ethylhexanol [55]. The higher activity of the catalyst enables operation at lower temperature and pressure. For
butanol, the linearity is over 90 %. The disadvantage is the high price of rhodium.

For a review of the oxo synthesis, see [56].

Figure 6. Flow diagram of the classical oxo process

2.4.3. Hydrogenation of Fatty Acids produced by Oxidation of Paraffinic Hydrocarbons

The process for the oxidation of paraffinic hydrocarbons, developed in Germany before 1940, is used on an industrial scale in
Russia for the manufacture of fatty acids. About 5 – 10 % of these synthetic fatty acids are converted to fatty alcohols. The
products are mainly linear, primary alcohols, with 5 – 15 % branched alcohols. An overview is given in [61].

A mixture of paraffins is oxidized above 100 °C in the presence of manganese catalysts. The complex product mixture
consists of aldehydes, ketones, esters, carboxylic acids, and other compounds. Since the byproducts cannot be completely
removed during further processing and distillation of the carboxylic acids, the uses of fatty alcohol produced by this method
are limited. As with the natural fatty acids, hydrogenation is carried out after esterification with methanol or butanol. The
suspension hydrogenation process is used (see Suspension Hydrogenation.). The distillation residue contains esters of C
10 – C20 alcohols, 25 % of which are secondary. These alcohols can be obtained by hydrolysis.

2.4.4. Bashkirov Oxidation

A variant of paraffinic hydrocarbon oxidation was developed in the 1950s in the Soviet Union by BASHKIROV [1], [3]. The
paraffins are oxidized in the presence of boric acid, which scavenges the hydroperoxides that are formed as intermediates.
This results in the formation of boric acid esters of secondary alcohols. These esters are relatively stable to heat and
oxidation. Hydrolysis leads to a statistical distribution of secondary alcohols in which the hydroxyl function may occupy any
position on the carbon chain.

Industrial oxidation is carried out at about 160 °C with a nitrogen – air mixture containing about 3.5 % oxygen [62], [63] (
Alcohols, Aliphatic – Oxidation of Saturated Hydrocarbons). The conversion of paraffins is limited to a maximum of 20 %
in order to minimize side reactions. The principle reaction steps are depicted in Figure 7.

Figure 7. Bashkirov oxidation

The process is used in the former Soviet Union and in Japan (Nippon Shokubai). A plant operated by Union Carbide in the
United States since 1964 is closed.

2.4.5. Other Processes

Fatty alcohols can also be obtained by reaction of -olefins with hydroperoxides in the presence of transition-metal catalysts,
especially molybdenum [65]:

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If tert-butyl hydroperoxide is used, the coproduct isobutanol can be readily separated from the epoxide.

After separation of the low molecular mass alcohol and purification, the epoxide is hydrogenolyzed in the presence of a nickel
catalyst to form the primary alcohol. About 10 – 15 % of the secondary alcohol and 2 % paraffin are obtained as byproducts
[66].

Mixtures of linear, primary alcohols with average molecular masses between 400 and 700 (corresponding to a chain length of
30 – 50 carbon atoms) are marketed under the trade name Unilin [67]. The hydrocarbon content of these mixtures is about
20 %. Ethylene oligomers are oxidized to produce oxygen-containing products on an industrial scale [68].

1-Triacontanol, which does not occur in the common natural raw materials and is produced only in minute quantities in
petrochemical processes such as the Alfol process, is of interest because of its ability to stimulate plant growth [69]. Several
research groups investigated synthetic pathways based on cheap raw materials [70-75].

2.5. Uses
Fatty alcohols are mainly employed as intermediates. In Western Europe, only 5 % are used directly and ca. 95 % in the form
of derivatives [76].

Surfactants. The amphiphilic character of fatty alcohols, which results from the combination of a nonpolar, lipophilic carbon
chain with a polar, hydrophilic hydroxyl group, confers surface activity upon these compounds. Surfactants account for 70 –
75 % of fatty alcohol production [77].

Due to the their amphiphilic properties fatty alcohols orient themselves at phase interfaces and can therefore be used in
emulsions and microemulsions. In cosmetic emulsions (creams, lotions) the main function of the fatty alcohols is to provide
consistency, in technical emulsions they are used as cosurfactants and solution aids.

If the hydroxyl group of the fatty alcohols is replaced by other, larger hydrophilic groups, the polar character is enhanced and
surfactants are obtained [4]. The most important surfactants derived from fatty alcohols are described in the following (see
also Laundry Detergents, Surfactants).

Alkyl polyglycol ethers, fatty alcohol polyglycol ethers, fatty alcohol ethoxylates, RCH2(OCH2CH2)nOH, were the first nonionic
surfactants produced on an industrial scale. They are synthesized in a base-catalyzed reaction. Fatty alcohol-alkylene oxide
adducts, which are produced in a base-catalyzed reaction of fatty alcohols, ethylene oxide, and propylene oxide, are low-
foaming surfactants.

Alkyl sulfates, fatty alcohol sulfates, belong to the group of anionic surfactants and are the longest known synthetic
surfactants. In order to synthesize this class of compounds, fatty alcohols are treated with sulfur trioxide, chlorosulfuric acid,
oleum, or sulfuric acid. The resulting semiesters are subsequently neutralized with alkali, mostly aqueous NaOH.

Alkyl polyglycol ether sulfates, fatty alcohol ether sulfates, also belong to the group of anionic surfactants. They are produced
by reaction of fatty alcohols with ethylene oxide and the resulting adducts are then treated with sulfur trioxide or chlorosulfuric
acid. The subsequent neutralization is carried out with caustic soda, ammonia, or ethanolamine.

Alkyl methylammonium chlorides belong to the group of cationic surfactants and are produced using fatty alcohols especially
in the range of C16 – 18.

Alkylpolyglycosides (APG) are prepared from fatty alcohols and sugars following various procedures. They have good skin
compatibility and, if necessary, can be manufactured from renewable raw materials only. However, high production costs are
usually a limiting factor for their application.

Other Uses. In addition, the polar character of the fatty alcohols allows their use as lubricants. Esters of fatty alcohols with
fatty acids, the so-called wax esters, e.g., as lubricants in polymer processing and as raw materials for waxes and creams in
technical applications. Esters are used also in cosmetic applications, but here usually liquid products on the basis of
unsaturated fatty alcohols and/or fatty acids are preferred.

Acrylic and methacrylic acid esters of fatty alcohols are precursors of polymethacrylates, which are utilized as flow enhancer
and viscosity index improvers in oils. Fumaric acid esters have similar applications. Esters of adipic, acelaic, sebacic,
trimellitic, citric, and phthalic acid are used as plasticizers for PVC. The various specific applications of specialty plasticizers
are based on their chemical structure, their high cold flexibility, compatibility, high thermostability, high aging stability, and low
fogging-values in the finished product. Each of the mentioned esters offers special chemical and physical properties for the
different application areas.

A further high volume application is in the area of fragrances and flavors. Aldehydes, esters, or alkyl groups on the basis of
fatty alcohols are sometimes incorporated into more complex molecules like cinnamon aldehyde. Important for this
application are high-purity single cuts which can be processed into these products without any loss in quality.

Alcohols with a chain length of C8 – 10 are used as so-called tobacco sucker control agents in the cultivation of tobacco.

Especially fatty alcohols with chain lengths ≥ C18 — either in an emulsified form or as derivatives — are suitable for
protection of water reservoirs against evaporation during dry seasons. If fatty alcohols are emulsified with interface-active
substances, the resulting emulsion can be applied to the water surfaces. The layer, which is formed fast and easily on the

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water surface, prohibits the evaporation and therefore protects the water reserves. Field tests in Europe and in Africa have
proved the effectiveness. The evaporation can be reduced to up to 50 %.

The same higher fatty alcohols can also be used as defoamer systems for papers to be produced in modern, fast operating
paper machines. Products on the basis of fatty alcohols show the following advantages compared to silicon-based
defoamers: high effectiveness, good biodegradability, good drainage and deaeration, water recycling, and high cost
effectiveness. Each paper quality and each production facility demands different defoamer qualities, which contain
emulsifiers and additives in addition to the alcohol.

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3. Unsaturated Fatty Alcohols

Unsaturated fatty alcohols are special products and can only be obtained from natural sources; petrochemical processes for
their manufacture do not exist. Unsaturated fatty alcohols contain at least one olefinic group in addition to the hydroxyl
function. Therefore they can react both as alcohols and as olefins. The physical properties of the most important unsaturated
fatty alcohols are listed in Table 4. The melting points are below those of the corresponding saturated alcohols and are
influenced by the configuration of the double bond.

Table 4. Physical and chemical properties of primary unsaturated fatty alcohols

IUPAC name Common CAS Molecular Mr Hydroxyl Iodine

mp, bp, ° Density, Refractive
name °C C
registry formula number number (p, g/cm3 index
kPa)
number (t, °C) (t, °C)

10-Undecen- [112-43-6] C11H22O 170.3 329 149 –2 133 0.8495 1.4509

1-ol (2.1) (15) (20)
(Z)-9- oleyl [143-28-2] C18H36O 268.4 209 95 –7.5 208 – 0.8489 1.4606
Octadecen-1- alcohol 210 (20) (20)
ol (2.0)
(E)-9- elaidyl [506-42-3] C18H36O 268.4 209 95 36 – 216 0.8388 1.4552
Octadecen-1- alcohol 37 (2.4) (20) (40)
ol
(Z,Z)-9,12- linoleyl [506-43-4] C18H34O 266.5 211 191 –5 153 – 0.8612 1.4782
Octadecadien- alcohol to – 154 (20) (20)
1-ol 2 (0.4)
(Z,Z,Z)- linolenyl [506-44-5] C18H32O 264.5 212 288 133 0.8708 1.4775
9,12,15- alcohol (0.27) (25) (25)
Octadecatrien-
1-ol
(Z)-13- erucyl [629-98-1] C22H44O 324.6 173 78 34 – 240 – 0.8416
Docosen-1-ol alcohol 35 242 (33)
(1.3)
(E)-13- brassidyl [ C22H44O 324.6 173 78 53 – 238 –
Docosen-1-ol alcohol 5634-26-4] 54 243
(1.05)

Production. The first large-scale hydrogenation plant (Henkel) went into operation in the late 1950s. Previously, unsaturated
fatty alcohols could be obtained only by hydrolysis of whale oil (Section Hydrolysis of Wax Esters) or by the Bouveault –
Blanc reduction (Section Reduction of Wax Esters with Sodium).

Today, a broad range of raw materials based on animal or vegetable fats and oils are available. Both market factors and the
degree of unsaturation (iodine number) required in the final product influence the selection.

For products with iodine numbers around 50, cheap beef tallow or vegetable raw materials are available. Products with iodine
numbers of 80 – 100 can be produced from technical oleic acid (animal or vegetable based). Polyunsaturated products are
undesirable as they tend to autoxidation. For special applications products with higher iodine numbers (> 110) based on
sunflower or soybean oils are produced. Unsaturated alcohols with iodine numbers > 150 are produced, e.g., from linseed oil.

The hydrogenation processes described in Section Hydrogenation Processes are suitable for the large-scale production of
unsaturated fatty alcohols. The fixed-bed processes are preferred because of the mild reaction conditions. In suspension
hydrogenation, the prolonged contact between fatty alcohol and catalyst results in side reactions such as saturation of the
double bond and formation of trans isomers, which leads to a higher solidification point and, hence, loss of quality. With
polyunsaturated fatty acids, the formation of conjugated double bonds cannot be completely prevented.

Hydrogenation is generally carried out at 250 – 280 °C and a pressure of 20 – 25 MPa. Catalysts include zinc oxide in
conjunction with aluminum oxide, chromium oxide, or iron oxide, and possibly other promoters [84-89]; copper chromite
whose activity has been reduced by the addition of cadmium compounds; and cadmium oxide on an alumina carrier [90].
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Selective hydrogenation can also be carried out in a homogeneous phase with metallic soaps as catalysts. An overview of
early catalyst developments is given in [78]; further references can be found in [79-83]. Patent applications of the 1980s
indicate great interest in selective catalysts [91-96].

Unsaturated fatty alcohols are produced in the Federal Republic of Germany (Henkel, Ecogreen) and in Japan (New Japan
Chemical).

Uses. Unsaturated fatty alcohols are used in detergents, in cosmetic ointments and creams, as plasticizers and defoamers
and in textile and leather processing [23], [97-99]. Oleyl alcohol is also used as an additive in petroleum and lubricating oils.

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4. Guerbet Alcohols
Condensation of primary alcohols at 180 – 300 °C in the presence of alkaline condensation agents leads to primary, -
branched dimeric alcohols. The difference in structure between Guerbet and other branched fatty alcohols is shown in
Figure 8. The physical and chemical properties of Guerbet alcohols are listed in Table 5.

Figure 8. Examples of different types of branched fatty alcohols

Table 5. Physical and chemical properties of Guerbet alcohols

IUPAC name CAS Molecular Mr Hydroxyl mp, ° bp, °C Density, Refractive

registry C g/cm3
number formula number (p, kPa) (t, °C) index (t, °
C)

2-Methyl-1- [105-30-6] C6H14O 102.18 549 147.9 0.8263 1.4182

pentanol (101.3) (20) (20)
2-Ethyl-1- [104-76-7] C8H18O 130.23 431 <–76 118 0.8328 1.4328
hexanol (10.7) (20) (20)
2-Propyl-1- [ C10H22O 158.29 354 117 (2.7)
heptanol 10042-59-8]
2-Butyl-1- [3913-02-8] C12H26O 186.34 301 126 – 1.4457
octanol 128 (20)
(1.5)
2-Pentyl-1- [5333-48-2] C14H30O 214.39 262 154 (1.7) 0.8352 1.4460
nonanol (24) (24)
2-Hexyl-1- [2425-77-6] C16H34O 242.45 231 –30 175 (1.5) 0.8380 1.4476
decanol to – (20) (25)
26
2-Heptyl-1- [5333-44-8] C18H38O 270.50 207 –26 198 (2.0) 0.8446 1.4550
undecanol (15) (15)
2-Octyl-1- [5333-42-6] C20H42O 298.56 188 –20 135 – 0.8329 1.4545
dodecanol 137 (21) (19)
(0.007)
2-Nonyl-1- [ C22H46O 326.61 172 164 – 0.8476 1.4582
tridecanol 54439-52-0] 167 (17.5) (17)
(0.013)
2-Decyl-1- [ C24H50O 354.67 158 173 – 0.8413 1.4606
tetradecanol 58670-89-6] 175 (17) (17)
(0.007)
2-Undecyl-1- [ C26H54O 382.72 147
pentadecanol 79864-02-1]
2-Dodecyl-1- [ C28H58O 410.77 137 203 –
hexadecanol 72388-18-2] 207
(0.007)
2-Tridecyl-1- C30H62O 438.83 128
heptadecanol
2-Tetradecyl-1- [ C32H66O 466.88 120 38 – 308 –
octadecanol 32582-32-4] 39 310
(2.0)
2-Pentadecyl-1- C34H70O 494.94 113
nonadecanol

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2-Hexadecyl-1- [ C36H74O 522.99 107 43 – 270 –
eicosanol 17658-63-8] 45 280
(0.013)
2-Heptadecyl-1- C38H78O 551.05 102
heneicosanol
2-Octadecyl-1- C40H82O 579.11 98
docosanol
2-Nonadecyl-1- C42H86O 607.16 95
tricosanol
2-Eicosyl-1- [ C44H90O 635.22 93
tetracosanol 73761-81-6]

The condensation reaction was first observed by M. GUERBET [100]. Its mechanism and selection of catalysts has been
thoroughly studied [3], [5]. Figure 9 illustrates the reaction mechanism in simplified terms.

Figure 9. Mechanism of the Guerbet reaction

Today this reaction is performed on a technical scale with a worldwide production capacity of several thousand tons per year.
The alcohol which is to be dimerized is mixed with an alkaline condensation agent and a hydrogenation/dehydrogenation
catalyst and then heated to 180 – 300 °C. The water formed in the reaction is distilled off continuously together with the
monomeric alcohol. Since the reaction proceeds faster at higher temperatures, especially the reaction of short-chain
monomeric alcohols (C6 – C10 alcohols) is performed under pressure to perform it in a suitable temperature range. However,
low-molecular, -branched dimeric alcohols, e.g., 2-ethyl-1-hexanol, can be produced more economically by other methods (
2-Ethylhexanol).

Physical Properties. The physicochemical properties of Guerbet alcohols can be summarized as follows [101]:

– Melting point or pour point are considerably lower than those of linear alcohols with the same molecular mass.
– Volatility and vapor pressure are significantly lower than those of linear alcohols with comparable consistency (but lower
molecular mass).
– As compared with other liquid unsaturated alcohols the Guerbet alcohols are stable against oxidation and autoxidation.

Uses. Based on these properties Guerbet alcohols in the range of C12 – 36 can be used in the following application areas:

– Cosmetic-pharmaceutical oil components with high stability against autoxidation (rancidity)

– Plasticizers for synthetic resins, e.g., nitrocellulose lacquers (for the production of permanent templates)
– Solvents or solution aids for printing inks and specialty inks
– Lubricant components, e.g., for metal processing oils and fiber preparations
– Chemical intermediates, e.g., for production of branched carboxylic acids
– Starting materials for textile auxiliaries, e.g., esters, sulfates, phosphates, ethersulfates

The Guerbet alcohols C32 – 36, which can be manufactured from C16 – 18-alcohols, are used as:

– Esterification components for the manufacture of specialty waxes

– Raw materials for cosmetic stick preparations

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5. Bifunctional Fatty Alcohols

Some natural oils which contain double bonds, hydroxyl groups, or other functional groups can be converted into long-chain
diols. These are usually , -diols or diols whose hydroxyl groups lie far apart. Table 6 lists physical properties of
bifunctional fatty alcohols.

Table 6. Physical and chemical properties of bifunctional fatty alcohols

IUPAC name CAS registry Molecular Mr Hydroxyl mp, °C bp, °C Density,

number formula g/cm3
number (p, kPa) (t, °C)

1,6-Hexanediol [629-11-8] C6H14O2 118.17 949 42 134 (1.3) 0.9580

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(45)
1,7-Heptanediol [629-30-1] C7H16O2 132.20 849 18 151 (1.9) 0.9570
(25)
1,8-Octanediol [629-41-4] C8H18O2 146.23 767 61 167 – 168 0.9200
(2.4) (60)
1,9-Nonanediol [3937-56-2] C9H20O2 160.26 700 45 173.2 0.9160
(1.9) (50)
1,10-Decanediol [112-47-0] C10H22O2 174.29 644 73 175 – 176 0.8960
(1.9) (75)
1,11-Undecanediol [765-04-8] C11H24O2 188.31 596 63 178 (1.6)
1,12-Dodecanediol [5675-51-4] C12H26O2 202.34 555 81 183 – 184
(1.25)
1,13-Tridecanediol [13362-52-2] C13H28O2 216.37 519 75 – 76 195 – 197
(1.3)
1,14- [19812-64-7] C14H30O2 230.39 487 85 200 (1.2)
Tetradecanediol
1,15- [14722-40-8] C15H32O2 244.42 459 70.6 – 205 – 207
Pentadecanediol 71.6 (1.3)
1,16- [7735-42-4] C16H34O2 258.45 434 91.4 195 – 200
Hexadecanediol (0.53)
1,17- [66577-59-1] C17H36O2 272.48 412 96 – 204 – 205
Heptadecanediol 96.5 (0.27)
1,18- [3155-43-9] C18H38O2 286.50 392 97 – 98 210 – 211
Octadecanediol (0.27)
1,19- [7268-65-7] C19H40O2 300.53 373 101 212 – 214
Nonadecanediol (0.2)
1,20-Eicosanediol [7735-43-5] C20H42O2 314.56 357 102.4 – 215 – 217
102.6 (0.2)
1,21- [95008-70-1] C21H44O2 328.58 342 105 – 223 – 224
Heneicosanediol 105.5 (0.2)
1,22-Docosanediol [22513-81-1] C22H46O2 342.61 328 105.7 –
106.2
1,23-Tricosanediol [95491-58-0] C23H48O2 356.64 314
1,24- [22513-82-2] C24H50O2 370.67 302
Tetracosanediol
1,25- [92238-33-0] C25H52O2 384.69 292 109
Pentacosanediol
(Z)-9-Octadecene- [540-11-4] C18H36O2 284.49 394 89 182/0.06
1,12-diol

1,2-Diols can be produced by epoxidation of internal or -olefins with subsequent hydrolytic cleavage of the epoxide ring (
Alcohols, Polyhydric).

Dimerization of unsaturated fatty acids such as soybean, linseed, and tallow fatty acid, followed by esterification and catalytic
hydrogenation, gives saturated diols [102].

, -unsaturated fatty alcohols can be produced by pyrolysis of castor oil (Atochem) or by metathesis of oleic acid methyl
ester [103].

Thermal or catalytic dimerization of unsaturated alcohols yields viscous dimers with complex structure and an average of two
hydroxyl groups per molecule [104], [105].

1,12-Octadecanediol, 1,10-decanediol, and 9-octadecene-1,12-diol are obtained from castor oil by transesterification and
hydrogenation, or by alkali splitting, esterification, and hydrogenation. , -Diols with high purity can be produced from the
corresponding dicarboxylate esters [106], e.g.,

Suberate 1,8-Octanediol
Sebacate 1,10-Decanediol
Dodecanedioate 1,12-Dodecanediol

Sebacic acid is based on castor oil. Nature offers today new plants and new renewable raw materials for different
applications by cultivation or genetic engineering.

Bifunctional fatty alcohols are mainly used in the production of polyesters and polyamides and as intermediates.

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[Top of Page]

6. Quality Specifications
Analytical methods defined by DIN [107] and ASTM [108] standards and by the Deutsche Gesellschaft für Fettwissenschaft
(DGF) [109] are used for the quality control of fatty alcohols (see Table 7). In addition, analytical methods from the different
fatty alcohol suppliers might be used.

Composition of fatty alcohol mixtures is determined by gas chromatography, which can be combined with mass
spectrometry. Alcohols from different sources can thus be identified; typical examples are given in Figure 10.

Figure 10. Typical fatty alcohol compositions obtained by different processes

(Blue = n-alcohols; Violet = isoalcohols; Yellow = unsaturated alcohols; L = linearity)

Table 7. Analytical methods for the characterization of fatty alcohols

DGF * DIN ASTM

Composition by gas chromatography

Hydrocarbon content by column chromatography on silica
Color (Hazen, APHA) 53409 D 1686–81
Color (Lovibond) C-IV 4b D 1209–84
Refractive Index C-IV 5 53491 D 1218–82
Density C-IV 2b 51757 D 1298–80
D 891–59 (1976)
Viscosity C-IV 7 53015 D 445–83
Solidification point M-III 4a 51570 D 87–77 (1982)
Boiling range 51751 D 1078–83
E 133–78 (1984)
Flash point C-IV 8 51758 D 56–82
D 93–80
Ignition temperature 51794 D 2155–66 (1976)
Hydroxyl number C-V 17a/b D 1957 (1984)
Carbonyl number C-V 18 E 411
Peroxide number C-VI 6a D 1022–76
Iodine number (Kaufmann) C-V 11b
Iodine number (Wijs) C-V 11d D 1959 (1984)
Acid number C-V 2 53402 D 1613–81
Saponification number C-V 3 53401 D 94–80
Water content C-III 13a 51777 D 1744–83

* DGF = Deutsche Gesellschaft für Fettwissenschaft.

Linearity L is defined as the percentage of normal alcohols present in the mixture:

Coconut alcohol gives very few impurity peaks. It contains < 0.1 % n-tridecanol and varying amounts of n-alkanes, depending
on the hydrogenation process.

Tallow alcohol contains up to 2 % isomeric pentadecanols (isopentadecanol, anteisopentadecanol, and n-pentadecanol) and
n-hexadecane, and up to 4 % isomeric heptadecanols (isoheptadecanol, anteisoheptadecanol, and n-heptadecanol) and n-
octadecane.

Ziegler alcohols (Alfol and Epal alcohols) are primary, straight-chain alcohols with an even carbon number. Gas
chromatography shows up to 1 % impurities, consisting of numerous even-numbered, isomeric fatty alcohols.

Oxo alcohols from statistical, cracked olefins or from paraffin dehydrogenation by the Pacol process or SHOP olefins contain

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a large number of isomers that cannot be completely separated, even in the most efficient capillary columns. Both odd- and
even-numbered isoalcohols occur. Oxo alcohol mixtures can be identified by spectroscopic determination of the degree of
branching, i.e., the ratio of n-alcohols to isoalcohols, which depends on the production process and the raw materials used.

Fatty acids obtained by oxidation of paraffinic hydrocarbons yield even- and odd-numbered primary alcohols with a low
degree of branching. Branched alkanes present in the original paraffins are lost by oxidative degradation.

The boric acid-catalyzed process (Bashkirov oxidation) yields secondary alcohols with a statistical distribution of isomers.

Guerbet alcohols are primary, -branched fatty alcohols with two straight-chain alkyl groups of approximately equal length.

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7. Storage and Transportation

During production, processing, and storage, fatty alcohols are handled as liquids. Fatty alcohols starting from C12OH solidify
at ambient temperatures. Products with a melting point above 40 °C can therefore be transferred to, stored, and handled as
flakes or pastilles.

Fatty alcohols are sensitive to oxidation and should be stored under an inert gas; the temperature should not be higher than
20 °C above the melting point. Low-pressure steam or warm water are recommended for heating. Water increases stability to
autoxidation; as little as 0.1 % has a stabilizing effect. The use of antioxidants depends on further processing and quality
requirements.

Stainless steel or an Al – Mg – Mn alloy (DIN 1725/1745) is used as container material; ordinary steel should have a zinc
silicate coating, e.g., Dimetcote. Pumps, valves, and pipes exposed to the product should be made of stainless steel.

Fatty alcohols are considered as flammable materials and are classified according to properties such as flash point and
boiling point. Their transport is governed by national and international regulations dealing with volatile and combustible
materials.

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8. Economic Aspects

The economic significance of fatty alcohols is reflected by the worldwide installed production capacities of ca. 2.4 × 106 t/a in
2004, which will increase to ca. 2.8 × 106 t/a by the year 2007. Table 8 shows these production capacities categorized by
volume, location and raw materials. In summary, ca. 50 % of the fatty alcohols are produced from natural raw materials, but
the split per geographical region is different from continent to continent and will shift to 60 % in favor of natural-based fatty
alcohols by 2008. Worldwide production and consumption are estimated at 1.8 – 1.9 × 106 t/a for 2004 with a yearly increase
of 2 – 3 %. In Europe only ca. 5 % of this volume is used directly as fatty alcohols. A share of 70 – 75 % is used in
surfactants exclusively [76], [77], [110-114].

Table 8. Estimated production capacities for fatty alcohols in 2005, 103 t

Continent Natural alcohols, ≥ C10 Synthetic alcohols, ≥ C11 Total

USA 190 560 750

Europe/South Africa 395 529 924
Asia 651 142 793
Total 1236 1231 2467

In the United States the synthetic fatty alcohol capacities predominate with ca. 70 % share of the total capacity. The largest
producers of synthetic alcohols are Shell (SHOP/oxo process), and Sasol North America (Ziegler/Alfol process). Natural fatty
alcohols are produced by Procter & Gamble and Cognis (formerly Henkel).

In Europe/South Africa, ca. 40 % of the production capacity is based on natural raw materials. The largest manufacturer is
the Sasol Group, exploiting all three technologies, i.e., Ziegler, oxo and natural production processes. Other European
manufacturers, such as BASF, ICI, Exxon, and Shell, predominantly use the oxo process. As the second largest Western
European manufacturer for fatty alcohols, Cognis, produces exclusively from natural raw materials using high pressure
hydrogenation processes.

In the Far East the share of production capacities from natural raw materials is ca. 80 %. This share will further increase by
planned additional capacities of about 600 000 t by 2008. The currently largest manufacturers of natural fatty alcohols are
Ecogreen, Sawit Mas, and Kao Soap Corp. Synthetic fatty alcohols are manufactured by the oxo process, e.g., by Mitsubishi
Chemical, Mitsubishi Petrochemical and Fushun, or by the Ziegler process, used in Jilin.

In Eastern Europe fatty alcohols are manufactured predominantly on the basis of the paraffin oxidation process.

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Considering the existing production capacities and based on the announced capacity increases, assuming an estimated
yearly increase of the fatty alcohol demand of 2 % to 3 %, ca. 80 % of the capacities will be utilized through the year 2005
[76], [77], [116], [118]. The planned new capacities will be based on fats and oils and on petrochemical or Fischer – Tropsch
raw materials, respectively.

The capacity utilization of each production unit depends on the overall economic development, the product mix and the
prices for the used raw materials. Figure 11 shows the differences in price for raw materials based on crude oil, fats, and oils.

Table 9. Fatty alcohol production capacities (C10 and higher) by company, country, location, process and raw
material 2005/2006

Raw Capacity,
Country Location Company material Process 103 t
USA Cincinnati Cognis oleochemical methyl ester 45
hydrogenation
USA Sacramento P&G oleochemical methyl ester 145
hydrogenation
USA Lake Charles SASOL ethylene Ziegler 60
USA Geismar Shell ethylene modified oxo 500
Total America 750
China Dalian Dalian Oil+Fats oleochemical methyl ester 15
hydrogenation
China Guandong Jiangman oleochemical methyl ester 15
hydrogenation
China Fushun Fushun olefins oxo 50
China Jilin Jilin Chem. ethylene Ziegler 47
India Jalgaon Aegis Chem. oleochemical fatty acid 4
hydrogenation
(Lurgi)
India Anklesshawar Godrey oleochemical fatty acid 65
hydrogenation
(Lurgi)
India Bombay VVF oleochemical wax ester 60
hydrogenation(Lurgi)
Japan Tokushima NewJapanChem oleochemical methyl ester 7
hydrogenation
Japan Mizushima Mitsubishi olefins oxo 10
Japan Yokkaichi Mitsubishi olefins modified oxo 35
Indonesia North Ecogreen oleochemical fatty acid 35
Sumatra hydrogenation
(Lurgi)
Indonesia Batam Ecogreen oleochemical methyl ester 80
hydrogenation
Malaysia Kuantan P&G/Felda oleochemical methyl ester 75
hydrogenation
Malaysia Selangor Cognis oleochemical methyl ester 30
hydrogenation
Malaysia Penang Kao/Palmco oleochemical methyl ester 165
hydrogenation
Philippines Lucena Colgate oleochemical methyl ester 5
hydrogenation
Philippines Jasaan Kao oleochemical methyl ester 30
hydrogenation
Philippines Primofina / oleochemical methyl ester 30
Pencentury hydrogenation
(Davey)
Philippines Bauan United Coconut oleochemical fatty acid 35
hydrogenation
(Lurgi)
Total Asia 793
Romania Government paraffins oxidation (idle 10
capacity)
Russia Government paraffins oxidation (idle 60
capacity)
Russia Ufa Government ethylene Ziegler 20
Belgium Ertevelde Oleofina oleochemical methyl ester 35

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hydrogenation
France Boussens Sidobre/Cognis oleochemical methyl ester 40
hydrogenation
Germany Brunsbüttel SASOL oleochemical fatty acid 35
hydrogenation
(Lurgi)
Germany Rodleben Ecogreen oleochemical methyl ester 10
hydrogenation
Germany Düsseldorf Cognisl oleochemical methyl ester 180
hydrogenation
Germany Marl SASOL oleochemical methyl ester 95
hydrogenation
Germany Ludwigshafen BASF olefins oxo 50
Germany Brunsbüttel SASOl ethylene Ziegler 42
UK Stanlow Shell ethylene modified oxo 107
Italy Augusta SASOL olefins oxo 120
S. Africa Secunda SASOL FT olefins oxo 120
Total 924
Europe/Africa

Figure 11. Price development of raw materials used for the production of fatty alcohols

While until 1973 crude oil based, synthetic fatty alcohol production units had considerable advantages, this picture changed
significantly due to the price increases for crude oil in 1973 – 1974 and 1979 – 1980 and subsequently for secondary
products such as naphtha, paraffins, and ethylene. On the long run the price increase rate for fats and oils was considered to
be lower than for crude oil [76], [77], [115], [116], [120-127], leading to an expansion of the natural production capacities. In
the beginning of 1999 the price for crude oil was again nearly as low as the price in 1974. Therefore, fatty alcohols on the
basis of petrochemical raw materials had a cost advantage over natural-based fatty alcohols. This changed again in the
second half of 1999, whereas in 2005 the natural-based products enjoy the advantage of high crude oil prices again. The
period 1995 – 2005 was a decade of change [119]. Some units were shut down or reinstalled at other places, and larger
plants were build to take advantage of economy of scale. Pants with a size of 100 000 t/a are now regarded as standard.

The long-term estimate was based on an increase in crop yields for fats and oils, new hybrids of oil plants, a wider
geographical distribution of their cultivation areas, and the renewable character of these raw materials in contrast to crude oil.
All of this guaranteed a reliable supply. Therefore, the ratio of the production capacities of synthetic to natural fatty alcohols
changed in favor of natural products (2005). In spite of production increases for coconut oils, increased utilization of palm
kernel and babassu oils, and the new hybrids of C12-rich oils like cuphea varieties, natural products are mainly limited to the
C16 – C18 range (90 % of all products) [128]. Synthetic alcohols, however, show their strength especially in the C12 – C15
range, which plays an important role in surfactant applications. Therefore, the C16 – C18 C-chain range is predominantly
based on natural, the C12 – C15 range on petrochemical based raw materials. However, due to logistical, economical and
political reasons, overlapping and reversals can occur [76], [115], [116].

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9. Ecotoxicology and Toxicology

The following toxicological characterization covers alcohols with C-chain lengths from C6 to C24. Besides data regarding the
acute toxicity (after single intake of the substance) and regarding local effects (skin- and mucous membrane irritation, data
on sensitization effects), especially data regarding the toxicity after repeated intake of small amounts of a substance need to
be taken into account for the toxicological characterization. This is especially valid for substances which have virtually no
acute toxicity as e.g. fatty alcohols. Questions regarding a possible carcinogenic effect or regarding possible reproduction
damage or teratogenic effects are the main focus point today when the toxicological properties of chemical substances are
assessed.

For the assessment of the properties of fatty alcohols Condea data and data from scientific publications were used. Here
especially the IUCLID-data [129] were consulted, which were compiled by the manufacturers according to the
ECAltstoffverordnung (EEC 793/93).

9.1. Ecotoxicology and Environmental Aspects

Linear fatty alcohols are in general easily biodegradable. The biological degradation of secondary fatty alcohols proceeds
slightly slower, however, the decomposition rates in standardized lab tests are comparatively high. For the assessment of the
page 18 of 23
Fatty Alcohols : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
data it has to be considered that the solubility of fatty alcohols in water decreases with increasing C-chain length. Therefore,
the alcohols are present only in an extremely low concentration in aquatic environments. Effects, which are detected in
various test systems, often have to be regarded as secondary effects caused by undissolved, finely dispersed substance
particles, and therefore have to be distinguished from “real” substance effects.

For aquatic organisms fatty alcohols possess only moderate acute toxicity. In general, in the concentration range of their
water solubility no toxic effects are observed. However, a number of studies was performed with concentrations which are
considerably above the water solubility. The observed toxic effects can also be attributed to the aforementioned secondary
effects. The available data for the chronic toxicity neither indicate a special toxicological potential of fatty alcohols. Dodecanol
shows a more distinct toxicity in the studies. However, this toxicity cannot unmistakably be attributed to a direct substance
effect, but can possibly be induced by physical effects as well. A complete separation of the aqueous solution from
undissolved but finely dispersed dodecanol is virtually impossible. Therefore, a rest of undissolved dodecanol always
remains in the water.

9.2. Toxicology
Linear fatty alcohols are predominantly metabolized by oxidation. The resulting fatty acids can be subsequently integrated
into the fatty acid metabolism. A further metabolic reaction is conjugation of the fatty alcohols with glucuronic acid and
subsequent excretion.

Fatty alcohols possess virtually no acute toxicity after oral intake or after exposure to the skin. Especially fatty alcohols with a
shorter C-chain length irritate the skin in higher concentrations, in animal tests eye irritations were observed as well. The
irritating effect decreases with increasing C-chain length. In studies with volunteers some fatty alcohols show a considerably
lower skin irritating effect. This has, at least in part, to be attributed to the different test conditions of studies with volunteers
as compared with animal experiments. The available data and the chemical structure of fatty alcohols do not indicate a
sensitizing potential of fatty alcohols. From today's point of view even after long-term intake of the typical linear fatty alcohols,
substance induced damage is not to be expected. The available data show that fatty alcohols do not possess genotoxicity,
which is not to be expected anyway on grounds of their chemical structure. Valid data regarding a carcinogenic effect are not
available. But, based on structure-effect considerations, it can be assumed that fatty alcohols do not have a carcinogenic
potential.

For some of the fatty alcohols at least guidance data on reproduction toxicity are available. These data show that under the
study conditions fatty alcohols neither reduced the fertility nor had an embryo or fetotoxic effect.

In Table 10 data on the toxicity of fatty acids after short-term exposure are listed. Table 11 summarizes data on the acute
toxicity to aquatic organisms and degradability data [129-134].

Table 10. Acute toxicity (oral and dermal), skin Irritation, eye Irritation, and sensitization of fatty alcohols (data from
animal experiments)

Substance LD50 (oral) LD50 (dermal) Skin Eye Sensitization

Irritation Irritation

1-Hexanol 3100 – 1500 – moderately irritant no sensitization

5000 mg/kg (rat) >5000 mg/kg irritant
(rabbit)
1-Octanol > 3200 – > 5000 mg/kg moderately irritant no sensitization
>5000 mg/kg (rabbit) irritant
(rat)
Decanol 5000 mg/kg (rat) > 3500 mg/kg irritant irritant -
(rabbit)
Dodecanol > 5000 mg/kg > 8300 mg/kg moderately moderately -
(rat) (guinea pig) irritant irritant
Tetradecanol 5000 – > 5000 mg/kg slightly slightly -
20 000 mg/kg (rabbit) irritant irritant
(rat)
Hexadecanol > 5000 – > 5000 mg/kg - - no sensitization
> 7500 mg/kg (rabbit)
(rat)
Octadecanol > 5000 – - - - -
> 8000 mg/kg
(rat)
Eicosanol >10 000 mg/kg - not irritant slightly -
(rat) irritant
Docosanol > 10 000 mg/kg - not irritant slightly -
(rat) irritant
2-Butyloctanol 27 – 33 g/kg (rat) - not irritant not irritant no sensitization
(human data)
2-Hexyl-1- > 33 000 mg/kg - slightly not irritant no sensitization
decanol (rat) irritant (human data)
C16 – C20- > 39 000 mg/kg - not irritant not irritant no sensitization

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Fatty Alcohols : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
Branched (rat) (rabbit) (guinea pig) (guinea pig,
Alcohols human data)
2- > 5000 – - slightly slightly no sensitization
Octyldodecanol > 42 000 mg/kg irritant irritant (guinea pig,
(rat) (guinea pig) (guinea pig) human data)
2-Decyltetra- > 39 000 mg/kg - not irritant not irritant no sensitization
decanol (rat) (human data)

Table 11. Ecotoxicity of fatty alcohols

Acute
Bio- Acute Fish Daphnia Algae Bacteria
Substance Degradability Toxicity Toxicity Toxicity Toxicity

1-Hexanol biodegradable > 100 mg/L > 100 mg/L 10 – 3000 –

100 mg/L 10 000 mg/L
1-Octanol biodegradable 10 – 10 – 100 mg/L 10 – 350 –
100 mg/L 100 mg/L > 10 000 mg/L
Decanol easily 1 – 10 mg/L 1 – 10 mg/L - > 10 000 mg/L
biodegradable
Dodecanol easily < 1 mg/L < 1 mg/L < 1 mg/L > 10 000 mg/L
biodegradable
Tetradecanol biodegradable - - - -
Hexadecanol biodegradable - - > 100 mg/L -
Octadecanol biodegradable > 100 mg/L > 100 mg/L > 100 mg/L > 10 000 mg/L
Eicosanol - - - - -
Docosanol - - - - -
2-Butyloctanol biodegradable - - - -
2-Hexyl-1-decanol easily > 100 mg/L - - -
biodegradable
C16 – C20-Branched - - - - -
Alcohols
2-Octyldodecanol biodegradable > 100 mg/L - 100 mg/L > 10 000 mg/L
2-Decyltetradecanol biodegradable - - - -

[Top of Page]

References
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page 23 of 23
 Felts 1

Felts
Nonwoven Fabrics and Wool are separate keywords.

Friedrich Dornedden, Filzfabrik Fulda GmbH & Co., Fulda, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . 1 3.3. Properties . . . . . . .. . . . . . . . . . 6

2. Felting Process . . . . . . . . . . . . . . 2 3.4. Uses . . . . . . . . . . .. . . . . . . . . . 6
3. Pressed Felts . . . . . . . . . . . . . . . 2 3.5. Testing . . . . . . . . .. . . . . . . . . . 7
3.1. Raw Materials . . . . . . . . . . . . . . 2
4. Needled Felts . . . . .. . . . . . . . . . 7
3.2. Production . . . . . . . . . . . . . . . . 2
4.1. Production . . . . . .. . . . . . . . . . 7
3.2.1. Batt Production . . . . . . . . . . . . . . 2
3.2.2. Piece Felts . . . . . . . . . . . . . . . . . 3 4.2. Properties and Uses . . . . . . . . . . 8
3.2.3. Formed Felts . . . . . . . . . . . . . . . . 6 5. References . . . . . . .. . . . . . . . . . 9

1. Introduction
Felt (nonwoven) is defined as a material made
entirely from mechanically consolidated fibers
(DIN 61 205).
Pressed felts (wool and hair felts) are materi-
als, composed either of fibers that can be felted
or of a mixture of these and other fibers. These
nonwoven fabrics are consolidated by the uti-
lization of moisture, heat, pressure, and mechan-
ical work (felting and, if necessary, pressing).
Needled felts are materials made from fibers
that are consolidated by using a large number of
needles. The needles alternately penetrate and Figure 1. Scanning electron micrograph (× 3500) of a
Merino wool fiber
are withdrawn from the fibers in a process called
needling.
Nonwovens (→ Nonwoven Fabrics) are dis- 2. Felting Process
tinguished in DIN 61 210 from needled felts be-
cause they are consolidated by the following dif- The felting process ist still not completely under-
ferent methods: stood [3], [4]. The felting ability of wool fibers
1) by use of a binding agent depends primarily on the scales on their surface
2) by partially dissolving the fibers (Fig. 1) and on their elastic properties (see also
3) by melting the fibers → Wool). The scales of any one fiber all point in
4) by shrinking the fibers under the influence of the same direction, thereby creating a directional
heat and/or a swelling agent frictional effect that allows the fibers to move
5) by the action of liquid jets more easily in the direction of their roots when
6) by needling and subsequent consolidation, force is applied. Only fibers with scales can be
using methods 1 to 4 [1] felted. During felting and fulling of fibrous webs
(batt), the individual fibers are pressed together,
The felting of wool and animal hair was forced to move against one another, and become
discovered in ancient times. Felt caps, 3500 mutually intertwined. Ends or parts of fibers that
years old, were found in the megalithic graves of are not interlocked escape into the interspaces in
Jutland. The Chinese referred to felt as far back the felt. On removing the applied compressing
as 2300 b.c. [2]. force (stress relief), the fibers try to spring back

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 297
2 Felts

into their original stress-free positions. How- 3.2.1. Batt Production

ever, friction prevents complete stress relief. The
original position and form of each fiber is perma- The raw fiber material is fed into one or more
nently changed at the end of felting and fulling, carding willows either in pneumatic mixing
and the fibers are firmly interlocked. plants or multiple mixers. The fiber flocks are
loosened (opened), and uniformly blended dur-
ing repeated passage through the machine. Ad-
3. Pressed Felts dition of carding oil makes the fibers pliable
for further processing. The loosened fibers are
then fed in batches into a carding machine via a
3.1. Raw Materials
weigh feeder which may be electronically con-
trolled or via a volumetrically controlled hopper.
Wool and/or other animal hair are the basic
The carding machine separates the fiber flocks
raw materials for the production of pressed felts
into their individual fibers. Different card sets
(wool felts, hair felts, and hair – wool felts). Only
are available, depending on the raw material,
these fibers possess the natural felting power
and the required quality and properties of the
that enables the fibrous web made from the
resulting batt. The fibers leaving the carding ma-
carded fibers to be consolidated by using moist
chine are longitudinally oriented in the form of
heat pressure, and mechanical work. Other fibers
a web which has a mass of 10 – 20 g/m2 . The
that cannot be felted (cellulose fibers, synthetic
carded web is laid in several layers on the 60 –
fibers, cotton, etc.) can be added to obtain special
70-m long, continuous cloth belt of a batt frame
effects, to produce felts with specific properties,
(Fig. 3) to produce a predetermined thickness or
or to reduce costs.
mass of batt. The resulting batt is subsequently
Hair – wool felts are produced from a mix-
rolled up.
ture of wool and animal hair (preferentially hair
In the continuous production of “cross-laid”
from cattle, calves, or goats). Since the fulling
or “cross-lapped” batt, carding is followed by
power of hair is lower than that of wool, the
the use of a cross lapper instead of a batt frame.
felted, semifinished product is soaked in hot, di-
The cross lapper picks up the carded web and
lute sulfuric acid before fulling.
deposits it at alternating angles of about 45 ◦
(i.e., in a zig-zag pattern) across a conveyor
Bating. Hat felts contain wool, rabbit fur, or
belt (→ Nonwoven Fabrics) so that the fibers are
hare fur (velour hats). The animal fur first has to
aligned crossways. The cross-lapped batt can be
be softened to improve its fulling power by a pro-
laid onto another oriented web and its mass can
cess known as bating. The fur is usually exposed
be changed by stretching. Ideally, a multidirec-
to a mineral acid – hydrogen peroxide solution
tional web is obtained whose tensile strengths
(bate). Poisonous mercury bates are employed
in the lateral and longitudinal directions are the
only in the production of velour from hare fur.
same [7].
In bating machines, only the ends of the hairs
Both methods yield batt in roll form; this is
are exposed to the bate making them softer, more
the starting material for the production of piece
pliable, and more resilient. As a result, they can
felts and formed felts.
intertwine more easily when the untreated hair
shafts move in the direction of their roots dur-
ing felting and fulling. Bating also increases the 3.2.2. Piece Felts
frictional coefficient of the animal hairs, and thus
improves their mutual adhesion [5]. Felting. The batts used to produce piece felts
are laid singly or on top of one another, depend-
ing on the thickness or mass desired in the fin-
3.2. Production ished product. The layers of batt are then con-
veyed between damp cotton cloths and fed into
The production of pressed felts is summarized a plate hardener or roller hardening machine.
schematically in Figure 2 (cf. [6]). Before entering the felting aggregate (vibrating
plates or felting rollers), the batts pass over a
 Felts 3

Figure 2. Production of piece and formed felts

steaming plate, where they are moistened and

heated by the steam that passes through them.
The circular vibrator motion of the felting
plates in the discontinuously operating plate
hardener (Fig. 4) coupled with the action of
moisture, heat, and pressure consolidate and felt
the fibers.

Figure 3. Schematic of a batt frame Figure 4. Plate hardener

The hardening plates are shown lifted for transporting the
felt, they are lowered during felting.
4 Felts

Figure 5. Roller hardening machine

a) Axially vibrating rollers: b) Heated rollers; c) Conveyor belt; d) Cotton cloth

Figure 6. Pilgrim Step roller fulling machine

a) Steam heating; b) Outlet table; c) Fulling rollers; d) Sprinkling device; e) Inlet table

In the continuous roller hardening machine, In a roller fulling machine (shown schemat-
the cotton cloths and the batt pass through two ically in Fig. 2, fulling of piece felts), the felt
horizontal rows of rollers, one row being above passes between two horizontal rows of 15, 21,
the other (Fig. 5). The lower rollers are made of or 24 rollers, one row being above the other. The
stainless steel and are heated, while the upper rollers are made of steel and are covered with
rollers are coated with plastic and vibrate axi- rubber. For light felts, lower rollers with a diam-
ally. The batt is pressed between each pair of eter of 90 mm are used, but for processing heav-
rollers and subjected to their vibrating action. ier felts, the diameter of the lower rollers must be
The pressure is released between two consecu- increased to 120 mm. Only the lower rollers are
tive pairs of rollers. The batt is thus consolidated powered and their speed decreases from roller to
and felted [8]. roller, which causes the material to “pile up” into
folds in the direction of transport. The diameter
Fulling. The production of felts with higher of the upper rollers is ca. 10 mm less than that of
densities involves the use of a procedure called the lower rollers mounted exactly below them.
fulling. In this process, the material is further The upper rollers have spring bearings and turn
felted by kneading, hammering, and pounding, on contact with the folds of material produced
often with the addition of fulling media. Some by the lower rollers. At high running speed, the
felts need no further consolidation by fulling, upper rollers hammer and beat the material as it
however. Felts used for upholstery and quilts, for passes through the machine [9].
example, are merely dried and, if necessary, fin- In the Pilgrim Step roller fulling machine
ished after felting. Lighter piece felts and indus- (Fig. 6), the felt is again transported on a con-
trial felts, which may not need to be processed veyor belt between two horizontal rows of
in a kicker mill, are fulled on a roller fulling ma- rollers. The rollers work in Pilgrim Step, i.e.,
chine or a Pilgrim Step roller fulling machine. they swing forward and backward, the backward
 Felts 5

movement being shorter than the forward move- ous cycle washing machines are used, primarily
ment. Thick folded layers of felt are thus formed, because they are less expensive and save water.
which are intensively kneaded and processed as The washed, natural-colored felt can be dried
they pass through the machine. and finished. However, lighter felts are generally
Kicker mills (also known as hammer fulling dyed by piece dyeing in high-temperature beam
machines) are used for fulling heavier piece felts dyeing machines, where the felt is wound on per-
with a thickness of several millimeters; they forated drums, or on winch becks in the form of
are indispensable for the processing of formed ropes.
felts, such as disks, sheets, or blocks. They are Squeeze foulards or centrifuges are employed
equipped with one to four hammers (Fig. 7). to remove water. The felt is then stretched and
dried with warm air on drying frames (single
layer or multilayer tenters). Finishing foulards
can also be used prior to the drying tenters.
The felt is held in place by means of chains
studded with needles or tenter clips as it passes
through the frame. Advancing or lagging results
in shrinkage or stretching and, thus, determines
the dimensions of the felt. Felts used for cloth-
ing, decorative purposes, and toys are subjected
to finishing, which involves shearing, steaming,
decatizing, and/or pressing. Felts may be given
other special finishing treatments, depending on
the purpose for which they are to be used; they
may, for example, be stiffened, softened, flame-
proofed, or mothproofed.

3.2.3. Formed Felts

In the production of formed felts (summarized in

Fig. 2), the carded fibrous web is roughly formed
into a defined shape (round, square, or rectangu-
Figure 7. Kicker mill lar) and is then built up by crosslaying succes-
a) Felt sheet; b) Filling material; c) Trough; d) Hammers
(only two of the three hammers are shown)
sive layers. The preformed web is conveyed bet-
ween cloths over a steaming plate and steamed
The type of fulling aid employed depends before being felted in a plate hardener. Felting
on the felt quality, mass, bulk density, and the in the hardener may take several minutes, de-
fulling method (machine). Steam or warm wa- pending on the thickness of the felt. The formed
ter is often sufficient for fulling light felts with felts are then treated with dilute sulfuric acid
a roller fulling machine or a Pilgrim Step roller and are either partially fulled on a Pilgrim Step
fulling machine. Fulling with a kicker mill re- roller fulling machine or completely fulled to
quires the addition of fulling aids such as sulfu- yield a specific density of 0.40 – 0.44 g/cm3 . A
ric acid, soaps, anionic fatty acid condensation kicker mill must be used if a high degree of hard-
products, or nonionic compounds based on high ness is required (greater than F 4 as specified in
molecular mass ethoxylated alcohols. DIN 61 200). During fulling the felt must be con-
stantly kept moist and warm with hot water or
Final Treatment. The wool used for felt with fulling liquor, i.e., hot dilute sulfuric acid.
production often contains marking ink (pitch The felt is subsequently deacidified in neutral-
marks), which is manually treated with pitch ization tubs and, if necessary, leveled in a Pilgrim
solvents before washing. These solvents should Step process. It is then centrifuged to reduce its
then be washed off along with the lubricants, moisture content to ca. 60 % and dried in a dry-
fulling media, wool grease, and dirt. Continu- ing room until the residual moisture content is
6 Felts

5 – 10 %. The felt disks, sheets, and blocks are 3.4. Uses

then pressed and their surfaces are sanded. This
material may be punched, cut, drilled, molded, Felts are sold as piece felts in lengths (rolled
or machined to provide a large variety of items. or doubled) or as formed felts (blocks, sheets,
Hat felt must be very carefully fulled. Only disks) and processed as such into felt goods.
hard, compact felts should be used for making They are used industrially in the manufacture
hats; these felts are produced as described in Sec- of machines, equipment, and automotive vehi-
tion 3.2.1 by blending, opening, and cleaning the cles. The natural properties of felt are exploited
wool or bated hair. The resulting material is sub- for a wide range of applications, e.g., for dust
sequently formed on a cone, and is then felted and oil seals, oil wicks, roller coverings, air and
and fulled to a specific size on machines spe- liquid filters, polishing and buffing wheels, self-
cially constructed for hat production. The form adhesive insulating tapes, prepunched insulating
thus obtained is finally dyed, stiffened, formed, components, sound proofing, shock absorption
prepared, and decorated. linings, pads, piano felts, and orthopedic and sur-
gical felts [10].

3.3. Properties
3.5. Testing
The properties of felt are determined primarily
The most imortant tests performed on indus-
by the choice of raw materials and by the man-
trial felts are the determination of their hardness
ufacturing method used. Felts can be as soft and
characterized by the bulk density
RX in g/cm3
pliable as fabrics, flexible/resilient, or even hard.
and their thickness. Felt hardness classes, as de-
Bulk densities of up to 0.80 g/cm3 have been
fined in DIN 61 200, are given in Table 1. Felt
attained under optimal conditions. Top-quality
hardness is directly related to the pore volume,
products with a density of 1.0 g/cm3 can be made
compressibility, and elasticity. The bulk density,
in special cases by adding thermoplastic fibers
according to DIN 53 855 and ASTM D461-59,
and further pressing.
is calculated from the mass and the volume of
Felt displays the following special proper-
the felt [11].
ties: elasticity, porosity (high pore volume),
tensile strength combined with extensibility; Table 1. Hardness classification of felts (DIN 61200)
high, density-dependent compressibility and re-
Bulk density
Rx , g/cm3 Felt hardness
covery; thermal insulation (heat retention) and 0.10 – 0.16 soft
shock (vibration) and sound absorption; forma- 0.18 – 0.30 intermediate
bility; permeability to air and moisture (“breath- 0.32 – 0.48 compact
0.52 – 0.68 hard
ing,” moisture exchange); absorptive capacity;
and uniform dyeing. The properties of wool felt
are not significantly altered by long-term expo- Standard procedures for testing felt thick-
sure to lubricants and organic solvents. A low ness are described in DIN 53 855 and largely
concentration of an inorganic acid, such as sul- correspond to those stipulated in ISO 4603 and
furic or hydrochloric acid, does not have an ad- ISO 5084. The standard thickness of wool felt
verse effect on wool felts, but a strong alkaline is measured on a circular testing area of 10 cm2 .
solution does. Unlike some other industrial ma- A testing pressure of 5 cN/cm2 must be applied
terials, wool felts are affected very little by at- to felt with a bulk density < 0.14 g/cm3 , and
mospheric factors, such as moisture, heat, cold, a pressure of 25 cN/cm2 to felts with a bulk
sun, and ozone. Felt is unchanged by temper- density > 0.14 g/cm3 . For smaller testing areas
atures from − 50 to 100 ◦ C. Two of the most (<10 cm2 ), the testing pressure must be reduced
important features of wool felt as a mechanical proportionately.
and industrial material are that it is durable and The relative compressibility ZRx is defined in
relatively maintenance-free. DIN 53 855 as:
ax −a10x
ZRx = 100 %
ax
 Felts 7

where ax is the standard thickness of the felt de- 4.1. Production

termined by using the normal testing pressure
(average of more than three determinations) and The choice of raw materials depends on the de-
a10x is the thickness when a 10-fold higher pres- mands made on the needled felts and, thus, on
sure is applied. the manifold uses of the finished product. Syn-
The pore content V px is calculated from the thetic fibers consisting of natural and synthetic
density of the fibers,
N , and the bulk density, polymers and inorganic fibers are preferred, but

Rx : carbon fibers can also be employed. Fibers based
on aromatic polyamides (e.g., Nomex, Kevlar)
N −Rx
Vpx = 100 % and on polytetrafluoroethylene (e.g., Teflon) are
N
of considerable industrial importance. Needled
In the case of mixed felts, the density of the floor coverings are made chiefly from polyamide
fibers,
N , is obtained from the densities of the and polypropylene fibers. Products used for in-
components of the mixture. sulation and upholstery are made from low-
Further tests can be conducted for special grade fibrous material or from recycled natural
purposes, some being performed in both lon- fibers, cellulose, or synthetic fibers.
gitudinal and lateral directions. These tests are The raw material is first loosened (opened)
described in DIN 61 206 and ASTM D461-77 and blended in a willower. A lubricant or an-
and include the determination of the follow- tistatic agent can be added at this stage. The
ing properties: tensile strength and elongation fibers are then aerodynamically built up as a mul-
at break, rupture strength, washing or ironing tidirectional web. Alternatively, a crosslapped
shrinkage, wool content, length and width, ba- web can be produced on a carding machine and
sic mass (mass related to area), air permeabil- may subsequently be stretched; a multidirec-
ity, abrasion loss, pH value, residual fat con- tional web can then be obtained with additional
tent, longitudinal resistance to fluid flow, degree equipment.
of sound absorption, thermal conductivity, and In the needling machine (Fig. 8), the web
fiber damage based on the measurement of the fibers pass between two parallel perforated
alkali solubility of wool. Other properties are oil plates and are penetrated by numerous barbed
absorption, intrinsic vibration frequency, vibra- needles. The barbs force the fibers down and,
tion damping, and heat resistance. The vibration as needling progresses, they become increas-
test can be used to determine the felting capacity ingly intertwined thus consolidating the web.
of wool [12]. Alkali and acid solubility tests can The fibers remain locked in their new posi-
also be employed in the case of bated rabbit and tions when the needles are withdrawn because
hare fur [13]. the barbs all face in one direction, i.e., toward
the needle point. To attain greater compaction
and consolidation, several needling machines
4. Needled Felts are usually employed in series. These machines
often differ from each other in their needle fit-
The use of needled felts for industrial purposes tings or in the direction of penetration. The web
dates from the 1870s. The technique of needling can be subjected to needling from one side ei-
creates feltlike structures from fibers that are ther above or below, or from both sides, either
otherwise incapable of being felted by means alternately or simultaneously.
of numerous barbed needles that vertically pen- In felts required for some industrial uses, the
etrate and compress the fibers. web is needled into a base material made of wo-
The appearance in the 1950s of new synthetic ven or spunbonded threads, or foil to produce
fibers with novel properties stimulated further high tensile strength, low stretching, and high
development of the needling technique. New, ef- resistance to deformation [15].
ficient needling machines, in combination with Mechanical and thermal treatments as well
improved felting needles, led to the development as chemical finishing (singeing, shrinkage, ther-
of products with new properties that could not mofixation, spraying, coating, etc.) produce spe-
be obtained by other methods [14]. cial effects and influence the dimensions and
8 Felts

physical properties of the felt, such as thickness, are available in a wide variety of colors, surface
porosity, elasticity, and volume. The surface of a structures, and patterns. Needled felts are also
needled felt is generally smooth, but the texture employed as floor coverings for indoor tennis
can be manipulated to give a velour, looped, or courts. Other uses include interior decorations,
patterned surface [16]. soundproofing in cars, wall coverings, mattress
covers, thermal insulation, and shock and sound
absorption. A more recent application of needled
felts is their use a geotextiles which are modern
construction materials used in water and dam
construction, land recovery, and other sectors of
civil and hydraulic engineering [17].

5. References
1. H. Dietrich, Verfahrenstechnik (Mainz) 2
(1971) 68; Staub Reinhalt. Luft 5 (1974) 176;
Wasser Luft Betr. 17 (1973) 248.
2. W. Voegelin, W. A. Vetterli, Ciba-Rundsch. 12
(1958) no. 139, 22 – 23.
3. G. Blankenburg: Chemische und physikalische
Eigenschaften von unveränderter und
veränderter Wolle in Beziehung zum
Filzvermögen, vol. 36, Deutsches
Wollforschungsinstitut an der T. H. Aachen,
Figure 8. Needling machine 1963, pp. 9 – 23. P. A. Koch, G. Satlow, in
a) Incoming fibrous web; b) Rollers; c) Holddown plate; Großes Textil-Lexikon, “Filze,” Deutsche
d) Perforated plate; e) Needle board; f) Felting needle; Verlagsanstalt, Stuttgart 1965, pp. 427 – 440.
g) Needled felt; h) Magnified view of needles showing barbs 4. A. J. P. Martin, J. Soc. Dyers Colour 60
and attached fibers
(1944) 325. G. Blankenburg, Th. Laakmann,
Melliand Textilber. 4 (1971) 467 – 470. Wool
Sci. Rev. 24 (1964) 34 – 48; Text. Prax. 2
4.2. Properties and Uses (1965) 166. R. Walther, Melliand Textilber. 39
(1958) 1240 – 1242
The properties and uses of needled felt prod- 5. R. D. B. Fraser, T. A. Pressly, Text. Res. J. 6
ucts are directly related to the fibrous raw ma- 478 – 485, and Text. Prax. 12 (1958) 1291.
6. I. Holme: “Wool pressed felt manufacture,”
terial, to the method of batt formation, and to
Wool Sci. Rev. 61 (1985) 36 – 44. H. Dietrich,
the needling technique employed. The uniform
Melliand Textilber. 39 (1958) 977 – 982.
distribution of fibers combined with an almost 7. H. Dietrich, Melliand Textilber. 40 (1959)
uniform density throughout the felt makes nee- 591 – 596.
dled felts more suitable for filtration than woven 8. H. Dietrich, Text. Prax. 12 (1960)
or roughened sheet structures. Therefore, nee- 1238 – 1242.
dled felt filters have proved to be an efficient 9. H. Dietrich, Melliand Textilber. 55 (1974)
medium for commercial air filtration (dust sep- 714 – 717.
aration, product recovery, and air purification) 10. L. R. Mizell: “The properties, functions and
and for the separation of solids from liquids. uses of pressed wool felts,” Wool Sci. Rev. 61
In the paper industry, needled felts that are (1985) 3 – 35.
more than 15 m wide and are made from syn- 11. Cl. Sustmann, M. Greul, Textilingenieurschule
thetic fibers have almost completely replaced the Aachen, Erfahrung u. Forschung 9 (1957) 71,
conventional woven felts made from wool or as- and Melliand Textilber. 44 (1963) 443, 560,
bestos (woven in tubular form as round felts) 674. Broschüre des Verbandes d.
[17]. Durable floor coverings for living areas Wollfilzindustrie: Filze 1964.
 Felts 9

12. G. Blankenburg, H. Zahn, Text. Praxis 16 15. J. Lünenschloß, V. P. Gupta, K. Berns,

(1961) 228. G. Blankenburg, H. Philippen, Textilbetrieb (Würzburg) 95 (1977) Okt.,
Melliand Textilber. 51 (1970) 1345. 32 – 34; Nov., 23 – 28; Dez. , 47 – 54.
13. H. G. Fröhlich, Z. Gesamte Textilind. 58 16. J. Ph. Dilo: “Herstellung strukturierter
(1956) 947. Nadelvliesstoffe,” Chemiefaser Text. Ind. 31/
14. J. Lünenschloß, H. Külter, TPJ Text. Prax. Int. 83 (1981) 674 – 679, E 73 – 76.
10 (1977) 1227 – 1229. 17. Ch. Schaerer, Textilveredlung 21 (1986) 81.

Fermentation → Biotechnology
Fermium → Transuranium Elements
Ferrites → Magnetic Materials
 Ferroalloys 1

Ferroalloys
Rudolf Fichte, Gesellschaft für Elektrometallurgie mbH, Nürnberg, Federal Republic of Germany

Ferroalloys are master alloys containing el- The large-volume ferroalloys – ferrosilicon,
ements that are more or less soluble in molten ferromanganese, ferrochromium – are prepared
iron and that improve the properties of iron and continuously by carbothermic reduction in large,
steel. These alloys usually contain a significant submerged-arc furnaces. The carbon is provided
amount of iron [7439-89-6]. Ferroalloys have by coke, and the power supply ranges from
been used for the last 100 years, principally in 15 to 100 MVA. Ferromanganese is also pro-
the production of cast iron and steel [1]. As addi- duced in blast furnaces. Both ferromanganese
tives, they give iron and steel improved proper- and ferrochromium, because of their affinity
ties, especially increased tensile strength, wear for carbon, contain high concentrations of car-
resistance, and corrosion resistance. These ef- bon (7 – 8 wt %). In contrast, ferrosilicon con-
fects come about through one or more of the tains little carbon; in fact, the carbon concentra-
following: (1) a change in the chemical compo- tion decreases as the silicon concentration is in-
sition of the steel; (2) the removal or the tying creased, e.g., ferrosilicon containing 25 wt % Si
up of harmful impurities such as oxygen, nitro- contains 1 wt % C, while that containing 75 wt %
gen, sulfur, or hydrogen; and (3) a change in the Si contains only 0.1 wt % C.
nature of the solidification, for example, upon Low-carbon ferromanganese (0.1 – 2 wt % C)
inoculation [2]. or ferrochromium (0.02 – 2 wt % C) is produced
Ferroalloys are also used as starting materials in the following way: a silicon-containing al-
in the preparation of chemicals and pure metal; loy, ferrosilicomanganese or ferrosilicochromi-
as reducing agents (e.g., the use of ferrosilicon to um, is made by carbothermic reduction of an ap-
reduce rich slags); as alloying elements in non- propriate ore and quartzite in a submerged-arc
ferrous alloys; as starting materials for special furnace. Then this silicon alloy is used for the sil-
products such as amorphous metals. The indi- icothermic reduction of an appropriate ore in an
vidual ferroalloys are treated in detail along with electric-arc refining furnace. Oxygen is seldom
the alloys of the non-iron component, e.g., fer- used to reduce the carbon content.
roboron is described under → Boron and Boron Ferrophosphorus is a byproduct of the car-
Alloys. Table 1 lists some commercial ferroal- bothermic production of → Phosphorus. Ferro-
loys. , Chap. 2., Chap. 3. tungsten is produced carbothermically in small,
Over the years, the binary ferroalloys have high-power electric furnaces. Ferroboron is pro-
been modified by the addition of further com- duced from carbon, iron, and boron oxide or
ponents. For example, magnesium is regularly boric acid in one- and three-phase electric
added to ferrosilicon, which, when used in cast furnaces. Zirconium-containing ferrosilicon is
iron, produces a spheroidal graphite; and man- made carbothermically in electric furnaces from
ganese or zirconium can be added to calcium – zircon (ZrSiO4 ) or baddeleyite (ZrO2 ); ferrosil-
silicon. icon, with either 75 or 90 wt % Si, is added.
Silicothermic reduction, with the addition of
Production. Generally, ferroalloys are pre- some aluminum, is used to prepare ferromo-
pared by direct reduction of oxidic ores or lybdenum in refractory-lined reaction vessels.
concentrates with carbon (carbothermic), sili- The energy released in the reaction is adequate
con (silicothermic), or aluminum (aluminother- to melt both metal and slag, and the solidified
mic, closely related to the Goldschmidt reac- block of ferromolybdenum can be recovered
tion; → Aluminothermic Processes). However, easily. Ferronickel is also mainly produced by
roasted ores (e.g., for ferromolybdenum) and silicothermic reduction. Aluminothermic reduc-
pure technical-grade oxides (for ferromolybde- tion is the method of choice for the production of
num and ferroboron) are also used as starting ferrovanadium. The starting materials are vana-
materials. dium(V) oxide, aluminum, and iron turnings,

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 305
2 Ferroalloys
Table 1. Ferroalloys

Alloy Composition, wt % Keyword in Ullmann’s

Calcium – silicon [37323-90-3] 28 – 35 Ca Calcium and Calcium Alloys

60 – 65 Si
6 Fe
Calcium – silicon – aluminum 15 – 25 Ca
10 – 40 Al
35 – 50 Si
Calcium – silicon – barium 15 – 20 Ca
14 – 18 Ba
55 – 60 Si
Calcium – silicon – magnesium 25 – 30 Ca
10 – 15 Mg
50 – 55 Si
Calcium – manganese – silicon 16 – 20 Ca
14 – 18 Mn
58 – 59 Si
Calcium – silicon – zirconium 15 – 20 Ca
15 – 20 Zr
50 – 55 Si
Ferroboron [11108-67-1] 12 – 24 B Boron and Boron Alloys
Ferrochromium [11114-46-8] 45 – 95 Cr Chromium and Chromium Alloys
0.01 – 10 C
Ferrosilicochromium [11114-46-8] 40 – 65 Cr
45 – 20 Si
Ferromanganese [12604-53-4] 75 – 92 Mn Manganese and Manganese Alloys
0.05 – 8.0 C
Ferrosilicomanganese [53200-80-9] 58 – 75 Mn
35 – 15 Si
Ferromolybdenum [11121-95-2] 62 – 70 Mo Molybdenum and Molybdenum Compounds
Ferronickel [11133-76-9] 20 – 60 Ni Nickel Alloys
Ferroniobium [11108-69-3] 55 – 70 Nb Niobium and Niobium Compounds
Ferroniobiumtantalum [11108-69-3] 55 – 70 Nb
2 – 8 Ta
Ferrophosphorus [8049-19-2] ca. 25 P Phosphorus
Ferroselenium [11108-70-6] ca. 50 Se Selenium and Selenium Compounds
Ferrosilicon [8049-17-0] 8 – 95 Si Silicon
Ferrotitanium [60591-60-8] 20 – 75 Ti Titanium, Titanium Alloys, and Titanium Compounds
Ferrotungsten [12604-57-8] 70 – 85 W Tungsten, Tungsten Alloys, and Tungsten Compounds
Ferrovanadium [12604-58-9] 35 – 80 V Vanadium and Vanadium Compounds
Ferrozirconium [11108-72-8] ca. 85 Zr Zirconium and Zirconium Compounds
Ferrosilicozirconium [51683-55-7] 35 – 42 Zr
ca. 50 Si

chips, stampings, or nail bits. The reaction is The production of ferroalloys is of great eco-
carried out in refractory-lined reaction vessels. nomic importance, especially in countries that
The reaction produces enough heat to melt both have the raw materials and the energy supply.
metal and slag. In fact, inert materials must be Alloy steels constitute an ever growing fraction
added to keep the peak temperature lower. Fer- of total steel production because of their supe-
rotitanium and ferroboron are also produced alu- rior properties. As an example of the impor-
minothermically. tance of ferroalloys, an estimated ¤ 0.9×109
The production and use of titanium as a large- (ca. $ 0.8×109 ) of ferroalloys were consumed
volume construction material yields enough in 1986 by the steel industry in the Federal Re-
scrap for ferrotitanium containing ca. 70 wt % Ti public of Germany.
to be made by melting iron and titanium scrap to-
gether. Ferrozirconium containing 80 – 85 wt % Environmental Aspects. During the pro-
Zr is also made by melting metal scrap and duction of ferroalloys, the emission of undesir-
iron together. Ferroselenium is produced by the able substances into the environment must be
exothermic reaction of iron and selenium pow- kept under control. There are guidelines for this,
ders. e.g., see [3]. ””
 Ferroalloys 3

References Additives Handbook, Shieldalloy Corp.,

Newfield, N. J., Metallurg Alloy Corp., New
1. R. Fichte, H.-J. Retelsdorf: “Stahlveredler” in York 1981.
Winnacker-Küchler, vol. 4, pp. 198 – 234. 3. VDI-Richtlinien VDI 2576 (May 1983):
Durrer – Volkert: Metallurgie der Emissionsminderung – Elektrothermische und
Ferrolegierungen, 2nd ed., Springer Verlag, metallothermische Erzeugung von
Berlin-Heidelberg-New York 1972. A. G. E. Ferrolegierungen (Emission Control –
Robiette: Electric Smelting Processes, Griffin, Electrothermic and Metallothermic Ferroalloy
London 1973. F. Leitner, E. Plöckinger: Production), vol. 2 of VDI-Handbuch
Edelstahlerzeugung, 2nd ed., Springer Verlag, Reinhaltung der Luft, Beuth Verlag,
Wien-New York 1965. Berlin-Köln 1983.
2. P. D. Deeley, K.-J. A. Kundig, H. R.
Spendelow, Jr.: Ferroalloys and Alloying
 Ferroelectrics 1

Ferroelectrics
Hans-Günther Unruh, Universität des Saarlandes, Fachbereich Physik, Saarbrücken, Federal Republic of
Germany

1. Fundamental Concepts and History 1 2.4. Oxidic Ferroelectrics . . . . . . . . . . 8

1.1. Fundamental Concepts . . . . . . . . 1 2.4.1. Barium Titanate . . . . . . . . . . . . . . 8
1.2. Early Development . . . . . . . . . . . 2 2.4.2. Other Oxides of the Perovskite Type . 10
1.3. Development of Lattice-Dynamic
2.4.3. LiNbO3 Family . . . . . . . . . . . . . . 10
Aspects . . . . . . . . . . . . . . . . . . . 3
2.5. Ferroelectric Ceramics . . . . . . . . 11
2. Properties of Specific Families . . . 5
2.1. KH2 PO4 (KDP) Family . . . . . . . . 5 2.6. Ferroelectric Polymers and Liquid
2.2. Triglycine Sulfate (TGS) Family . . 6 Crystals . . . . . . . . . . . . . . . . . . 12
2.3. (NH4 )2 SO4 (AS) Family . . . . . . . 7 3. References . . . . . . . . . . . . . . . . . 13

1. Fundamental Concepts and fields from the motions and interactions of the
History structural units.
Since any structural transition that is strictly
1.1. Fundamental Concepts or approximately second order can be charac-
terized by a suitable chosen order parameter Q,
Ferroelectrics are materials exhibiting a spon- where – Q – = 0 for T > T c and – Q – > 0 for
taneous dielectric polarization Ps , the direction T < T c , it is natural in the present case to iden-
of which can be reversibly changed by a suit- tify Q as the spontaneous polarization. Ferro-
able transient field. The electric dipole moment electrics for which this choice proves correct are
m = Ps V associated with Ps in a volume V re- called proper ferroelectrics. However, there exist
sults either from a displacement of the centers cases for which the physical quantity that consti-
of charge relative to each other or from an align- tutes a suitable order parameter does not directly
ment of existing dipoles, or from a combination result in a polarized state at T < T c . That a fer-
of these effects. The two limiting forms of ferro- roelectric phase can nonetheless arise is most
electrics are classified as displacive type and or- readily deduced from the existence of thermo-
der – disorder type, respectively. The reversible dynamic relations of the form P ∝ Qn ,
change in direction of Ps in the case of the dis- where n is called a faintness index. Such
placive type requires the existence of at least two ferroelectrics are called improper ferroelectrics.
distinct, physically equivalent arrangements of For proper ferroelectrics the spontaneous polar-
atoms or ions, while in the case of the order – ization Ps is the primary order parameter, while
disorder type it requires at least two equivalent for improper ferroelectrics it is a secondary one.
orientations of molecular dipoles. Examples are given in Section 1.3.
The ferroelectric state is, as a rule, observed As an extensive order parameter, Q can be
only below a temperature T c , the so-called Curie associated with a conjugate intensive variable, a
point, which is characteristic of the particular field h, and thus also a susceptibility, ∂Q/∂h.
material. The transition from the paraelectric In the case of proper ferroelectrics these en-
high-temperature phase, with Ps = 0, to the ferro- tities are the electric field E and the electric sus-
electric low-temperature phase is invariably as- ceptibility χ=∂P/∂E,
sociated with a structural phase transition at T c , tensor notation being avoided here in the in-
in which Ps arises as a result of cooperative dis- terest of simplicity. Since stability of a thermo-
placements in the structural units of the paraelec- dynamic phase requires the reciprocal suscep-
tric phase. If the displacements are viewed as a tibilities to be positive definite, a susceptibility
result of local fields, then the molecular field the- can be expected to exhibit singular behavior at
ory permits calculation of the strength of these a phase transition. Indeed, in the vicinity of the

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 309
2 Ferroelectrics

Curie point the static electric susceptibility χs and ferromagnetics, which, however, was not a
is found as a rule to have a temperature depen- fortunate choice. Occasionally, especially in the
dence in good agreement with the Curie – Weiss Russian literature, the term “Seignette electric”
law in the form is used. This term, which was in general use un-
til about 1940, relates the phenomenon to the
χs −χ∞ =ε0 C/ (T −T0 ) (1) first known ferroelectric, Seignette salt, another
< < name for Rochelle salt. The salt was first pre-
where C > 0 for T > T 0 and ε0 is the permittivity pared by E. Seignette in La Rochelle, France.
of vacuum.
The Curie temperature T 0 generally is only
slightly below the transition temperature T c . 1.2. Early Development
The term χ∞ represents the practically temper-
ature-independent contribution of those degrees Ferroelectric phenomena were first observed
of freedom of the system that do not belong to in 1920 by Valasek [21] in Rochelle salt
the order parameter. [304-59-6], KNaC4 H4 O6 ·4 H2 O. In his descrip-
A homogeneous ferroelectric possesses a tion, he called attention to the analogy with fer-
characteristic direction determined by sponta- romagnetic phenomena. Besides the dielectric
neous polarization. It is therefore polar, non- hysteresis in the function P (E)accompanying
centrosymmetric, and consequently piezoelec- reversal of the electric field E, Valasek also
tric. Since Ps is in general temperature depen- noted the extraordinarily high values of compo-
dent, ferroelectrics are also pyroelectric. If the nents of certain characteristic tensors, such as
temperature of a ferroelectric is lowered from the dielectric function e=c+1
T > T c to T < T c , as a rule no homogeneous and the piezoelectric modulus d, within
state is produced, even in the case of single crys- and near the ferroelectric temperature interval,
tals. Rather, the crystals exhibit a partitioning which for Rochelle salt is 255 – 297 K. The exis-
into macroscopic domains of homogeneous po- tence of a second Curie point, below which the
larization, analogous to the Weiss domains of crystal is once again paraelectric, is not com-
ferromagnetics. The form and organization of mon. The second structural transformation, oc-
these domains vary and depend not only on prop- curring at 255 K, gives rise to a nonpolar low-
erties of the material but also on lattice defects temperature phase. A satisfactory microscopic
of the particular sample. The linear dimensions theory of the ferroelectric behavior of Rochelle
of domains typically lie in the µm to mm range. salt has not yet been formulated. The first ther-
Structural phase transitions are in general re- modynamic analysis of ferroelectric transforma-
ferred to as ferrodistortive if no change in the tions was that of Mueller [22], using Rochelle
periodicity volume occurs during the transition, salt as an example. The central theme of this
and specifically are called ferromagnetic, ferro- analysis is a discussion of a suitable thermo-
electric, or ferroelastic if the (primary) order pa- dynamic potential, which, for a given reference
rameter is the magnetization, the polarization, state, is expanded in powers of independent state
or an elastic deformation, respectively. In addi- variables such as dielectric polarization and elas-
tion, however, the transition of a high-tempera- tic deformation. Among the most significant re-
ture to a low-temperature phase of a crystalline sults are the relationships between dielectric,
substance can also be accompanied by a change elastic, and piezoelectric constants of the ma-
in the translational symmetry owing to the in- terial. These relationships allowed the observed
crease of the periodicity volume by an integer anomalies of the latter material constants to be
factor. In particular, structures occur in which interpreted as consequences of the singular be-
the dipole moments in neighboring unit cells are havior of the dielectric function.
oriented antiparallel to each other. This results Initially, the ferroelectric effect was viewed
in a doubling of the unit cell. Such phases are as a rare curiosity, so it did not trigger any
called antiferrodistortive and, in the electrical systematic studies. Not until 1935 was a sec-
case, antiferroelectric. ond substance, potassium dihydrogen phos-
The nomenclature emphasizes several phe- phate, KH2 PO4 , discovered to be ferroelectric
nomenological analogies between ferroelectrics by Busch and Scherrer [23]. This discovery
 Ferroelectrics 3

was important for the further study of ferro- firming the possibility of spontaneous polar-
electrics in several respects. One consequence ization in chemically and crystallographically
was the prompt discovery that a series of alkali- distinct systems. The following are examples:
metal dihydrogen phosphates and arsenates iso- guanidinium aluminum sulfate hexahydrate
morphic with KH2 PO4 also exhibit ferroelec- [10199-21-0] (GASH), C(NH2 )3 Al(SO4 )2
tric behavior [24], thus pointing to a more gen- · 6 H2 O [34], methylammonium aluminum alum
eral significance of these phenomena. More- [15243-18-2], CH3 NH3 Al(SO4 )2 · 12 H2 O
over, KH2 PO4 has a considerably simpler lat- [35], ammonium sulfate (AS), (NH4 )2 SO4 [36],
tice structure than Rochelle salt, so that in 1941 triglycine sulfate (TGS), (NH2 CH2 CO2 H)3
Slater [25] was able to present a first success- · H2 SO4 [37], and sodium nitrite [7632-00-0],
ful microscopic model for the origin of the fer- NaNO2 [38].
roelectric effect. Of central importance in this The unusual dielectric and piezoelectric
model are ordering processes in the system of properties of ferroelectric materials soon led to
hydrogen bridges, which result in the develop- their utilization as ingredients of capacitors and
ment of dipole moments as a consequence of of diverse electroacoustic transducers, such as
a relative displacement of the anion and cation crystal phonograph pickups and microphones.
lattices. Unlike the water-soluble and moisture-sensitive
Since Kurchatov [26] had assumed in 1933 crystals, such as potassium dihydrogen phos-
that orientational processes of water dipoles phate and Rochelle salt, barium titanate is chem-
are the cause of the ferroelectric property of ically resistant. Moreover, this material is easily
Rochelle salt, a causal relationship between the manufactured as a polycrystalline ceramic in al-
presence of hydrogen bridges and the occur- most any desired shape. These considerations,
rence of the ferroelectric effect was now sus- as well as the possibility of varying the proper-
pected. However, this hypothesis had to be aban- ties of the material over a wide range by suitable
doned when, during the years 1945 – 1948, the doping, were fundamental to the extensive use
dielectric anomalies of BaTiO3 were indepen- of barium titanate [11], [13].
dently discovered in the United States, Rus-
sia, and Japan, and Wul and Goldmann [27]
then observed the ferroelectric transformations 1.3. Development of Lattice-Dynamic
of this substance. The extended phenomenolog- Aspects
ical treatment of ferroelectricity of Ginzburg
[28] was applied in 1949 – 1954 by Devonshire Anderson [39] and Cochran [40] in 1960
[29] to the description of the three successive fer- attributed ferroelectric transformations to the in-
roelectric transitions of BaTiO3 . Devonshire stability of the crystal lattices with respect to
expanded the Gibbs free energy of the cubic certain lattice vibrations, so-called soft modes.
high-temperature phase as a polynomial in po- Much earlier, Fröhlich [41] had associated
larization and deformation and showed that all the frequency ω T of a transverse optical lat-
three ferroelectric phases correspond to minima tice vibration, which appears in the Lyddane –
of the free energy when changes of crystal sym- Sachs – Teller equation
metry were taken into account. 2 2
ωT /ωL =ε∞ /εs
As a structure-sensitive property, ferroelec-
tric behavior was suspected to occur also in and anomalously high values of the static di-
related oxides, and indeed in the next years electric constant εs . However, the occurrence
Matthias and collaborators [30], [31] disco- of a particularly soft TO mode and the conse-
vered it in LiTaO3 , LiNbO3 , KTaO3 , and quent lattice instability if ω T → 0 as T → T +c
KNbO3 . These were followed by other titanates was clearly explained for the first time in 1960.
and, in 1951, by the first known antiferroelec- In particular, Cochran attributed the vanish-
tric, PbZrO3 [32]. In that same year Kittel [33] ing of the force constants proportional to ω 2T
published a phenomenological theory of antifer- at the transition temperature T c of ionic crys-
roelectricity. tals to an equilibrium between short-range repul-
During the 1950s a succession of other fam- sive forces and long-range attractive Coulomb
ilies of ferroelectrics were discovered, con- forces.
4 Ferroelectrics

The equations, which were presented in a where c∗ is a reciprocal lattice vector. Be-
form applicable only to certain cubic crystals, low the transformation at T i , the modulation
can be generalized to other lattices, and mo- imposed on the lattice, owing to the condi-
tivated a rapidly growing number of spectro- tion δ (T )  1, locally causes approximately
scopic studies, utilizing infrared absorption, Ra- a tripling of the unit cell. The temperature-
man scattering, and inelastic neutron scatter- dependent modulation is incommensurable with
ing, which confirmed the theoretical predictions the lattice of the unordered phase and in the case
[10]. Chaves and Porto [42] used a frequency- of potassium selenate gives rise to a structure
dependent representation of the dielectric func- locally polar, but globally centrosymmetric and
tion ε (ω) to generalize the Lyddane – Sachs – thus nonpolar. Potassium selenate becomes fer-
Teller equation, including the case that the roelectric at a temperature T c < T i as
temperature-dependent low-frequency excita- δ (T ) −→ 0
tion responsible for the transformation has the and a commensurable phase that has a tripled
character of a relaxation: unit cell is formed. The homogeneous polariza-
2 2 tion can be viewed as a secondary order param-
ε (ω) iωLO +ω
ωLj +iωγLj −ω
= 2
(2) eter that drives this lock-in process.
ε∞ iωTO +ω j ωTj +iωγTj −ω 2
For an understanding of ferroelectric trans-
Here ω TO and ω LO represent the transverse formations, structure determinations of the ut-
and longitudinal relaxation frequencies, respec- most precision have always been essential [2],
tively, and ω Tj and ω Lj the characteristic fre- [13]. Although considerable effort has been in-
quencies of the transverse and longitudinal os- vested in X-ray and neutron diffraction studies,
cillatory excitations, respectively. In ordered some qualitative and quantitative aspects still
phases the structural changes can, to a first ap- remain unelucidated, even for classical ferro-
proximation, be identified as those atomic dis- electrics such as barium titanate, because the
placements that are described by the eigenvector shifts in atomic coordinates are frequently ex-
of the soft mode. Conversely, the softening of a tremely small. If the symmetry of the disordered
TO mode as a function of temperature became and ordered phases is known, a phenomenolog-
evidence for a ferroelectric transformation. ical description of a ferroelectric can often be
In proper ferroelectrics the soft mode has a accomplished within the experimental accuracy
wave vector q = 0 (Γ point of the Brillouin zone), over a restricted temperature range by recourse
since the order parameter is homogeneous po- to thermodynamic methods [7], but a general mi-
larization. In improper ferroelectrics the corre- croscopic theory does not exist. The treatment of
sponding wave vector q lies within, or on the special models by the methods of the theory of
boundary of, the first Brillouin zone. An ex- phase transitions has been quite successful [8],
ample is gadolinium molybdate [14985-14-9], [15].
Gd2 (MoO4 )3 [43]. The wave vector of the mode
belonging to the order parameter lies at the
boundary of the Brillouin zone; accordingly, be- 2. Properties of Specific Families
low the transition temperature the unit cell is
doubled. In this case the crystal symmetry per- Ferroelectric substances are customarily clas-
mits a polarization proportional to the magnitude sified into families according to chemical and
of the two-component order parameter, as well structural considerations [19], [20], although
as a deformation. The resulting ferroelectric and this approach distinguishes neither the type
ferroelastic properties of the ordered phase were (order-disorder – displacive) nor the nature (fer-
correctly interpreted for the first time as effects roelectric – antiferroelectric, proper – improper)
of secondary order parameters by Pytte [44]. of the phase transformation. At present, the
Finally, the case that the instability involves a known pure compounds with ferroelectric prop-
soft mode for which the wave vector qi lies in the erties number about two hundred, which are
interior of the first Brillouin zone is exemplified classified into about forty families [20]. In ad-
by potassium selenate [7790-59-2], K2 SeO4 . By dition, there are numerous mixed systems, in-
means of inelastic neutron scattering, Iizumi et cluding many materials of commercial impor-
al. [45] in 1977 found q i = (1−δ (T )) c∗ /3, tance. In the following the properties of some
 Ferroelectrics 5

representative substances are presented. A short constant field E and constant mechanical stress
survey of characteristic data is given in Table 1. σ,
Table 1. Curie points and spontaneous polarizations (at a specific 1/εσ ∈ 2 D
33 = 1/ε33 −h36 s66
absolute temperature) for various ferroelectric compounds
1/sE D 2 ∈
66 = 1/s66 −h36 ε33 (3)
Substance Curie point Spontaneous
T c, K polarization Then the “free” permittivity εσ33
also obeys a
Ps , µC/cm2
Curie – Weiss law, but with a higher Curie tem-
PbTiO3 763 75 (295 K) perature than the “clamped” permittivity ε∈
33
LiNbO3 1483 71 (295 K)
Ba2 NaNb5 O15 833 40 (295 K)
Pb5 Ge3 O11 450 4.7 (295 K) Tc,σ =Tc,∈ +h36 sD
66 ε0 C
Gd2 (MoO4 )3 432 0.29 (295 K)
SbSI 295 20 (273 K) The elastic constant sE D
66 , unlike s66 , is also
HCl 98.4 3.7 (95 K) temperature dependent. The effects described
KH2 PO4 123 4.7 (110 K)
SC(NH2 )2 169 3 (140 K) by Equations (3) are the result of symmetry-
Ca2 Sr(CH3 CH2 COO)6 283 0.9 (200 K) allowed coupling terms between the order pa-
(NH2 CH2 COOH)3 · H2 SO4 323 4.5 (100 K)
NaKC4 H4 O6 · 4 H2 O 297 0.24 (275 K)
rameter and other state variables in the expres-
K2 SeO4 93 0.12 (40 K) sion for the energy density, and are characteristic
of ferroelectrics [7].
Microscopic theories of the transformation
of KDP begin with the structural units H2 PO− 4
and K+ , which are pictured in Figure 1. The
2.1. KH2 PO4 (KDP) Family hydrogen bridges oriented at right angles to
the tetragonal c axis connect adjacent phos-
The ferroelectric transition of potassium phate tetrahedra, and for T < T c cooperatively
dihydrogen phosphate [7778-77-0] (KPD), order themselves in such a way that preferen-
KH2 PO4 , occurs at T c = 123 K and is weakly tially the two upper or the two lower protons
first order. Potassium dihydrogen phosphate is lie near a phosphate tetrahedron. The resulting
tetragonal (point group 42 m) in the paraelectric atomic displacements lead to spontaneous po-
phase and orthorhombic (mm 2) in the ferro- larization. The pseudo-spin formalism often em-
electric phase, and thus is piezoelectric both ployed in connection with order – disorder trans-
above and below T c . The static electromechan- formations, together with the assumption of a
ical properties of the material are represented tunnel mechanism of the protons along the hy-
by the coefficients of a series expansion of the drogen bridges, permits interpretation of many
energy density U(Dj , ∈µ ) in the components experimental observations, including a notable
of the dielectric displacement D and the elastic isotope effect: KD2 PO4 [13761-79-0 ] has a
deformation ∈. If the experimental boundary transition temperature 90 K higher than that of
conditions require other independent variables, KH2 PO4 [10], [46].
a suitable thermodynamic potential can be ob- Properties resembling those of KH2 PO4 are
tained by a Legendre transformation of U. In the found for RbH2 PO4 [13774-16-8] (T c = 147 K),
case of KDP, such a Landau formulation yields KH2 AsO4 [7784-41-0] (97 K), and RbH2 AsO4
the following fundamental linear piezoelectric [13463-57-8] (110 K). The homologous ammo-
equations nium compounds are antiferroelectric.
 
E3 = 1/ε∈
33 D3 −h36 ∈6 Preparation and Applications. KH2 PO4
 
σ6 = −h36 D3 + 1/sD
66 ∈6
and its homologues can be prepared in the form
of transparent single crystals from aqueous so-
whereby the components in the polar c direction lutions at room temperature. Controlled growth
are taken into account. The only property of the is achieved by lowering the temperature or re-
material with an anomalous temperature depen- moving solvent from the saturated solutions in
dence is the permittivity at constant deformation, the presence of seed crystals. Occasionally a
ε∈
33 , which obeys a Curie – Weiss law (Eq. 1). For two-chamber process, with circulating solution,
the usual experimental boundary conditions of is employed. In one chamber polycrystalline
6 Ferroelectrics

substance is taken up by a slightly unsaturated are mirror images [47]. The nonequivalence of
solution, in the other chamber single crystals the glycine groups can be brought out by writing
grow at a somewhat lower temperature. the compound as
Members of the KDP family find use pri- (NH2 CH2 COOH) · (NH3 CH2 COOH)+ 2 SO4
2−

marily by virtue of their good piezoelectric, The spectrum of polarization fluctuations asso-
electro-optical, and nonlinear optical properties. ciated with the motions of the molecular dipoles
They are employed in the construction of Kerr can be measured in the form of the frequency
cells, high-frequency light modulators, and op- dependence of the complex permittivity
tical frequency doublers.
ε (ω) =ε (ω) −iε (ω)

2.2. Triglycine Sulfate (TGS) Family In the case of TGS, the dispersion of ε (ω)
is well described [48] by the Debye form for a
Triglycine sulfate [513-29-1] (TGS), relaxation,
(NH2 CH2 COOH)3 · H2 SO4 , is ferroelectric
at room temperature (point group 2) and at ca. ε (ω) =ε∞ + (εs −ε∞ ) / (1+iωτ ) (4)
323 K is transformed into a centrosymmetric, The frequency fε = 1/ (2πτ )
paraelectric phase with the point group 2/m. likewise obeys a Curie – Weiss law and as-
The transition is second order; the static per- sumes the role of the soft transverse relaxation
mittivity parallel to the ferroelectric direction frequency in Equation (2). In the complex ε
obeys the Curie – Weiss law, at T c exceeding plane, the graphs for ε (ω) given by Equation
3×105 ε0 . In the vicinity of T c , the temperature (4) are semicircles. Figure 3 shows the curves
dependence of the spontaneous polarization is for three temperatures.
1/2
given by P s ∝ (Tc −T ) ,
in agreement with thermodynamic theory [7],
[8]. Curves for Ps (T ) and ε0 /ε (T ), which were
determined by experiment, are shown in Fig-
ure 2.

Figure 3. Diagram of the relative complex permittivity

ε (ω)/ε0 of triglycine sulfate at three temperatures [48]
Figure 2. Temperature dependence of the reciprocal relative
permittivity ε0 /ε and of the spontaneous polarization Ps of Numerous other glycine compounds, such as
triglycine sulfate near T c triglycine selenate [920-25-2],
(NH2 CH2 COOH)3 · H2 SeO4
TGS is considered an excellent example of
and triglycine fluoroberyllate [2396-72-7],
a uniaxial ferroelectric of the order – disorder
(NH2 CH2 COOH)3 · H2 BeF4
type. Essentially, the transformation is attributed
have properties similar to those of TGS. In each
to the dynamics of a nonplanar glycine group,
case the deuterated compounds are ferroelectric.
which in the paraelectric phase possesses equiv-
The resulting increase in Curie temperature is
alent positions in a potential with a double mini-
small, 11 K in the case of TGS, so that the hy-
mum, thus giving rise to a crystallographic mir-
drogen bridges in these structures are considered
ror plane of the average structure. The other two
to play no special role in the transformation.
glycine groups of the unit formula are planar and
 Ferroelectrics 7

Preparation and Applications. The water- ferroelectric, zero in the case of an antiferroelec-
soluble crystals are prepared by the same pro- tric. Figure 4 also shows that sufficiently high
cedures as described for KDP ( see page 6). If fields convert the antiferroelectric state into a
the linear growth rate is ca. 0.5 mm/day, growth ferroelectric one. The height of the subloops in-
of a 100-g single crystal takes ten weeks. dicates the twofold polarization of a sublattice.
By virtue of its superb pyroelectric proper-
ties, TGS is used primarily in the construction
of heat sensors, infrared detectors, and thermo- 2.3. (NH4 )2 SO4 (AS) Family
graphic transducers. If the quantity p/(cp ε) is
taken as the figure of merit of a pyroelectric de- The ferroelectrics included in the (NH4 )2 SO4
tector, TGS has a favorable value at room tem- (AS) family belong to the extensive group of
perature owing to its high pyroelectric coeffi- substances with the empirical formula A2 BX4
cient p= ∂P /∂T that in their paraelectric high-temperature phase
and low permittivity ε [49]. have the β-K2 SO4 structure and exhibit ferro-
electric properties in various low-temperature
phases. Examples are (NH4 )2 SO4 [7783-20-2],
K2 SeO4 , Rb2 ZnCl4 [33724-11-7], and some ho-
mologous compounds. For these compounds the
polarization is, as a rule, not the primary order
parameter, and in many cases a transition into
an incommensurably modulated structure oc-
curs above the ferroelectric transition (see Sec-
tion 1.3).
A special case is that of (NH4 )2 SO4 , which
at 223 K undergoes a transition from the para-
electric to a spontaneously polarized low-tem-
perature phase. The transition is first order. The
temperature dependence of the spontaneous po-
larization is shown in Figure 5: Ps reaches zero
near 85 K, and its sign changes on further cool-
ing [52]. In this case, distinct sublattices with op-
posite but no equal polarization give rise to fer-
rielectric behavior resembling ferrimagnetism.

Figure 4. Hysteresis loop of ferroelectric betaine arsenate

(A) [50] and of antiferroelectric betaine deuteroarsenate (B)
[51]

Betaine Compounds. Ferroelectric phases

also exist for compounds of the amino acid be-
taine with various inorganic acids. Betaine arse-
nate, (CH3 )3 NCH2 COO · H3 AsO4 , is ferroelec-
tric below T c = 119 K [50]. Betaine deuteroarse-
nate, (CH3 )3 NCH2 COO · D3 AsO4 , has a transi-
tion temperature 53 K higher, which suggests a
significant role of hydrogen bonds in the trans-
formation. It is remarkable that, in contrast with Figure 5. Temperature dependence of the spontaneous po-
betaine arsenate, betaine deuteroarsenate be- larization of ferrielectric ammonium sulfate [52]
comes antiferroelectric at 172 K [51]. The hys-
teresis loops in Figure 4 show the remanent po-
larization at E = 0, namely, Pr in the case of a
8 Ferroelectrics

2.4. Oxidic Ferroelectrics where G 0 is the enthalpy density of the cubic

reference phase. The individual terms in the ex-
The most numerous, and commercially the most pansion are found as the expressions invariant
important, group of ferroelectric substances are with respect to the symmetries of the reference
oxides. Among these, the perovskites have been phase. The equilibrium conditions
most intensively studied; they also find the most
extensive industrial application in the form of ∂G/∂Pi =Ei = 0
polycrystalline ceramics. lead to the desired solutions:

Pa = Pb = Pc = 0 for the paraelectric, cubic phase

2.4.1. Barium Titanate Pa = Pb = 0 Pc = 0 for the tetragonal phase
Pa = 0, Pb = Pc = 0 for the orthorhombic phase
Pa = Pb = Pc = 0 for the rhombohedral phase
Of all ferroelectrics, the one most thor-
oughly studied is barium titanate [12047-27-7],
BaTiO3 . The paraelectric perovskite structure
(Fig. 6) is cubic and dielectrically isotropic. Be-
low the 403 K Curie point, essentially as the re-
sult of a relative displacement of the oxygen and
titanium sublattices, there arises a dipole mo-
ment parallel to one of the cubic axes and a
tetragonal distortion of the unit cell. On further
reduction of the temperature, corresponding dis-
placements and dipole moments also arise par-
allel to the cubic axes of the original phase that
were initially not affected. As a consequence,
at 278 K the crystal assumes an orthorhombic,
and finally at 183 K, a rhombohedral structure.
For the orthorhombic structure, Ps is parallel
to a face diagonal of the original cubic cell.
Figure 6. Unit cell of cubic barium titanate. The arrows in-
For the rhombohedral case Ps is parallel to a dicate the atomic displacements that result in the tetragonal
body diagonal of the original cubic cell. The structure of the ferroelectric phase.
permittivity obeys the Curie – Weiss law in the
paraelectric phase and below the first transition The temperature is explicitly introduced into
experiences an especially sharp drop parallel the function G by the assumption that
to the polar direction (here the c axis, Fig. 7). α=α0 (T −T0 )
An analogous temperature effect is observed for
the lower-temperature transitions. In its simplest This form of the coefficient α can be justi-
form, the thermodynamic description by De- fied on phenomenological [54] and latticedy-
vonshire [29] of the ferroelectric transforma- namic grounds [40]. Through the relation 1/χ =
tions of BaTiO3 begins with an expansion of the ∂ 2 G/∂P 2 ,
free elastic enthalpy density G in powers of the it leads to the Curie – Weiss law. The coef-
components of the polarization P, while the ex- ficients β, γ, and δ of the expansion are, to a
ternal mechanical stress is taken to be zero: first approximation, viewed as temperature in-
dependent. For the spontaneous polarization of
1   the tetragonal phase subject to equilibrium con-
G=G0 + α Pa2 +Pb2 +Pc2
2 straints, Equation (5) gives the result:
1  
+ β Pa4 +Pb4 +Pc4    1/2
4 Pc2 = − (β/2δ) ± β 2 / 4δ 2 −α0 (T −T0 )
1  
+ γ Pa2 Pb2 +Pb2 Pc2 +Pc2 Pa2 In the case of barium titanate, β < 0, and the
2
1   transition is first order [5], [29]. The maximum
+ δ Pa6 +Pb6 +Pc6 (5)
6 thermal hysteresis for the transition at 403 K is
10 K.
 Ferroelectrics 9

Figure 7. Lattice distortions and temperature dependence of the relative permittivitiy of BaTiO3
The numerical values in all phases are for the orientations parallel (εc ) and perpendicular (εa ) to the tetragonal axis. In the
two low-temperature phases they are only crude estimates, since in those cases the crystal has different principal axes of the
dielectric tensor, and in general there is no single domain state [53].

Barium titanate was long viewed as an ex-

ample of a displacive-type ferroelectric. How-
ever, structural investigations have shown that
the thermal displacements of the atoms exhibit
considerable anharmonicity, so order – disorder
mechanisms also had to be taken into considera-
tion. Results of infrared measurements [55] and
hyper-Raman scattering [56] for the soft mode
can be described within experimental error by
either an oscillator model or a relaxator model.
Oscillator parameters for the soft mode obtained
by hyper-Raman scattering are plotted in Fig-
ure 8.

Preparation and Applications. Single

crystals of BaTiO3 can be obtained in sizes up to
10 cm3 by lowering the temperature of a variety
of fluxes, which include KF, BaCl2 , or excess
TiO2 . Especially good results are obtained with
the top-seeded solution growth technique and a
TiO2 -rich melt at ca. 1630 K [16].
The standard technique of pulling single crys-
tals out of the pure melt cannot be used for cubic Figure 8. Temperature dependence of frequency ω T (•) and
barium titanate, for the melt (mp 1891 K) pro- damping coefficient γ T (
) of the soft mode of barium ti-
tanate obtained from measurements of the hyper-Raman ef-
duces a hexagonal phase, which at 1733 K fect [56]
10 Ferroelectrics

converts into the cubic form, with consequent temperature associated with the high sponta-
destruction of the crystals. neous polarization gives rise to strong piezoelec-
The technical uses of barium titanate single tric, electro-optic, and nonlinear optical effects.
crystals are limited. As a material with a strong Because of these properties, the materials find
linear electro-optic effect, it is above all a can- use in electro-acoustic filters, light modulators,
didate for use in light modulators, as well as for optical amplifiers, and frequency multipliers
applications in dynamic holography, optical im- [13], [57].
age intensification, and phase conjugation optics Materials with high electro-optical coeffi-
[57]. cients and high photoconductivity exhibit light-
induced changes in refractive index. This pho-
torefractive effect is a consequence of the pres-
2.4.2. Other Oxides of the Perovskite Type ence of fields associated with space charges
that are formed under conditions of nonhomo-
Other examples of oxidic perovskites include the geneous illumination. The mechanism is that
ferroelectrics KNbO3 [12030-85-2] and PbTiO3 charge carriers freed by light from defects are
[12060-00-3], which wholly or partly dupli- captured by traps in locations where the light
cate the succession of phases exhibited by intensity is low. Good photorefractive proper-
BaTiO3 , as well as the antiferroelectrics PbZrO3 ties, of use in the storage of phase holograms
[12060-01-4] and NaNbO3 [12034-09-2]. Other and for optical image processing, are found in
perovskites, for example KTaO3 [57126-93-9], LiNbO3 and KNbO3 , but also in BaTiO3 and
show a dielectric behavior conforming to the in Ba2 NaNb5 O15 [12323-03-4], a compound of
Curie – Weiss law, but no ferroelectric transition the tungsten bronze type. Photoconductivity is
is observed down to low temperatures (incip- often achieved by suitable doping, e.g., with
ient ferroelectrics). At temperatures below ca. iron.
2 K quantum-mechanical zero-point vibrations
can suppress the expected ferroelectric order-
ing. The ranks of ferroelectric perovskites are 2.5. Ferroelectric Ceramics
extended by a multitude of complex compounds
as well as solid solutions of simple or complex Perovskite-based ceramics are commercially
perovskites [19], [20]. produced in large quantities and find use princi-
pally in capacitors and positive temperature co-
efficient (PTC) thermistors and as piezoceram-
2.4.3. LiNbO3 Family ics.
Barium titanate ceramic is employed as a di-
The trigonal lattice structure of LiNbO3 electric in capacitors. The dependence of the
[12031-63-9] contains oxygen octahedra that permittivity on temperature and field strength,
are connected through their faces and that con- which as a rule is undesirable, can be minimized
tain Li, Nb, or no atom at all at their center. by partial substitution of Sr or Pb for Ba as well
(The oxygen octahedra in perovskite, in con- as Zr or Sn for Ti. At the same time, the tran-
trast, are connected through their corners.) The sition, which in any case is diffuse in heavily
ferroelectric transition occurs at T c = 1483 K, doped barium titanate, can be lowered to room
thus only slightly below the melting point of temperature, thus achieving high permittivities
1526 K. A member of the same family, LiTaO3 [11]. Attention must also be paid to the grain
[12031-66-2], has a substantially lower Curie size, because of the associated depolarization ef-
point, T c = 893 K. fects.
Light doping, e.g., a few tenths of mole per-
Preparation and Applications. Lithium cent of Sb, Nb, or rare earth, makes barium ti-
niobate and lithium tantalate can be produced tanate semiconducting. If the ceramic also con-
as single crystals of centimeter dimensions and tains traces of Cu, Fe, or Mn, accumulation of
good optical quality from their melts by the these elements at the grain boundaries causes
Czochralski technique. The acentricity at room electrically insulating layers to form, since these
impurities, as acceptors, capture free electrons.
 Ferroelectrics 11

If the acceptor concentration is sufficiently high, where k 2 is the fraction of the electric energy
the ceramic constitutes a blocking layer capaci- supplied that is stored as mechanical energy [6],
tor with high effective permittivity. Lighter dop- [11].
ing (< 0.01 %) produces so-called PTC thermis-
tors; their resistivity can increase by more than
four orders of magnitude in a 100-K interval
above the Curie temperature (Fig. 9) [58]. Below
the Curie point the potential barriers at the grain
boundaries are nullified by polarization charges
of the ferroelectric crystallites, and the electric
resistance of the ceramic is determined by that
of the semiconducting grains.

Figure 10. Phase diagram of the PbTiO3 – PbZrO3 (PZT)

solid solution
AF = antiferroelectric; F = ferroelectric; P = paraelectric

The good electro-optical properties of oxidic

Figure 9. Temperature dependence of the resistivity of bar-
ium titanate ceramic PTC thermistors with various Curie ferroelectrics and the advantages of ceramic ma-
temperatures terials are incorporated in opto-ceramics. High
transparency is achieved by selection of phases
For piezoelectric applications the macro- of minimal optical anisotropy and by special sin-
scopically isotropic ferroelectric ceramic is po- tering procedures as in the case of lanthanum-
larized in electric fields. The optimal orientation doped lead titanate – lead zirconate (PLZT) [13,
of the spontaneous polarization in the randomly pp. 540 – 544]. Materials with the composition
arranged grains is facilitated by elevated temper- Pb1−1.5x Lax
0.5x (Zr0.65 Ti0.35 )O3 with 0.07
atures. Ceramics of lead titanate – lead zirconate < x < 0.1 are used for electro-optical compo-
solid solutions (PZT) [12626-81-2] are particu- nents such as readouts or optical shutters.
larly well suited for piezoceramic applications
by virtue of their high Curie temperatures and Preparation. Ferroelectric ceramics are pre-
high spontaneous polarization as well as their pared by sintering the oxide mix for several
crystallographic properties. The phase diagram hours at temperatures between ca. 1450 and
is shown in Figure 10. Materials with a com- 1650 K. Starting materials are the milled oxides
position close to that of the morphotropic phase or, for especially fine-grained products, com-
boundary between the zirconate-rich rhombohe- pounds prepared by wet-chemical methods. The
dral phase and the titanate-rich tetragonal crystal low-porosity ceramics required for optical appli-
structure exhibit coupling factors up to k = 0.7,
12 Ferroelectrics

cations are obtained by hot pressing or vacuum tion can be altered as in the case of a regular fer-
sintering [11]. roelectric. An example of such a liquid crystal
ferroelectric is p-decyloxybenzylidene-p -ami-
no-2-methyl-butyl-cinnamate [97335-57-4]:
2.6. Ferroelectric Polymers and Liquid
Crystals
Mechanically stretched and electrically polar-
ized foils of the semicrystalline polymer poly-
(vinylidene fluoride) [24937-79-9] (PVDF),
The phase transformations of this system have
been studied in detail [64], [65]. As for incom-
mensurable systems, the dielectric polarization
is not the primary order parameter for this sys-
tem.
exhibit strong piezoelectric and pyroelectric ef-
fects. The further observation that PVDF shows
dielectric hysteresis led to the assumption that 3. References
it is ferroelectric, although no phase transition
occurs up to the melting point (∼ 440 K) of the 1. W. Känzig: Ferroelectrics and
crystallites of the orthorhombic β phase. Models Antiferroelectrics, Academic Press, New York
proposed by Kepler [59] and by Broadhurst 1957.
et al. [60] assume cooperative motions of the 2. H. D. Megaw: Ferroelectricity in Crystals,
polar chain molecules and predict a maximum Methuen & Co., London 1957.
spontaneous polarization of 22 µC/cm2 . A study 3. F. Jona, G. Shirane: Ferroelectric Crystals,
of copolymers of PVDF with polytrifluoroethyl- MacMillan, New York 1962.
ene [61] found evidence for a transformation of 4. H. J. Martin: Die Ferroelektrika, Akademische
a nonpolar high-temperature phase into a ferro- Verlagsgesellschaft, Leipzig 1964.
electric low-temperature phase. 5. E. Fatuzzo, W. J. Merz: Ferroelectricity,
Ferroelectric polymers find applications prin- North-Holland, Amsterdam 1967.
cipally as piezoelectric transducers in the form 6. B. Jaffe, W. R. Cook, H. Jaffe: Piezoelectric
of thin foils. Ceramics, Academic Press, London 1971.
Ferroelectric properties of liquid crystal sys- 7. J. Grindlay: An Introduction to the
tems were first predicted in 1975 by Meyer and Phenomenological Theory of Ferroelectricity,
Pergamon Press, New York 1970.
collaborators [62], [63]. The required symme-
8. H. E. Stanley: Introduction to Phase
try constraints are satisfied by certain mesogenic
Transitions and Critical Phenomena,
phases found in the smectic group of liquid crys- Clarendon Press, Oxford 1971.
tals: in the so-called C∗ phase, rod-shaped, chi- 9. G. A. Smolenskij, N. N. Krainik:
ral molecules are arranged in layers. The long Ferroelektrika und Antiferroelektrika,
axes of the molecules are parallel to each other Teubner, Leipzig 1972.
and inclined at an equal angle to the plane of the 10. R. Blinc, B. Zeks: Soft Modes in Ferroelectrics
layer; thus, the macroscopic symmetry belongs and Antiferroelectrics, Elsevier, New York
to the monoclinic class 2. The polar axis lies par- 1974.
allel to the twofold rotational axis in the plane 11. A. Bauer et al.: Technologie und Anwendungen
of the layer. However, the chiral character of the von Ferroelektrika, Akademische
molecules causes the molecular axes in adjacent Verlagsgesellschaft, Leipzig 1976.
layers to assume a helical arrangement with re- 12. T. Mitsui, I. Tatsuzaki, E. Nakamura: An
spect to the normal to the layer. Consequently, Introduction to the Physics of Ferroelectrics,
a macroscopic polarization does not arise in the Gordon and Breach, New York 1976.
field-free state. In a sufficiently strong electric 13. M. E. Lines, A. M. Glass: Principles and
field directed parallel to the planes of the lay- Applications of Ferroelectrics and Related
ers, the direction of the spontaneous polariza- Materials, Clarendon Press, Oxford 1977.
 Ferroelectrics 13

14. V. M. Fridkin: Photoferroelectrics, Springer 36. B. T. Matthias, J. P. Remeika, Phys. Rev. 103
Verlag, Berlin 1979. (1956) 262.
15. W. Gebhardt, U. Krey: Phasenübergänge und 37. B. T. Matthias, C. E. Miller, J. P. Remeika,
kritische Phänomene, Vieweg, Braunschweig Phys. Rev. 104 (1956) 849 – 850.
1980. 38. S. Sawada, S. Nomura, S. Fujii, I. Yoshida,
16. D. Elwell, H. J. Scheel: Crystal Growth from Phys. Rev. Lett. 1 (1958) 320 – 324.
High-Temperature Solutions, Academic Press, 39. P. W. Anderson in G. I. Skanavi (ed.): Fizika
London 1975. Dielektrikov, Akad. Nauk SSSR, Moscow
17. R. Bechmann et al.: “Elastic, Piezoelectric, 1960.
Piezooptic and Electrooptic Constants of 40. W. Cochran, Adv. Phys. 9 (1960) 387 – 423.
Crystals” in Landolt-Börnstein III/1 (1966); 41. H. Fröhlich: Theory of Dielectrics, Clarendon
Landolt-Börnstein III/2 (1969). Press, Oxford 1949, p. 159.
18. M. M. Choy et al.: “Elastic, Piezoelectric, 42. A. S. Chaves, S. P. S. Porto, Solid State
Pyroelectric, Piezooptic, Electrooptic Commun. 13 (1973) 865 – 868.
43. H. J. Borchardt, P. E. Bierstedt, J. Appl. Phys.
Constants, and Nonlinear Dielectric
38 (1967) 2057 – 2060.
Susceptibilities of Crystals” in
44. E. Pytte, Solid State Commun. 8 (1970)
Landolt-Börnstein III/11(1979).
2101 – 2104.
19. T. Mitsui et al.: “Ferro- and Antiferroelectric
45. M. Iizumi, J. D. Axe, G. Shirane, K.
Substances” in Landolt-Börnstein III/3
Shimaoka, Phys. Rev. B: Solid State 15 (1977)
(1969); Landolt-Börnstein III/9 (1975).
4392 – 4411.
20. T. Mitsui et al.: “Ferroelectric and Related 46. R. Blinc, J. Phys. Chem. Solids 13 (1960)
Substances” in Landolt-Börnstein III/16 a 204 – 211.
(1981); Landolt-Börnstein III/16 b (1982). 47. K. Itoh, T. Mitsui, Ferroelectrics 5 (1973)
235 – 251.
Specific References 48. G. Luther, H. E. Müser, Z. Naturforsch. A:
21. J. Valasek, Phys. Rev. 15 (1920) 537 – 538; 17 Astrophys. Phys. Phys. Chem. 24 A (1969)
(1921) 475 – 481. 389 – 392; Z. Angew. Phys. 29 (1970)
22. H. Mueller, Phys. Rev. 57 (1940) 829 – 839; 58 237 – 240.
(1940) 565 – 573; 805 – 811. 49. S. T. Liu, D. Long, Proc. IEEE 66 (1978)
23. G. Busch, P. Scherrer, Naturwissenschaften 23 14 – 26.
(1935) 737. 50. A. Klöpperpieper, H. J. Rother, J. Albers, K. H.
24. G. Busch, Helv. Phys. Acta 11 (1938) Ehses, Ferroelectr. Lett. Sect. 44 (1982)
269 – 298. 115 – 120.
25. J. C. Slater, J. Chem. Phys. 9 (1941) 16. 51. J. Albers, A. Klöpperpieper, H. E. Müser, H. J.
26. I. V. Kurchatov, Segnetoelektriki, Moscow Rother, Ferroelectrics 54 (1984) 45 – 48.
1933. 52. H.-G. Unruh, Solid State Commun. 8 (1970)
27. B. Wul, I. M. Goldmann, Dokl. Akad. Nauk 1951 –1954.
SSSR 46 (1945) 139; 49 (1945) 177; 51 53. W. J. Merz, Phys. Rev. 76 (1949) 1221.
(1946) 21. 54. L. D. Landau, E. M. Lifschitz: Statistische
28. V. L. Ginzburg, Zh. Eksp. Teor. Fiz. 15 (1945) Physik, Akademie Verlag, Berlin 1966, p. 469.
739; 19 (1949) 36. 55. J. L. Servoin, Y. Luspin, F. Gervais,
29. A. F. Devonshire, Philos. Mag. 40 (1949) Ferroelectrics 37 (1981) 523 – 526.
1040 – 1063; 42 (1951) 1065 – 1079; Adv. 56. H. Vogt, Jpn. J. Appl. Phys. Part 2 24 (1985)
Phys. 3 (1954) 85 – 130. 112 – 116.
30. B. T. Matthias, Phys. Rev. 75 (1949) 1771. 57. P. Guenter, Ferroelectrics 24 (1980) 35 – 42;
31. B. T. Matthias, J. P. Remeika, Phys. Rev. 76 49 (1983) 39 – 46.
58. W. Heywang, J. Am. Ceram. Soc. 47 (1964)
(1949) 1886 – 1887.
484; J. Mater. Sci. 6 (1971) 1214 – 1226.
32. E. Sawaguchi, H. Maniwa, S. Hoshino, Phys.
59. R. G. Kepler, Annu. Rev. Phys. Chem. 29
Rev. 83 (1951) 1078.
(1978) 497 – 518.
33. C. Kittel, Phys. Rev. 82 (1951) 729 – 732. 60. M. G. Broadhurst, G. T. Davis, J. E. McKinney,
34. A. N. Holden, B. T. Matthias, W. J. Merz, J. P. R. E. Collins, J. Appl. Phys. 49 (1978)
Remeika, Phys. Rev. 98 (1955) 546. 4992 – 4997.
35. R. Pepinsky, F. Jona, G. Shirane, Phys. Rev. 61. A. J. Lovinger, T. Furukawa, G. T. Davis, M. G.
102 (1956) 1181 – 1182. Broadhurst, Polymer 24 (1983) 1225 – 1239.
14 Ferroelectrics

62. R. B. Meyer, L. Liebert, L. Strzelecki, P. 64. G. Durand, Ph. Martinot-Lagarde,

Keller, J. Phys. Lett. 36 (1975) 69 – 71. Ferroelectrics 24 (1980) 89 – 97.
63. R. B. Meyer, Mol. Cryst. Liq. Cryst. 40 (1977) 65. B. Zeks, Mol. Cryst. Liq. Cryst. 114 (1984)
33. 259.

Ferromanganese → Manganese and Manganese Alloys

Ferrotitanium → Titanium and Titanium Alloys
Ferrotungsten → Tungsten, Tungsten Alloys, and Tungsten Compounds
Ferrovanadium → Vanadium and Vanadium Compounds
Fertilizers : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
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Heinrich W. Scherer1, Konrad Mengel2, Heinrich Dittmar3, Manfred Drach4, Ralf Vosskamp4, Martin E. Trenkel5, Topics
Reinhold Gutser6, Günter Steffens7, Vilmos Czikkely3, Titus Niedermaier8, Reinhardt Hähndel4, Hans Prün9, Karl-
Heinz Ullrich4, Hermann Mühlfeld10, Wilfried Werner11, Günter Kluge12, Friedrich Kuhlmann13, Hugo Steinhauser14,
Walter Brändlein3, Karl-Friedrich Kummer4
1Agrikulturchemisches Institut, Universität Bonn, Bonn, Federal Republic of Germany
2Institute for Plant Nutrition, Justus-Liebig-Universität Giessen, Giessen, Federal Republic of Germany
3BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
4BASF Aktiengesellschaft, Limburgerhof, Federal Republic of Germany
5Eusserthal, Federal Republic of Germany
6Lehrstuhl für Pflanzenernährung, Technische Universität München-Weihenstephan, Freising, Federal
Republic of Germany
7Landwirtschaftliche Untersuchungs- und Forschungsanstalt, Oldenburg, Federal Republic of Germany
8formerly BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
9formerly BASF Aktiengesellschaft, Limburgerhof, Federal Republic of Germany
10formerly Chemische Fabrik Kalk GmbH, Köln, Federal Republic of Germany
11Agrikulturchemisches Institut der Universität Bonn, Bonn, Federal Republic of Germany
12Bundesministerium für Ernährung, Landwirtschaft und Forsten, Bonn, Federal Republic of Germany
13Institut für Betriebslehre der Agrar- und Ernährungswirtschaft der Justus-Liebig-Universität Giessen,
Giessen, Federal Republic of Germany
14formerly Lehrstuhl für Wirtschaftslehre des Landbaues, Technische Universität München, Freising,
Federal Republic of Germany

Copyright © 2006 by Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.
DOI: 10.1002/14356007.a10_323.pub2
Article Online Posting Date: December 15, 2006

Abstract | Full Text: HTML

Abstract
The article contains sections titled:

1. Introduction
2. Plant Nutrition and Soil Science
2.1. Plant Nutrients
2.1.1. Definition and Classification
2.1.2. Function of Plant Nutrients
2.2. Soil Science
2.2.1. Soil Classes, Soil Types, and Parent Material
2.2.2. Nutrient Retention in Soils
2.2.3. Soil pH, Buffer Power, and Liming
2.2.4. Soil Water–Plant Relationships
2.2.5. Organic Matter of Soils and Nitrogen Turnover
2.3. Nutrient Availability
2.3.1. Factors and Processes
2.3.2. Determination of Available Plant Nutrients in Soils
2.4. Physiology of Plant Nutrition
2.4.1. Nutrient Uptake and Long-Distance Transport in Plants
2.4.2. Effect of Nutrition on Growth, Yield, and Quality
2.5. Nutrient Balance
2.5.1. Gains and Losses of Plant Nutrients
2.5.2. Alternative Plant Nutrition
3. Standard Fertilizers
3.1. Solid Fertilizers
3.1.1. Straight Fertilizers
3.1.2. Multinutrient Fertilizers
3.1.3. Lime Fertilizers
3.1.4. Magnesium Fertilizers
3.2. Liquid Fertilizers
3.2.1. Nitrogen Liquids
3.2.2. Multinutrient Liquids
3.2.2.1. NP Liquids
3.2.2.2. NPK liquids
3.2.2.3. UAS Liquids
3.2.3. Suspensions
4. Special Fertilizers
4.1. Water-Soluble Nutrient Salts
4.2. Foliar Fertilizers
4.2.1. Production
4.2.2. Application
4.2.3. Combination with Agricultural Pesticides

page 1 of 78
Fertilizers : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
4.3. Micronutrients
4.3.1. Micronutrient Forms
4.3.2. Production
4.3.3. Commercial Fertilizers
4.3.4. Use
4.4. Slow- and Controlled-Release Fertilizers
4.4.1. Introduction
4.4.2. Urea–Aldehyde Slow-elease Fertilizers
4.4.2.1. Urea–Formaldehyde Condensation Products
4.4.2.2. Other Urea– Aldehyde Condensation Products
4.4.2.3. Further Processing of Urea–Aldehyde Condensates
4.4.3. Other Organic Chemicals
4.4.4. Inorganic Compounds
4.4.5. Coated and Encapsulated Controlled-Release Fertilizers
4.4.5.1. Sulfur-Coated Controlled-Release Fertilizers
4.4.5.2. Sulfur-Coated, Polymer-Encapsulated Controlled-Release Fertilizers
4.4.5.3. Polymer-Encapsulated Controlled-Release Fertilizers
4.4.6. Anti-Float Materials
4.4.7. Controlled-Release Fertilizers on Carriers
4.4.8. Supergranules
4.4.9. Legislation
4.5. Nitrification and Urease Inhibitors
4.5.1. Introduction
4.5.2. Types of Nitrification and Urease Inhibitors
4.5.3. Pyridines
4.5.3.1. Nitrapyrin
4.5.3.2. Other pyridines
4.5.4. Dicyandiamide
4.5.5. Pyrazoles
4.5.5.1. 1-Carbamoyl-3-methylpyrazole
4.5.5.2. Outlook
4.5.6. Neem/Neem-Coated Urea
4.5.7. Urease Inhibitors
4.5.8. Environmental Aspects
4.5.9. Legal Requirements
4.6. Organic Fertilizers (Secondary Raw Material Fertilizers)
4.6.1. Fertilizers Based on Peat or Materials of Similar Stability
4.6.2. Fertilizers Based on Waste Materials of Animal Origin
4.6.3. Fertilizers Based on Wastes of Plant Origin
4.6.4. Fertilizers Based on Municipal Waste
4.7. Manure
4.7.1. Composition
4.7.2. Manure Nutrient Efficiency
4.7.3. Environmental Aspects
5. Fertilizer Granulation
5.1. Introduction
5.2. Granulator Feedstocks
5.3. Granulation Equipment
5.3.1. Pug Mill
5.3.2. Drum Granulator
5.3.3. Pan Granulator
5.3.4. The Granulator–Mixer
5.3.5. Roll Presses
5.4. Costs of Agglomeration
5.5. Bulk Blending
5.6. Quality Inspection
5.7. Fertilizer Conditioning
5.8. Environmental Aspects
6. Analysis
6.1. Sampling and Sample Preparation
6.2. Determination of Nitrogen
6.3. Determination of Phosphate
6.4. Determination of Potassium
6.5. Analysis of Calcium, Magnesium, and Trace Elements
7. Synthetic Soil Conditioners
7.1. Foams
7.1.1. Closed-Cell Expandable Polystyrene Foam
7.1.2. Primarily Open-Cell Urea–Formaldehyde Resin Foams
7.2. Colloidal Silicates
7.3. Polymer Dispersions and Polymer Emulsions
7.4. Tensides
8. Storage, Transportation, and Application
8.1. General Storage Requirements
8.2. Application

page 2 of 78
Fertilizers : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
9. Environmental Aspects of Fertilizer Application
9.1. Nitrogen
9.1.1. Ground Water
9.1.2. Surface Waters
9.1.3. Atmosphere
9.1.4. Biosphere
9.1.5. Pedosphere (Soil)
9.1.6. Countermeasures
9.2. Phosphorus
9.2.1. Eutrophication
9.2.2. Heavy Metals Buildup
10. Legal Aspects
11. Economic Aspects
11.1. Economics of Fertilization
11.1.1. Input–Output Relationships: The Yield Function
11.1.2. Factors Controlling the Optimal Nitrogen Fertilization Level
11.1.3. Factors Influencing the Optimal Nitrogen Fertilization Level
11.1.4. Environmental Aspects of Fertilization
11.2. World Consumption, Production, and Trade
11.3. Future Outlook
11.3.1. Food Situation
11.3.2. Development of Fertilizer Consumption

Fertilizers are products that improve the levels of available plant nutrients and/or the chemical and physical properties of soil. An overview is given over the
chemical and physical aspects of plant nutrition uptake and soil properties. The different categories of fertilizers are discussed, and special interest is given on
production processes and analyses, including storage and transportation as well as environmental, legal, and economic aspects.

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1. Introduction
Heinrich W. Scherer and Konrad Mengel

Fertilizers in the broadest sense are products that improve the levels of available plant nutrients and/or the chemical and physical properties of soil, thereby
directly or indirectly enhancing plant growth, yield, and quality.

Fertilizers are classified as follows in terms of their chemical composition:

1. Mineral fertilizers consist of inorganic or synthetically produced organic compounds.

2. Organic fertilizers are waste products from animal husbandry (stable manure, slurry manure), plant decomposition products (compost, peat), or
products from waste treatment (composted garbage, sewage sludge).
3. Synthetic soil conditioners are products whose main function is to improve the physical properties of soils, for example, friability and water and air
transport.

The following categories are distinguished with respect to nutrient content:

1. Straight fertilizers generally contain only one primary nutrient.

2. Compound (complex or multinutrient) fertilizers contain several primary nutrients and sometimes micronutrients as well.
3. Micronutrient fertilizers contain nutrients required in small quantities by plants, as opposed to macronutrients; quantities range from 1 to 500 g ha–1a–1.

Finally, fertilizers can be classified as solid or liquid fertilizers and as soil or foliar fertilizers, the latter being applied exclusively by spraying on an existing plant
population.

History. Fertilizing substances were applied even in antiquity. Their use can be attributed to the observation in nature that plants developed especially well in
locations where human or animal excreta, ash residues, river mud, or dying plants were left. For example, the Egyptians knew about the fertility of the Nile
mud, and the Babylonians recognized the value of stable manure; for example, HOMER mentions manure in the Odyssey. PLINY reports that the Ubians north of
Mainz used “white earth,” a calcareous marl, to fertilize their fields. The Romans acknowledged the advantages of green manuring, cultivating legumes and
plowing them under. At the end of the first millenium, wood ash was much used as fertilizer in Central Europe. Not until the beginning of the 19th century did
guano, at the suggestion of ALEXANDER VON HUMBOLDT (1800), and Chilean caliche, on the recommendation of HAENKES (1810), come into use as fertilizers.
Up to that time, however, it was still believed that the organic matter of soil, humus, was the true source of plant nutrition.

Around 1800, the nutrition problem entered a critical phase in Europe. In 1798, MALTHUS set forth his pessimistic theses, saying that the quantity of food could
increase only in arithmetic progression while the population grew geometrically. Combining results obtained by others (SPRENGEL, BOUSSINGAULT) with his own
pathbreaking studies, J. VON LIEBIG set forth the theoretical principles of plant nutrition and plant production in Chemistry in Its Application to Agriculture and
Physiology (1840). He took the view, now considered obvious, that plants require nitrogen, phosphate, and potassium salts as essential nutrients and extract
them from the soil. LIEBIG's mineral theory was well supported by experimental data of J. B. BOUSSINGAULT (1802 – 1887) in France. He and also J. B. LAWES
(1814 – 1900) and J. H. GILBERT (1827 – 1901) in England showed that plants benefit from inorganic N fertilizers. LIEBIG thus became the founder of the theory
of mineral fertilizers, and his doctrines led to an increasing demand for them. A number of companies were subsequently founded in Europe to produce
phosphate and potash fertilizers. Superphosphate was manufactured for the first time in 1846, in England.

In Germany, this industrial development started in 1855. The importation of saltpeter on a large scale began in the area of the German Federation (56 000 t in
1878). Peruvian guano soon came into heavy use (520 000 t in 1870). Ammonium sulfate, a coke-oven byproduct, was later recognized as a valuable fertilizer,
and the mining of water-soluble potassium minerals was undertaken in the 1860s [1].

The demand for nitrogen that developed at the end of the 19th century soon outstripped the availability of natural fertilizers. A crucial breakthrough came about
with the discovery and large-scale implementation of ammonia synthesis by HABER (1909) and its industrial realization by BOSCH (1913).

Around the turn of the century, the technique of hydroponics led to the discovery of other essential plant nutrients. Research showed that plants in general
require ten primary nutrients: carbon, hydrogen, oxygen. nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, and iron. JAVILLIER and MAZE (1908)
pointed out for zinc and AGULHON (1910) pointed out for boron the nutritional effects on plants. WARINGTON (1923) first described the symptoms of boron
deficiency, and BRANDENBURG (1931) clearly recognized dry rot in the sugar beet as boron deficiency. Generally micronutrients were made available to the
plant as liquid foliar fertilizer, a method first suggested for iron by GRIS in 1844. By 1950, this list of micronutrients had been expanded to include manganese,
copper, and molybdenum.

Almost 70 years ago, serious research began on the best nutrient forms for individual plant species under various soil and climatic conditions. Besides the
classical fertilizers, for example, controlled-release fertilizers, improved foliar fertilizers, nutrient chelates, and nitrification inhibitors have been developed in

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recent decades. This development of new nutrient forms is still in full swing in the special fertilizers sector.

In the developed market economies of Western Europe, the United States, and Japan, however, the level of mineral fertilizer use has not been increasing
since the beginning of the 1980s. In some countries, genuine agricultural overproduction has occurred recently. Since better delivery of plant nutrients has led
to increasing self-reliance even in the Third World economies (e.g., China, India, Brazil), these countries are not so important as purchasers of nutrients on the
world market, so that surpluses cannot be exported without limit. The production of fertilizers is also on the increase in these countries. Thus overproduction
plus regional environmental problems (nitrates entering the ground water) are actually leading to a decrease in mineral fertilizer use in some areas. This
decline will be limited by diminishing soil fertility in localities where fertility has been enhanced by decades of proper fertilization.

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2. Plant Nutrition and Soil Science

Heinrich W. Scherer and Konrad Mengel

The science of plant nutrition is situated between soil science and plant physiology. It comprises the definition of the elements nutritive for plants; the uptake of
plant nutrients and their distribution in the plant; the function of the nutritive elements in plant metabolism; their effect on plant growth; yield formation and
quality parameters in crops; soil nutrient exploitation by plant roots; factors and processes that control the plant nutrient availability in soils; toxic elements in
soils and their impact on plant growth; the application of plant nutrient carriers (fertilizers) and their turnover in soils; nutrient balance; and the maintenance of
soil fertility.

Plant nutrition is considered mainly from two aspects, an agronomic one and an ecological one. The former is focused on the question of fertilizing soil as an
efficient means to increase crop yield and to maintain or even improve soil fertility. The latter, the ecological aspect of plant nutrition, is concerned with the
nutritive condition of a soil and a location and with its effect on plant growth and plant communities. Since fertilizers are the topic of this article, the agronomic
aspects of plant nutrition are treated with greater depth.

The science of plant nutrition is closely associated with the science of soils. The latter comprises a broad field of scientific activity and thus cannot be
considered here in all its facets. In this article only those problems of soil science relevant to understanding plant nutrition are treated.

2.1. Plant Nutrients

2.1.1. Definition and Classification
From a scientific point of view, the term plant nutrient is not especially precise. More appropriate is to distinguish between nutritive elements of plants and
nutritive carriers. Essential nutritive elements for plants are the chemical elements that are required for a normal life cycle and that satisfy the following criteria:

1. A deficiency of the element makes it impossible for the plant to complete its life cycle.
2. The deficiency is specific for the element in question.
3. The element is directly involved in the nutrition of plants because of either its chemical or its physical properties.

According to this definition, the following chemical elements are nutritive elements for plants: C, H, O, N, P, S, K, Ca, Mg, Fe, Mn, Cu, Zn, Mo, B. Further
elements, such as Na, Cl, and Si, may affect plant growth positively, and there are particular plant species for which these elements are of great importance.
Nevertheless, they are not essential nutritive elements for plants in the strict sense of the definition. Cobalt is required by some bacteria, e.g., by dinitrogen-
fixing bacteria and thus may also benefit plant growth indirectly.

Generally it is not the element itself that is provided to and taken up by the plant, but an ion or a molecule in which the nutritive element is present, e.g., C is
present in CO2, P in , N in or , and B in H3BO3. The particular molecule or ion in which the nutritive element is present is termed the nutrient
carrier. In the case of metals, the corresponding ion or salts of ion species in question, e.g., K+, Ca2+, Zn2+, can be considered the carrier. In this sense
fertilizers are nutrient carriers.

Plant nutrients may be grouped into macronutrients and micronutrients. Macronutrients are required in high amounts and thus are present in plant tissues in
much higher concentrations than the micronutrients. Carbon, H, O, N, P, S, K, Ca, and Mg belong to the macronutrients. Their concentration in the dry plant
matter is in the range 1 – 50 mg/g, except for C, H, and O, which have much higher concentrations (see Table 2). The concentration of the micronutrients in
the dry plant matter is in the range 1 – 1000 µg/g.

From the viewpoint of fertilization, those nutrients that are required by plants in high quantities and that must be regularly supplied by fertilization are of
particular interest. These nutrients are N, K, P, and to a minor degree also Ca, Mg, and S. Calcium is a soil nutrient, which means that it is important for an
optimum soil structure. Application of micronutrients is not a common practice, but they are applied at locations where soils are low in a particular micronutrient
or where soils may bind this micronutrient very strongly. This is the case for heavy metals (Fe, Mn, Cu, Zn) and B in calcareous and alkaline soils (soils with a
high pH value), while Mo is strongly fixed in acid soils. Acid organic soils are known for their low available Cu content.

According to the different quantitative requirements for macronutrients and micronutrients, the former are taken up in much higher quantities than the latter.
Thus a wheat stand with a yield potential of 7 t of grain per hectare requires about 100 kg K but only 100 g Cu.

From a physiological point of view, plant nutrients are grouped into four groups, as shown in Table 1. The first group, comprising C, H, O, N, and S, includes all
major elementary constituents of organic plant matter. Their carriers are present mainly in the oxidized form, and they must be reduced during the process of
incorporation. The energy required for this reduction originates directly or indirectly from photosynthetically trapped energy. Assimilation of H is basically an
oxidation process, namely, the oxidation of water with the help of light energy (photolysis):

Table 1. Physiological classification of plant nutritive elements, nutrient carriers, and form in which the nutrient is taken up

Nutritive element Nutrient carrier Uptake

First group
C CO2, CO2 by leaves, by roots

H H2 O H2O by leaves, H2O and by roots

O CO2, , O2 O2 and CO2 by leaves, and O2 by roots

N , NH3, , NOx and by roots, NH3 and NOx by leaves

S , SO2, SO3, H2S by roots, SO2, SO3, and H2S by leaves

Second group
P , and by roots

B H3BO3, borates H3BO3 and by roots

Si silicates Si(OH)4 by roots

Third group
K K+, K salts K+ by roots
Mg Mg2+, Mg salts Mg2+ by roots

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Ca Ca2+, Ca salts Ca2+ by roots
Mn Mn2+, Mn salts Mn2+ by roots
Fourth group
Fe, Cu, Zn, Mo ionic form or metal chelates, by roots in ionic form or in the form of soluble metal
minerals containing these chelates, Mo in the form of the molybdate
elements

The second group (P, B, Si) comprises elements that are taken up as oxo complexes in the partially deprotonated (P) and protonated (B, Si) form. The oxo
complex is not reduced in the plant cell, but may form esters with hydroxyl groups of carbohydrates, thus producing phosphate, borate, and silicate esters.

The third group comprises metals that are taken up from the soil solution in ionic form. They are only partially incorporated into the organic structure of the
plant tissue: Mg in the chlorophyll molecule, Mn in the electron donor complex of photosystem II, and Ca2+ as countercation of indiffusible anions in cell walls
and particularly in biological membranes. Potassium is virtually not incorporated into the organic plant matter. It is only weakly adsorbed by Coulombic forces.
There exist, however, some organic molecules that may bind K+ very selectively (ionophores, see Section Nutrient Uptake and Long-Distance Transport in
Plants). These ionophores are likely to be involved in K+ uptake.

The fourth group comprises heavy metals, of which Fe, Cu, and Zn are taken up as ions or in the form of soluble metal chelates, while Mo is taken up as
molybdate. These molecules are easily incorporated into the organic structure, where they serve as essential elements of enzyme systems: Fe in the heme
group and in ferredoxin, Mn in arginase [2], Cu in oxidases (polyphenol oxidase, cytochrome oxidase, ascorbate oxidase [3]), Zn in RNA polymerase [4], and
Mo in nitrate reductase [5] and nitrogenase [6].

All nutritive elements of plants, therefore, are taken up in the form of inorganic complexes, mostly in oxidized form or as metal ions, i.e., in forms characterized
by a low energy level. This is a unique feature of plants, and a feature in which they contrast sharply with animals and most kinds of microorganisms (bacteria
and fungi). Animals and most microorganisms must take up food that is rich in chemical energy in order to meet their energy requirements. Plants, at least
green plants, meet their energy requirement by converting radiation energy into chemical energy. This energy conversion process is manifest in the reduction
of plant nutrient carriers ( , , CO2 ) as already mentioned. Thus important processes of plant nutrition are closely linked with the unique function of
plants in the great cycle of nature, i.e., the conversion of inorganic matter into organic form. Liebig [7] was correct in commenting on plant nutrition: “Die ersten
Quellen der Nahrung liefert ausschließlich die anorganische Natur.” (The primary source of nutrition is provided exclusively by the inorganic materials in
nature.)

2.1.2. Function of Plant Nutrients

Most plant organs and particularly plant parts that are metabolically very active, such as young leaves and roots, are rich in water (ca. 80 – 90 wt % of the total
fresh matter), while their organic material is ca. 12 – 18 wt % and their mineral content is 2 – 6 wt %. As shown in Table 2, in the dry matter of plant material O
and C are by far the most abundant elements, followed by H, N, and K. The elements C, O, H, and, to some extent, N are mainly structural elements in plant
matter. They can, however, form chemical groups that are directly involved in metabolic processes, e.g., carboxyl groups, amino groups, hydroxyl groups.

Table 2. Mean content of chemical elements in the dry matter of green plant material

Element Content, g/kg

O 440
C 420
H 60
N 30
K 20
P 4
All other elements 26

Since in many soils the available N is low, nitrogen [7727-37-9] is the most important fertilizer element, and for this reason its function in plant metabolism
deserves particular interest. Nitrogen is an essential element for amino acids, proteins, nucleic acids, many coenzymes, and some phytohormones. Basic
biochemical processes of meristematic growth, such as the synthesis of proteins and nucleic acids, require N. If this nutrient is not supplied in sufficient
amounts, the growth rate is depressed and the synthesis of proteins affected. Nitrogen-deficient plants are characterized by low protein and high carbohydrate
contents. This relationship is shown in Table 3 [8].

Table 3. Effects of N supply on yield of dry matter and the content of organic N and carbohydrates in the dry matter of young timothy plants
(Phleum pratense) [8]

Yield and content N supply

Low Sufficient

Yield, g/pot 15.7 20.2

Content, mg/g
Organic N, 20.5 31.5

Sucrose 46.9 22.6

Fructans * 22.2 9.2

Starch 32.8 11.7

Cellulose 169 184

* Polysaccharides of fructose.

Nitrogen is also essential for the formation of chloroplasts, especially for the synthesis of chloroplast proteins. Hence N deficiency is characterized by low
chlorophyll content; the leaves, especially the older ones, are pale and yellow; the stems thin and the plants small. Nitrogen-deficient plants senescence
earlier, probably because of a deficiency of the phytohormone cytokinin. Abundant N supply increases the protein content, especially the content of free amino

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acids, and often also the content of in plants. An example of this is shown in Table 4 [9]. Excess nitrogen nutrition results in luxurious plants that
frequently are susceptible to fungi attack.

Table 4. Relationship between N fertilizer rate and nitrogenous fractions in the dry matter of rye grass [9]

Nitrogen Nitrogenous fraction, g/kg

fertilizer Total N Protein N Free amino and N

rate, kg/ha acid N

0 13.2 9.8 1.6 0.4

110 18.9 12.6 2.1 0.6
440 37.3 20.6 5.6 3.5

The ratio of N to S in plant matter is ca. 10 : 1. Hence sulfur [7704-34-9] is required in much lower quantities than N. Their functions are, however, similar.
Sulfur is an elementary constituent of most proteins; the SH group in involved in various enzymatic processes and it is the reactive group of coenzyme A.
Disulfide (S – S) bridges are essential structural elements in the tertiary structure of polypeptides and in many volatile S compounds, such as diallyl disulfide,
which is the main component in garlic oil. Mustard oils occurring in many species of the Cruciferae contain a S-glycosidic bond and a sulfuryl group:

Insufficient S supply results in a decrease of growth rate with extremely low levels of and high concentrations of free amino compounds and in the
leaves, which is due to hampered protein synthesis. Sulfur plays an important role in the baking quality of wheat, since the concentration of S compounds in
the gluten fraction is responsible for the linkages between the protein molecules [10]. Sulfur deficiency may also affect N2 fixation of legumes by causing
unfavorable conditions in the host plant or because of the relatively high S content of nitrogenase and ferredoxin [11]. Deficiency symptoms of S appear at first
in the youngest leaves, which turn light green to yellow. Abundant supply with S results in an accumulation of sulfate in plant tissues.

Sulfur oxide can be taken up by the leaves and metabolized and thus can contribute to the S nutrition of plants. Too high SO2 concentrations in the
atmosphere may be toxic. The toxicity symptoms are necrotic spots in the leaves. According to SAALBACH [12], the critical SO2 level in the atmosphere for
annual plants is 120 µg/m3. For trees and other perennials it is about half this level. The currently much discussed damage to trees in the forest of the Federal
Republic of Germany (mainly spruce and silver fir) is not caused by toxic SO2 levels.

Phosphorus [7723-14-0] is an essential element in nucleic acids and various phospholipids (phosphoglyceride and phosphosphingolipids). In both cases.
phosphate is esterified with sugars (nucleic acid) or with alcohol groups of glycerol or sphingosine. Phosphate is also present in various coenzymes; the most
prominent is adenosine triphosphate (ATP), which carries a kind of universal energy that is used in a number of biochemical processes. Metabolites and
enzymes can be activated by phosphorylation, a transfer of the phosphoryl group from ATP to the metabolite according to the following reactions:

Activation of glucose

Glucose + ATP Glucose-6-phosphate + ADP

Phosphorylation of an enzyme

Enzyme – OH + ATP Enzyme–O + ADP

Such reactions demonstrate the essential role of P not only in plant metabolism but also in all living organisms. Undersupply with P results in a reduced growth
rate, and seed and fruit formation is affected. The leaves of P-deficient plants often show a gray dark green color; the stems may turn red. The P reserve in
seeds is the Mg (Ca) salt of the inositol hexaphosphate (phytic acid):

The physiological role of boron has remained obscure until now, and therefore various hypotheses with numerous modifications exist concerning the
physiological and biochemical role of boron in higher plants. Depending on the pH of the soil, boron seems to be taken up mainly as undissociated boric acid
or as the borate anion. Plant species differ in their boron uptake capacity, reflecting differences in boron requirements for growth. However, there is still some
controversy about boron translocation in plants. At least in higher plants, a substantial proportion of the total boron content is complexed in the cell walls in in a
cis-diol configuration [14]. According to BIRNBAUM et al. [13], B is involved in the synthesis of uracil and thus affects UTP formation. (UTP is an essential
coenzyme for the synthesis of sucrose and cell-wall components.) Also the synthesis of ribonucleic acid is hampered in the case of B deficiency. Since uracil is
an integral part of ribonucleic acid (RNA), the formation of RNA may also be related to the synthesis of uracil. POLLARD et al. [15] suggest that B has a specific
influence on plant membranes by the reaction of borate with polyhydroxy compounds.

Boron deficiency appears as abnormal or retarded growth of the apical growing points. The youngest leaves are misshapen and wrinkled and show a darkish
blue-green color. The fact that B deficiency primarily affects the apex is in accord with the impaired synthesis of ribonucleic acids required for meristematic
growth. High levels of available B in the soil may cause B toxicity in plants. This is mainly the case in arid areas; however, B toxicity can also be the
consequence of industrial pollution [16]. The toxicity is characterized by yellow leaf tips followed by progressive necrosis. The leaves take on a scorched
appearance and drop prematurely.

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Silicon [7440-21-3] is not an essential element for plants; however, it has a beneficial effect on various plant species, mainly grasses [17]. In plants well
supplied with Si, cuticular water losses are diminshed and resistance against fungal attack is improved [18]. The favorable effect of Si on rice growth is well
known. Silicon-containing fertilizer is frequently applied in rice production.

Among the metal cation species, the potassium [7440-09-7] ion, K+, is the nutrient plants take up from the nutrient medium at the highest rates. The K+
concentration in the cytoplasm is about 100 mM and thus much higher than the concentration of other ion species [19]. Probably this high K+ concentration
has a favorable influence on the conformation of various enzyme proteins [20]. Potassium ions can easily penetrate plant membranes (see Section Nutrient
Uptake and Long-Distance Transport in Plants), which often leads to a depolarization of the membranes. Membrane depolarization, it is supposed, has a
favorable effect on meristematic growth, photophosphorylation, aerobic phosphorylation, and phloem loading [21]. These basic processes are important for the
long-distance transport of photosynthates, the synthesis of various organic compounds, and CO2 assimilation.

The data in Table 5 show that with an increase of K+ in alfalfa leaves (Medicago sativa), the CO2 assimilation rate increased, while the mitochondrial
respiration rate decreased [22]. In the case of low K, the respiration was about 2/3 of the CO2 assimilation, while with high K the C gained by assimilation was
about 11 times higher than the C lost by respiration. This typical behavior indicates that under the conditions of K+ deficiency much of the stored carbohydrates
must be respired in order to meet the ATP demand of the plant. Plants undersupplied with K+ have therefore a low energy status. Such plants are highly
susceptible to fungal attack, water stress, and frost damage.

Table 5. Relationship between K+ concentration in the dry matter of alfalfa leaves, CO2 assimilation, and mitochondrial respiration [22]

Concentration Carbon gain and loss, mg dm–2 h–1

of K+, mg/g CO2 Mitochondrial

assimilation respiration

13 11.9 7.56
20 21.7 3.34
38 34.0 3.06

Potassium is important in determining the osmotic pressure of plant fluids, and K+-deficient plants are characterized by inefficient water use. Sodium ions may
replace some K+ functions, e.g., the less specific osmotic functions. Important counterions of K+ in plant tissues are Cl–, , and organic anions. The
frequently observed favorable effect of Na+ and Cl– on plant growth is related to their osmotic functions.

Plants suffering from K+ deficiency show a decrease in turgor, and under water stress they easily become flaccid. Plant growth is affected, and the older
leaves show deficiency symptoms as necrosis beginning at the margins of tips and leaves. In K+-deficient plant tissue, toxic amines such as putrescine and
agmatine accumulate.

The most spectacular function of magnesium [7439-95-4] is its integral part in the chlorophyll molecule. Besides this function, Mg2+ is required in various other
processes and, the Mg fixed in the chlorophyll molecule amounts only to about 20 % of the Mg present in green plant tissues. Magnesium is an essential ion in
ribosomes and in the matrix of the cell nucleus. Here Mg2+ is bound by phosphate groups, since the Mg2+ is strongly electrophilic and thus attracts oxo
complexes such as phosphate [23]. The magnesium ion activates numerous enzymatic reactions in which phosphate groups are involved. The activation is
assumed to be brought about by bridging the phosphate group with the enzyme or with the substrate. This is an universal function of Mg2+ not only relevant for
plant metabolism but also for practically all kinds of organisms.

Deficiency of Mg2+ affects chlorophyll synthesis: leaves turn yellow or red between the veins. The symptoms begin in the older leaves. Protein synthesis and
CO2 assimilation are depressed under Mg2+ deficiency conditions. Recent results [24] have shown that the yellowing of spruce needles in the Black Forest is
due to a Mg2+ deficiency and can be cured by Mg2+ fertilizer application.

Calcium [7440-70-2] is the element of the apoplast (cell wall and “free space”) and of biological membranes. Here it is adsorbed at the phosphate head groups
of membrane lipids, thus stabilizing the membranes [25]. Most of the Ca2+ present in plant tissues is located in the apoplast and in the vacuole, some in the
mitochondria and in the chloroplasts, while the cytoplasm is extremely low in Ca2+ (10–7 to 10–6M). The maintenance of this low cytoplasmic Ca2+
concentration is of vital importance for the plant cell [26]. Higher cytoplasmic Ca2+ concentrations interfere with numerous enzymatic reactions and may even
lead to a precipitation of inorganic phosphates. This low Ca2+ concentration suffices to form a complex with calmodulin, a polypeptide of 148 amino acids. The
Ca – calmodulin complex is a universal enzyme activator. The activation is brought about by allosteric induction.

Direct Ca2+ deficiency in plants is rare, since most soils are relatively rich in Ca2+. Physiological disorders as a consequence of an insufficient Ca2+ supply of
particular plant parts, however, occur frequently. Calcium is mainly translocated by the transpiration stream. Hence plant parts such as fruits, which mainly
feed from the phloem and less from the xylem sap, may suffer from an insufficient Ca2+ supply. Shear [27] cites a list of 35 such Ca2+-related disorders in
fruits and vegetables. Two of the most important ones involve storage tissues and result in poor crop qualities [28]: bitter pit in apples, characterized by small
brown spots on the surface, and blossom-end rot in tomatoes, a cellular breakdown at the distal end of the fruit, which is then susceptible to fungal attack.

Manganese [7439-96-5] is an integral part of the superoxide dismutase and of the electron donor complex of photosystem II. Manganese may activate
enzymes in the same way as Mg2+ by bridging the phosphate group with the enzyme or the substrate. Deficiency of Mn2+ leads to the breakdown of
chloroplasts. Characteristic deficiency symptoms are smaller yellow spots on the leaves and interveinal chlorosis. Manganese toxicity may occur, especially on
flooded soils, because of the reduction and thus solubilization of manganese oxides. Toxicity symptoms are generally characterized by brown spots of MnO2 in
the older leaves surrounded by chlorotic areas [29].

Iron [7439-89-6] is an essential element for haem and ferredoxin groups. Iron deficiency leads to chloroplast disorders; the synthesis of thylakoid membranes
is disturbed and the photochemical activity affected [30]. Iron deficiency is characterized by yellow leaves. The symptoms are at first visible in the younger
leaves. There is evidence that the deficiency, mainly occurring in plants growing on calcareous soils, is not induced by an insufficient Fe uptake from the soil
but by a physiological disorder in leaves, affecting the Fe distribution in the leaf tissue [31].

Iron toxicity can be a problem under reducing soil conditions, which prevail in flooded soils. Under such conditions iron(III) oxides are reduced and the iron is
rendered soluble. This may increase the Fe concentration in the soil solution by a factor of 102 to 103 [32] so that plants may suffer from Fe toxicity,
characterized by tiny brown spots on the leaves, which later may turn uniformally brown. Iron toxicity is known as “bronzing.”

Copper [7440-50-8] is an essential element of various enzymes, such as superoxide dismutase, polyphenol oxidases, plastocyanin of the photosynthetic
transport chain, and cytochrome c oxidase, the terminal oxidase in the mitochondrial electron transport chain. Deficiency in Cu leads to pollen sterility and thus
affects the fruiting of plants. Copper-deficient plants often are characterized by white twisted leaf tips and a tendency to become bushy.

Zinc [7440-66-6] is an integral part of carbonic anhydrase, superoxide dismutase, RNA polymerase, and various dehydrogenases. It is closely involved in the
N metabolism of plants. In Zn-deficient plants, protein synthesis is hampered and free amino acids accumulate. There is evidence that Zn is involved in the

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synthesis of tryptophan, which is a precursor of indole acetic acid, an important phytohormone. Zinc deficiency is characterized by short internodes, small
leaves, and chlorotic areas in the older leaves. Frequently the shoots die off and the leaves fall prematurely.

Molybdenum [7439-98-7] is present in the nitrate reductase and in the nitrogenase system that catalyzes the bacterial fixation (reduction) of dinitrogen.
Deficiency of Mo frequently appears first in the middle and older leaves as a yellowish green coloration accompanied by a rolling of leaf margins. Cruciferae
species are particularly susceptible to Mo deficiency. The most well-known Mo deficiency is the “whiptail” of cauliflower. For further information on the
physiology of plant nutrition, see [3], [23], [33].

2.2. Soil Science

2.2.1. Soil Classes, Soil Types, and Parent Material
According to SCHROEDER [34], “soil is the transformation product of mineral and organic substances on the earth's surface under the influence of
environmental factors operating over a very long time and having defined organisation and morphology. It is the growing medium for higher plants and basis of
life for animals and mankind. As a space-time system, soil is four dimensional.”

Soils are complex, quite heterogeneous, and may differ from each other considerably. Nevertheless, all soils have some common features. They possess a
mineral, an organic, a liquid, and a gaseous component. In an ideal soil, the percentage proportions of these components are 45 %, 7 %, 23 %, and 25 %,
respectively. The volumes of the liquid and gaseous components may change quickly. For example, in a water-saturated soil all pores are filled with water, and
in a dry soil the soil pore volume is almost completely filled with air. The mineral and organic components contain plant nutrients and adsorb plant nutrients at
their surfaces, and they are therefore of importance for the storage and retention of plant nutrients. The liquid phase of the soil is the soil solution. It contains
dissolved plant nutrients and is the medium for the translocation of plant nutrients from various soil sites towards the plant roots. The gaseous soil component
is essential for gas exchange, especially for the supply of plant roots with oxygen and for the release of CO2 from the soil medium into the atmosphere.

For the description, comparison, and assessment of soils, a grouping according to general criteria is indispensable. There are two main grouping systems for
soils: (1) soil classes or soil texture and (2) soil types. Textural classes are defined according to the particle size of soils. Soil types relate to the parent material
of soils, to the pedological genesis, and to typical properties evident in the soil profile i.e., the horizontal layers of soils, called soil horizons.

Soil Classes. Soil particle sizes as a main characteristic of soil classes are grouped into four major groups as shown in Table 6. The major groups (sand, silt,
and clay) are subdivided into coarse, medium, fine. Designation of the soil texture (soil class) depends on the percentage proportions of the sand, silt, and clay
fraction in the total fine earth, which is sand + silt + clay. Soils in which the sand fraction dominates are termed sandy soils, soils consisting mainly of silt and
clay are silty clays, and soils which contain all three fractions in more or less equal amounts are called loams. In the German terminology, abbreviations for the
fractions are used (S = sand, U = silt, T = clay, L = loam). For example, if the major fraction is silt (U) and the next sand (S), the abbreviation is sU = sandy silt.
Figure 1 shows the designations of the various soil classes according to the percentage proportion of the three main particle fractions.

Table 6. Particle size of soil fractions relating to soil texture

Diameter, mm Designation Abbrevation

>2 pebbles, gravels

0.06 – 2 sand S
0.002 – 0.06 silt U
< 0.002 clay T

Figure 1. Diagram of soil textural classes, German system of SCHROEDER [34]

The vertical axis shows the percentage of silt, the horizontal the percentage of clay, and the dashed line the percentage of sand.

In the farmer's practice, sandy soils are called light soils, soils rich in clay heavy soils. This distinction relates to the force required to work (plough, cultivate) a
soil. Soils rich in clay, but also silty soils, tend to compaction when dried and hence are heavy to work.

Although the grouping according to particle size is based on a physical factor, particle size is also associated with the chemical properties. This can be seen
from Figure 2: the sand fraction consists mainly of quartz, which is a sterile material. Primary silicates (micas, feldspars) contain K, Ca, Mg, and other plant
nutrients, which are released during the process of weathering. Clay minerals are less rich in plant nutrients than the primary silicates, but they possess large
negatively charged surfaces that are of the utmost importance for the adsorption of plant nutrients and water.

Figure 2. Mineral composition of the sand, silt, and clay fractions [34]

The various soil particles form aggregates in which organic matter is also involved. This aggregation forming fine pores and holes in the soil is of relevance for
soil structure. A good soil structure is characterized by a relatively high pore volume, ca. 50 % of the total soil volume. Soil structure depends much on the Ca
saturation (see Cation exchange capacity). The richer the soil is in clay, the more important a good soil structure is.

Soil Type. Soil type is related to the parent material from which a soil is developed and from the history of development, which is much influenced by climate
and vegetation. Main groups of parent material are igneous rocks, sedimentary rocks, and metamorphic rocks. Also organic matter may be the main parent
material. Content of plant nutrients, capacity to store plant nutrients, soil pH, and the rooting depth depend much on the parent material, but are also
influenced by soil development.

In the following, a limited number of important soil types are considered according to the FAO World Soil Classification. Besides this system there are other
systems, e.g., the U.S. Soil Taxonomy. The FAO classification comprises 26 classes.

A distinction can be made between young soils and old soils. The latter are generally highly weathered, their inorganic material consisting mainly of quartz and
iron aluminum oxide hydroxides. Such soils are characterized by poor cation retention capacity (cation exchange capacity), low pH values, and a high
phosphate fixing power. This soil type, called ferralsol, is frequent in the tropics, whereas in moderate climates highly weathered soils belong mainly to the
podsols.

Young soils may be derived from the sedimentation of rivers and oceans (fluvisols) or from volcanic ash (andosols). These soils are generally rich in plant

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nutrients and thus form fertile soils. The most fertile soils belong to the black earths (chernozem). They are frequent in Russia, Central and East Europe as
well as North America and are derived from loess. They are characterized by a neutral pH, by a well balanced content of clay and organic matter and by a
deep rooting profile. They are naturally rich in plant nutrients and possess a high nutrient storage capacity. Soils in which the parent material loess is more
weathered as compared with the chernozems belong to the luvisols. This soil type is common in Germany, Austria, and France where it represents the most
fertile arable land. Gleysols are soils with a high water table, rendzinas are shallow soils derived from limestone, histosols are rich in only partially decomposed
organic matter.

Under arid conditions salt may accumulate in the top soil layer. Solonchaks (white alkali soils) are saline soils with a pH of ca. 8 and with neutral anions as the
most important anion component. Solonetz soils (black alkali soils) possess bicarbonate and carbonate as major anion component. Their pH is in the range
8 – 10. Crop growth on saline soils is extremely poor, and in many cases only a salt flora can grow under such conditions. This is particularly true for the
solonetz soils.

For further information on soil texture and soil types, see [34-37], and the Soil Taxonomy of the Soil Conservation Service of U.S. Department of Agriculture
[38].

2.2.2. Nutrient Retention in Soils

Nutrient retention is an important characteristic of fertile soil.

Cation Exchange. Cations are retained on soil colloids having a negative charge: the cations are bound at the surface of these particles by Coulomb forces.
The most important cation species are Ca2+, Mg2+, K+, Na+, Al3+, Al(OH)2+, , and H+. This is represented in Figure 3. A distinction can be made
between inorganic and organic soil colloids capable of cation adsorption. Inorganic particles belonging to the clay fraction are known as secondary clay
minerals because they are mainly derived by weathering of primary minerals such as orthoclase, plagioclase, and particularly mica. Organic soil colloids
capable of cation adsorption belong to the humic acids. The negative charge of the inorganic soil colloids originates from the so-called isomorphic substitution
and from deprotonation. Isomorphic substitution is the replacement of Si4+ in the crystal lattice by Al3+, Fe2+, or Mg2+, thus leading to a surplus of negative
charge, because the anionic groups of the lattice are not completely balanced by Al3+, Fe2+, or Mg2+. Such a negative charge is a permanent charge, in
contrast to labile charges that result from deprotonation. Labile charges are typical for organic colloids (humic acids): carboxylic groups and acid hydroxylic
groups of phenols may be protonated or not depending on the pH of the environment.

Figure 3. Schematic presentation of cations adsorbed to the negatively charged surface of a soil colloid

The secondary clay minerals are grouped into 1 : 1 clay minerals, in which a Si layer alternates with an Al layer, and 2 : 1 clay minerals, in which an Al layer is
sandwiched by two Si layers. The most important representatives of the 1 : 1 clay minerals are the kaolinites. The 2 : 1 secondary clay minerals comprise the
illite, transitional minerals, vermiculite, chlorite, and smectites ( Clays). Most of these 2 : 1 clay minerals possess inner surfaces. They are therefore
characterized by a high cation retention (= cation exchange) capacity.

These negatively charged soil colloids, often also called sorption complexes, function like a cation exchanger. Adsorbed cations can be replaced by other
cation species. The cation exchange is stoichiometric. Adsorption and desorption depend on the concentrations of the cation species in the surrounding
solution. If a soil colloid completely saturated by K+ is exposed to increasing Ca2+ concentrations, for example, adsorbed K+ is more and more replaced by
Ca2+ until eventually the sorption complex is completely saturated by Ca2+ (Fig. 4). In soils, such exchange and equilibrium reactions are complex as
numerous cation species and sorption complexes with differing preferences for particular cation species are involved. The principle, however, is that cations
adsorbed by Coulomb forces at soil colloids equilibrate with free cations in the soil solution. Thus adding cations to a soil by fertilization, e.g., the application of
a potassium salt, results in replacing adsorbed cations with the newly added cations until a new equilibrium is reached. The adsorbed cations are protected
against leaching. but they are available to plant roots. The strength of cation adsorption increases with the the charge of the cation species and with the
thinness of the hydration shell. Provided that there are no specific adsorption sites, the strength of cation adsorption follows Hofmeister's cation sequence:

Figure 4. Ca2+ – K+ exchange, K+ desorption brought about by increasing Ca2+ concentration

At equilibrium, cation-exchange reactions are a helpful tool for predicting the distribution of ions between the adsorbed and solution phases of the soil as the
amounts of cations present are changed. When a soil saturated with potassium is placed in a NaCl solution, the following equilibration occurs:

The exchange equation for this reaction is

Brackets refer to ions on the exchange site and parenthesis to the activity of ions in the solution. Since the proportionate strength of adsorption of the ions
varies with the exchange site, values for k1 differ for different exchange materials.

The divalent/monovalent system, which almost represents the situation in the soil, with K+, Ca2+, and Mg2+ as the dominant exchangeable cations, is more
complex. The following equation, developed by GAPON [39], is widely used to describe monovalent/divalent exchange:

Cation exchange capacity (CEC) is defined as the quantity of cation equivalents adsorbed per unit soil or clay mineral. In Table 7 the exchange capacities of
some soil classes are shown. The exchange capacity of the organic soil appears high if it is based on unit weight of soil. A more realistic picture is obtained,
however, when the exchange capacity is based on soil volume, since under field conditions it is soil volume, not soil weight, that is related to a crop stand.
Table 8 shows the cation exchange capacities of some important clay minerals and of humic acids in relation to the surface of these particles.

Table 7. Cation exchange capacity based on soil weight and soil volume as well as the specific weight of some soil classes

Soil class Specific weight, kg/L Cation exchange capacity *

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cmol/kg cmol/L

Sandy soil 1.5 3 4.5

Loam 1.5 15 22.5
Clay soil 1.5 30 45.0
Organic soil 0.3 75 22.5

* cmol = centimole.

Table 8. Cation exchange capacity and inner and outer surfaces of some soil colloids

Total surface, Inner surface, % Cation exchange capacity,

m2/g mol/kg

Kaolinite 20 0 10
Illite 100 0 30
Smectite 800 90 100
Humic acids 800 0 200

The cation exchange capacity of kaolinites and particularly of humic acids depends much on the pH of the medium. At low pH, most groups are protonated
and hence the exchange capacity is low. Increasing soil pH, e.g., by liming, increases the cation exchange capacity if kaolinites and humic acids are the
dominating exchange complexes.

Cation saturation of negatively charged soil colloids has some impact on soil structure, which is defined as the arrangement of soil particles into aggregates.
High percentage of adsorbed Ca2+ favors the formation of aggregates. In well structured soils, such as in chernozems, 70 to 80 % of the total cation exchange
capacity is occupied by Ca2+. In acid solids, H+ and Al cations (Al3+, Al(OH)2+, ) and in saline soils Na+ and Mg2+ are the dominating cation species
adsorbed to soil colloids.

Anion Exchange. Soil particles may also adsorb anions. The adsorption occurs at the OH groups of aluminum and iron oxides as well as of some clay
minerals. One may distinguish between a nonspecific adsorption and a specific anion adsorption. The nonspecific anion (A–) adsorption originates from
protonated hydroxylic groups.

Protonation depends on soil pH and is particularly high under acid conditions. Hence nonspecific anion adsorption only plays a role in acid soils.

The specific anion adsorption is a ligand exchange. This is, for example, the case for phosphate. In step 1 replaces OH–, resulting in a mononuclear
bond between the phosphate and the iron oxide. In step 2, a further deprotonation of the phosphate occurs, followed by a second ligand exchange (step 3) to
form a binuclear bond between the surface of the iron oxide and the phosphate.

The final structure is supposed to be very stable, and the phosphate so bound is hardly available to plant roots. This reaction sequence explains why anion
(phosphate) adsorption is promoted under low pH conditions. In mineral soils with pH < 7, the adsorbed phosphate represents a major phosphate fraction.
Increasing the soil pH, e.g., by liming, increases phosphate availability [40]. The relationship between free and adsorbed anions can be approximately
described by the Langmuir equation:

A = surface concentration of adsorbed anions

Amax = maximum surface concentration
c = concentration of free anion
k = constant related to adsorption energy, the adsorption strength increasing with k

Adsorption strength depends also on anion species decreasing in the order [41]:

Borate and silicate may also be adsorbed, but only at high pH. Under these conditions, boric acid and silicic acid may form anions according to the following
equations:

This is why in neutral to alkaline soils boron can be strongly adsorbed (fixed) by soil particles, which may lead to boron deficiency in plants. The formation of a

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silicate anion can improve phosphate availability since and phosphates compete for the same ligands at anion-adsorbing surfaces.

2.2.3. Soil pH, Buffer Power, and Liming

Proton concentration (pH) is of vital importance for all living organisms and also has an impact on soils and soil constituents. High H+ concentrations (pH<4)
attack soil minerals, dissolving metal cations out of the crystal lattice, and eventually lead to mineral degradation. Under low soil pH conditions (pH<5),
bacterial life is suppressed while fungal life is relatively favored, which affects the decomposition of organic matter. Low soil pH (pH < 4) also affects root
growth.

In many cases, however, it is not so much the H+ but the toxic level of soluble Al species and Mn2+ associated with low pH conditions that considerably
hamper root development and plant growth. A decrease in soil pH increases the solubility of aluminum oxide hydroxides and maganese oxides considerably.
Under acid soil conditions Al3+, Al(OH)2+, are dissolved in the soil solution or adsorbed to soil colloids. Of the three Al species, Al(OH)2+ is considered
to be the most toxic. Aluminum toxicity of plants is characterized by poor root growth: root tips and lateral roots become thickened and turn brown [42]. In the
cell, Al interferes with the phosphate turnover and may even be adsorbed on the DNA double helix.

A distinction is made between the actual acidity, which is determined by the H+ concentration in the soil solution, and the potential acidity, which is determined
by both the H+ of the soil solution and the adsorbed H+. The actual acidity is measured by hydrogen-ion electrodes; the potential acidity, by titration with a
base. Titration includes the Al species, which also consume OH–

Potential acidity may be high in Al-rich soils as well as in soils with a high cation exchange capacity. Such soils are characterized by a high hydrogen-ion buffer
power: a pH change in the soil solution requires a relatively large amount of H+ or OH–.

In soils, different buffer power systems can be distinguished. Soils containing carbonates are buffered according to the following equation:

Reaction may be promoted by the presence of CO2 originating from root and microbial respiration.

At lower pH levels soils are buffered by adsorbed cations (Fig. 5) and by Al complexes, e.g.,

Figure 5. Principle of hydrogen-ion buffering by adsorbed cations

Soil acidification results from different processes. Plant roots extrude H+ ; net release of H+ is especially high when plants are fed with , while
nutrition results in a net release of OH–. Leguminous species living in symbiosis with Rhizobium extrude H+ at particularly high rates from their roots. Microbial
oxidation of organic N, organic S, and elementary S leads to the formation of strong acids, such as HNO3 and H2SO4, which have a marked acidifying effect on
soils. Also SO2 and NOx as gases as well as the acid rain formed by these oxides have an acidifying effect. In Central Europe these pollutants carry ca. 3 –
5 kmol H+ ha–1a–1 into soils.

Under anaerobic soil conditions, e.g., after flooding, protons are consumed by the reduction of FeIII and MnIII or MnIV as well as by the microbial reduction of
(denitrification):

Some species of Azalea, Calluna, Vaccinium, and also tea (Camellia sinensis) are able to grow on acid habitats. These species can mask the Al with phenols
and organic acids and thus avoid Al toxicity. Rye, potatoes, oats, and lupines tolerate weakly acid soils, whereas beets (Beta vulgaris), barley, rape, and most
leguminous crops prefer more neutral soils. Wheat takes an intermediary position with regard to soil pH. In the case of leguminous crops, it is not so much the
crop itself, rather it is the Rhizobium bacteria living in symbiosis with the crop that are affected by low soil pH. The mulitplication of the Rhizobium in the soil is
depressed by soil acidity.

Low pH levels can be easily overcome by liming, the application of alkaline materials, mainly Ca/Mg oxides, carbonates, and silicates. They react with soil
acidity as follows:

The quantity of lime required depends on the soil pH level and the buffer power. The lower the pH and the higher the buffer power, the more lime required.

Soil acidity is mainly a problem in humid zones, where the H+ formed in the upper soil layer replaces the adsorbed metal cations (Ca2+, Mg2+, K+ ), which are
then leached. Under arid conditions, salts may accumulate in the top soil layer. If a major part of the anions accumulated are and (solonetz soils),
high soil pH levels prevail, which affect plant growth and soil structure considerably. Such soils can be meliorated by heavy applications of elementary sulfur.
Under aerobic conditions the S is oxidized to H2SO4 by soil microorganisms. The strong acid neutralizes the and

2.2.4. Soil Water – Plant Relationships

Plants continuously require water that is taken up from the soil by roots and transported from them to the upper plant parts, particularly to the leaves. From
here water is released into the atmosphere. This last process is called transpiration. Water in the plant tissues is required to maintain optimum cell turgor,
which is crucial for most metabolic processes.

Plants frequently have to overcome long dry periods during which they must feed from the soil water. Very crudely, the soil can be considered as a sponge that

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can store water in its pores and holes. The storage water in the soil must be retained against gravitation. The forces responsible for this retention are
adsorption and capillary forces by which the water is sucked to the surface of the soil particles. This suction force can be considered as a negative pressure,
and hence the strength of water binding in soils is measured in Pascals (Pa), the unit for pressure. The strength of water binding in soils is termed water
potential (in older terminology, water tension). The higher the strength, the lower (more negative) the soil water potential. Water potentials in soils range from 0
to – 1 × 106 kPa. Generally, however, soil water potentials of – 10 to – 1500 kPa prevail.

The total amount of water that can be adsorbed by a soil (all pores and holes filled with water) is called maximum water capacity. This is of minor importance;
more relevant is the water quantity that can be retained against the gravitation force, the field capacity. Not all water of the field capacity fraction is available to
plant roots. A proportion of the field capacity water is so strongly adsorbed that it can not be taken up by the roots. For most plant species this is water with a
water potential < – 1500 kPa: at such a low water potential, plants wilt. Therefore, this critical water potential is also called wilting point. The soil water fraction
not available to plants is called dead water. The available soil water thus equals the difference between the field capacity and dead water.

Soils differ much in their capacity to store water. The higher the clay content of a soil, the larger the total surface of soil particles, and the more water that can
be adsorbed. The water storage capacity of soils increases with the clay content. On the other hand, the water molecules are strongly adsorbed to the surface
of clays and therefore the fraction of dead water increases with the clay content. For this reason, generally medium textured soils (loamy soils), and not the
clay soils, possess the highest storage capacity for available soil water. Besides soil texture, also soil structure and the rooting depth of the soil profile
determine the storage capacity for available soil water.

An important criterion of available soil water is the relationship between the percent water saturation of the soil and the water potential. This is shown in
Figure 6 for a sandy, a loamy, and a clay soil. The section between field capacity (– 10 kPa) and the wilting point (– 1500 kPa) is the highest for the loamy soil.

Figure 6. Relationship between the soil water content and the soil water potential and the resulting available water (AW) for three soil classes

Field capacity is –10 kPa; wilting point is – 1500 kPa.

The capability to use soil water economically differs considerably among plant species. A measure of this capability is the transpiration coefficient, the water
quantity in kg (or L) required for the production of 1 kg plant dry matter:

Sorghum 277
Maize 349
Sugar beet 443
Spring wheat 491
Barley 527
Potatoes 575
Oats 583
Spring rye 634
Red clover 698
Flax 783
Alfalfa 844

Water loss under a vegetation cover results from evaporation (water release from the soil to the atmosphere) and transpiration (water release of the plant to
the atmosphere). Evaporation is unproductive, transpiration productive. The relation between the two depends on plant nutrition, as can be seen in Table 9,
which shows the favorable effect of N fertilizer on the productive use of soil water [43].

Table 9. Relationship between N fertilizer rate, grain yield of barley, evaporation, and transpiration [43]

Nitrogen fertilizer rate, Grain yield, Transpiration, * Evaporation,*

kg/ha t/ha L/m2 L/m2

30 1.02 85 235
125 1.65 121 278
225 2.69 217 212

* Transpiration and evaporation in liters per square meter of soil surface.

2.2.5. Organic Matter of Soils and Nitrogen Turnover

Organic matter of soils differs considerably. Soils can be classified according to the content of organic carbon in the soil (g/kg):

Low <5
Medium low 5 – 10
Medium 10 – 20
High 20 – 40
Rich 40 – 80
Muck 80 – 150
Peat >150

Soils with an organic carbon content of 50 g/kg are termed organic soils, in contrast to mineral soils. Enrichment of organic matter in soils depends on location
and climatic conditions. Low temperature and a lack of oxygen favor the accumulation of organic matter in soils because these conditions hamper breakdown
by soil microbes. Therefore, under cold continental climate conditions (frost, long winters) and under hydromorphic soil conditions (swamps, moors, bogs),
organic matter accumulates.

The fertility status of organic soils differs considerably. Moors located on the tops of mountains are generally poor in nutrients, especially in N and K, since they
are fed mainly from rain. Moors in lowland fed from rivers and streams may be rich in plant nutrients, especially in N. The C : N ratio of the organic matter and
soil pH are suitable indicators of the fertility status. Fertile soils possess C : N ratios of ca. 20 in their organic matter and pH values in the weak acid to weak
alkaline range. Acid organic soils (highland moors) have much higher C : N ratios, ca. 50 or more in their organic matter. The C : N ratio has direct impact on
the decomposition of organic N by soil microbes; the higher the ratio the lower the net release of mineral N by microbial activity.

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Nitrogen turnover in soils is related not only to biological processes but also to physicochemical processes. In addition, there is a rapid exchange of N between
the biosphere, the soil, and the atmosphere. The main processes of this nitrogen cycle are shown in Figure 7. Inorganic nitrogen, mainly and ,
including fertilizer N, can be easily assimilated by higher plants as well as by microbes (fungi, bacteria). Also dinitrogen (the N2 of the atmosphere) can be
reduced to NH3 by some soil bacteria. The N2 fixation capacity of the so-called free living bacteria, mainly species of Azotobacter, Beijerinckia, Azospirillum,
and some species of the Cyanobacteria (Anabaena, Nostoc, Rivularia) is moderate, amounting to ca. 5 – 50 kg ha–1a–1. Symbiontic N2-fixing bacteria, mainly
species of Rhizobium and Actinomyces, have a fixation capacity about 10 times higher: for pulses (grain legumes) 50 – 100 kg/ha per growth period and for
forage legumes even 200 – 500 kg ha–1a–1. They are of utmost importance in the N turnover and N availability in soils.

Figure 7. N cycle in nature. Transfer of N between soil, plant, and atmosphere

Inorganic nitrogen (N2, , ) assimilated by living organisms is mainly used for the synthesis of proteins, amino sugars, and nucleic acids. As soon as
these organisms die, the organic N can be attacked by other microorganisms, which are able to convert the organic N into an inorganic form, a process called
nitrogen mineralization. This starts with ammonification, and under aerobic conditions and favorable soil pH ammonification is followed by nitrification in the
sequence:

Ammonification is carried out by a broad spectrum of heterotrophic organisms; nitrification only by a small number of autotrophic bacteria [44]. The microbial
oxidation of to and to requires oxygen and hence proceeds only under aerobic conditions. The oxidation of to is brought about
by species of Nitrosomonas, Nitrosolobus, and Nitrospira, oxidation of to by species of Nitrobacter. They all require weak acid to neutral soil
conditions; in acid soils nitrification is more or less blocked.

Ammonium ions produced by microbial breakdown of organic N, including urea, as well as fertilizer can also be fixed by 2 : 1 clay minerals. In this form,
is protected against nitrification and leaching, but, depending on the type of clay minerals, may still be available to plant roots [45]. This fixed fraction
is of major significance for plant nutrition in soils derived from loess.

The concentration of ammonium ion in the soil solution is governed by the equilibrium

At pH < 6, there is virtually no NH3 present; with an increase in pH the deprotonation of increases, and so does the risk of NH3 loss by volatilization. In
alkaline and calcareous soils considerable amounts of N can thus be lost by the soil system [46]. High losses of NH3 may also occur from the application of
slurries, which generally have an alkaline pH [47].

Ammonium as well as are taken up by plant roots at high rates, and vigorous crop stands can deplete the concentration in the soil to a great extent.
Nitrate is very mobile in soils since it is virtually unadsorbed on soil colloids. It can be leached by rainfall to deeper soil layers or even into the ground water
(see Section Gains and Losses of Plant Nutrients). Nitrate losses may also occur under anaerobic soil conditions, for some bacterial species are able to use
the oxygen of the as e– acceptor for respiration. Nitrate is thus reduced to volatile NO, N2O, and N2 [49]:

This process, brought about mainly by species of Pseudomonas, Alcalignes, Azospirillum, Rhizobium, and Tropionibacterium, is called denitrification. It may
cause considerable soil N losses particularly in flooded rice soils, in which anaerobic conditions prevail [50].

Loss of by leaching or denitrification can be reduced by blocking the formation by application of nitrification inhibitors such as Nitrapyrin (2-chloro-6-
trichloromethylpyridine), AM (2-amino-4-chloro-6-trimethylpyrimidine), or terrazole (5-ethoxy-3-trichloromethyl-1,2,4-thiadizole). There are also some natural
compounds that are nitrification inhibitors [51]. The most important is neem, which occurs in the seeds of Azadirachta indica, a tree common in the tropics.

Some of the organic N in the soil may be incorporated into a very stable organic form. This nitrogen, which mainly occurs in humic acids, is hardly mineralized.
In most soils the humus-N fraction is by far the largest, comprising 80 – 90 % of the total soil N. It is of great importance for soil structure, but has hardly any
relevance as a nutrient reserve.

The fraction of hydrolyzable soil N can be mineralized and thus may serve as a source for N absorbed by plants. The most important fraction in this respect is
the N of the biomass, which comprises ca. 40 – 200 kg/ha, thus only a small fraction of total soil N, which may be 2000 – 8000 kg/ha in arable soils.

2.3. Nutrient Availability

2.3.1. Factors and Processes
From the total amount of N present in the soil, only a small proportion can be made available for plants (see above). This is also true for other plant nutrients.
For example, in a clay-rich soil ca. 200 000 kg K+ may be present in 1 ha within the rooting depth of 80 – 100 cm, but only 1 % may be available to plant roots.

Plant nutrient availability depends on physicochemical and biological factors. A young root pushing into a soil directly contacts only a small amount of
macronutrients, which would contribute only a few percent of the total nutrient demand. By far the greatest proportion of nutrients ( , , K+, Ca2+, Mg2+ )
required by the plant must be transported towards the plant roots. This transport can be brought about by mass flow and/or diffusion. In mass flow, the
nutrients are moved with the water flow from the soil towards the roots. Therefore mass flow depends much on water uptake and transpiration conditions. At
zero transpiration (100 % relative humidity, rainy, or foggy weather) mass flow is also zero. Mass flow plays a major role for the transport of Ca2+, Mg2+, and
also for in cases where the concentration of the soil solution is high, e.g., after fertilizer application.

Nutrients that are taken up at high rates by plant roots (K+, ; , phosphate) but that have relatively low total concentration in the soil solution are
mainly transported by diffusion. Uptake of nutrients by roots decreases the nutrient concentration near the root surface and establishes a concentration
gradient, which drives the diffusive flux of nutrients from the soil towards the plant roots. Absorbing roots thus act as a sink for plant nutrients. Typical depletion
profiles are shown in Figure 8 for phosphate [52]. Phosphate and K+ concentrations in the soil solution at the root surface may be as low as 1 M, whereas in
the bulk soil solution concentrations of 50 to 300 M phosphate and 500 to 1000 M K+ may prevail. Fertilizer application increases the nutrient
concentration of the soil solution and hence the concentration gradient that drives the nutrients towards the roots. Therefore, the level of the nutrient
concentration in the bulk soil solution is an important factor of nutrient availability.

Figure 8. Phosphate depletion around a corn root: P concentration in the soil solution as a function of the distance from the root surface [52]

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Diffusive flux and mass flow in the soil depend much on soil moisture. The dryer a soil, the smaller the water cross section (the size of soil pores that are still
filled with water) and the more the nutrient flux is hampered. Therefore, soil moisture is another important factor of nutrient availability [53]. A third important
factor of nutrient availability is the nutrient buffer power of a soil, a factor of particular relevance for phosphate, K+, and . Here buffer power means the
capability of a soil to maintain the nutrient concentration level in the soil solution (in analogy to the hydrogen-ion buffer power, see Section Soil pH, Buffer
Power, and Liming). In well-buffered soils nutrients absorbed from the soil solution by roots are replenished by nutrient desorption, e.g., by cation exchange.

The most important biological factor for nutrient availability is root growth [54]. For most plant nutrients, only the soil volume around the root can be exploited
by the plant. For phosphate the depletion zone extends only a few millimeter from the root surface and depends much on the length of root hairs, as can be
seen from Figure 8. For K+ and , the depletion zone is more extended, ca. 1 – 4 cm from the root surface. Root mass, root length, and root hairs therefore
are of great importance for the portion of soil volume that can be exploited by a crop stand.

Roots excrete organic materials such as organic acids, sugars, and slimes from which bacteria feed. As a result, the bacterial colonization in the rhizosphere
(the volume around the root) is much denser than in the soil apart from the roots. These bacteria are involved in the N turnover, e.g., for the N2 fixation of free-
living bacteria and for denitrifying bacteria [55].

Proton excretion of roots affects bacterial activity in the rhizosphere, the dissolution of calcium phosphates, and the cation exchange. Net proton release of
plant roots is strongly affected by the type of N supply. Ammonium nutrition results in a high net release of H+, nitrate nutrition in release of OH– and .
Leguminous species living in symbiosis with Rhizobium are known for a high H+ release by roots and therefore have a strong acidifying effect on soils.

Nutrient deficiency, e.g., phosphate or Fe deficiency, also increases net release of H+, which may contribute to the dissolution of iron oxides and calcium
phosphates. The release of avenic acid and mugineic acid by plant roots is of particular importance for the mobilization of Fe in the rhizosphere [56].

Plant growth may be enhanced after infection with mycorrhizal fungi, which leads to increased nutrient uptake due to increases in the effective absorptive
surface of the root, mobilization of sparingly available nutrient sources, or excretion of ectoenzymes or chelating compounds. Furthermore, mycorrhizal fungi
may protect roots from soil pathogens [57] and and in this way enhance root growth and nutrient acquisition of the host plant. This is particularly important
when considering the nutrition of plants with immobile nutrients such as phosphorus, as fungal hyphae are known to absorb P and translocate it into the host
plant [58].

2.3.2. Determination of Available Plant Nutrients in Soils

The level of available plant nutrients in soils can be assessed by means of plant analysis and soil analysis. In the case of plant analysis, the nutrient content of
a particular plant organ at a certain physiological stage may reflect the nutritional status of the plant, hence also the nutrient status of the soils [59]. Such
diagnostic plant analysis is particularly common for perennial crops, including fruit trees and forest trees.

In soil analysis, soil samples are extracted with special extractants. The quantity of nutrients extracted reflects the level of available nutrients in the soil.
Numerous soil extractants have been developed. In Central Europe the DL method (double lactate method) and the CAL method (calcium acetate lactate
method) are widely used for the determination of available soil K and P. In the Netherlands, available P is extracted by water (P-water method). In the United
States, the Olsen method (extraction with NH4F + HCl) is used for the determination of available soil phosphate [60]. Ion-exchange resins are also useful tools
for the determination of available plant nutrients [61].

Of particular interest is the determination of available soil N early in spring before the first application of N fertilizer. Mineral N ( , exchangeable ) is
extracted with a CaCl2 or K2SO4 solution [62]. This technique, called the Nmin method, provides reliable information on the level of directly available soil N.
The easily mineralizable N in the soil, which frequently is the important fraction for the release of available N during the growth period, is not obtained by the
Nmin method.

Electro-ultrafiltration (EUF method) has been used for the determination of available soil nutrients [63]. This method uses an electric field to separate nutrient
fractions from a soil suspension. Most plant nutrients can be extracted. The advantage of this method is that, besides inorganic nitrogen, the readily
mineralizable organic N fraction is extracted [64].

In the last decade S has attracted interest as a plant nutrient. Numerous procedures have been proposed for the determination of plant-available S in soils.
The procedures include extraction with water, various salts and acids, and S mineralization by incubation [65].

The relationship between soil analysis data and the response of crops to fertilizer application is not always satisfying since other factors may interfere, such as
rooting depth, root morphology, soil moisture, and particularly the clay content. These factors should be taken into consideration in interpreting soil test data.

2.4. Physiology of Plant Nutrition

2.4.1. Nutrient Uptake and Long-Distance Transport in Plants
Oxygen and CO2 are mainly taken up by aboveground plant parts. The process of uptake is a diffusion of CO2 and O2 into the plant tissue. For the entry of
these gases into the plant, the stomata are of major importance. Water and other plants nutrients are mainly absorbed from the soil solution. The rate of
nutrient uptake increases with the concentration of the particular nutrient in the soil solution, the rate of uptake leveling off at higher soil-solution
concentrations.

Plant nutrients in the soil solution, mainly present in ionic form, diffuse into the root tissue. The outer plasma membrane of the cells (plasmalemma) is a great
diffusion barrier. The transport of nutrients across this barrier is the proper process of ion uptake. This transport is not mere diffusion, but is related to specific
membrane components and to metabolic processes that allow selective uptake of the plant nutrients, which is often associated with an accumulation of the
nutrient in the cell. For example, the K+ concentration in the cell (cytoplasm) may be higher by a factor of 102 – 103 than the K+ concentration in the soil
solution.

Nutrient uptake is initiated by an enzyme located in the plasma membrane called ATPase (ATP hydrolase). Its substrate is ATP. Hydrolyzation of ATP results
in the splitting of H2O into H+ and OH–, from which the latter remains in the cytosol of the cell while H+ is extruded into the outer medium (Fig. 9). Thus an
electrochemical potential is created between the two sides of the membrane. The proton motive force (p.m.f.) obtained in this way is described by the following
equation [66]:

Figure 9. Scheme of plasmalemma-located ATPase, hydrolyzing ATP and pumping H+ into the apoplast (proton pump)

The p.m.f. is the driving force for ion uptake. Cations are directly attracted by the negatively charged cell. Since the plasma membrane, however, represents a
strong barrier, the entry of cation species must be mediated by particular carriers and ion channels. Little is known about these carriers and channels in plant
membranes. These are assumed to be ionophores like valinomycin, nonactin, or gramicidin, which bind selectively to cation species and hence mediate a
selective cation transport across the membrane. Such a type of carrier transport is shown in Figure 10. The carrier is hydrophobic and therefore quite mobile in

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the membrane, which consists mainly of lipids. At the outer side of the membrane it combines selectively with a cation species, e.g., K+. The cation carrier
complex then diffuses to the inner side of the membrane, where the K+ is released. Release and combining with K+ depend on the electrochemical difference
between the two sides of the membrane. High K+ concentration and a positive charge favor the combining process; low K+ concentration and a negative
charge favor the release of K+. Net transport rate becomes zero as soon as the electrochemical equilibrium is attained, which is governed by the Nernst
equation:

E = electrical potential difference between the two sides of the membrane

F = Faraday constant
z = oxidation state of the cation
ao = activity of the cation species in the outer solution
ai = activity of the cation species in the inner solution

Figure 10. Scheme of K+ carrier transport across the plasmalemma

The uptake of anions ( , ) is also assumed to be driven by the plasmalemma-located ATPase. The anions presumably form protonated carriers at
the outer side of the membrane and then are selectively tranported across the membrane. The protonated carrier – anion complexes are positively charged.
Hence the electropotential difference between either side of the plasmamembrane represents the driving force for anion uptake.

Ion absorbed by cells of the root cortex are translocated via the symplasm in centripetal direction towards the central cylinder, where they are secreted into the
xylem vessels. The actual process of this secretion is not yet understood. In the xylem the ions are translocated to the upper plant parts with the transpiration
stream. They thus follow the vascular system of the plant and are distributed along the major and minor vein system of leaves from where they diffuse into the
pores and intercellular spaces of cell wall (apoplast). The transport from the apoplast across the plasmamembrane into the cytoplasm of leaf cells is a process
analogous to the nutrient uptake of root cells.

Some plant nutrients, such as N, P, K, and Mg, but not Fe and Ca, may also be translocated against the transpiration stream via the phloem tissue. These
nutrients therefore may be transported from the tops to the roots or from older leaves to younger leaves.

2.4.2. Effect of Nutrition on Growth, Yield, and Quality

Meristematic growth requires plant nutrients: N and P for the synthesis of proteins and nucleic acids, K and Mg for the activation of enzymes and for
membrane potentials, and all the other nutrients for various processes. The quantities required differ greatly but for practical purposes mainly N, K, and P, in
some cases also Mg and Ca, limit plant growth. The growth rate is controlled by the nutrient with the lowest availability (LIEBIG's law of minimum). Application
of this particular nutrient results in a growth response. This response is not linear, but rather follows a saturation type of curve (Fig. 11). Also crop yields as a
function of increasing rates of fertilizer applicaton reflect this curve, which is also called the Mitscherlich curve since MITSCHERLICH [67] investigated these
relationships extensively. The curve is described by the following equation:

A = maximum yield
y = obtained yield
x = growth factor, e.g., fertilizer rate
c = constant
The term (A – y) is the increment that is required to attain the maximum yield. This increment becomes smaller as the variable x (growth factor) becomes
greater. Such growth factors include not only plant nutrients, including CO2, but also light intensity and temperature. The growth response obtained by these
factors also follows the saturation type of curve shown in Figure 11.

Figure 11. Mitscherlich curve, response curve of diminishing increments (i) with each further unit of growth factor

Growth and metabolic processes in plant tissues depend not only on the rates of plant nutrients supplied but also on the ratio in which the nutrients are
provided. If the N supply is relatively high as compared with the supply of other nutrients, the synthesis of N-containing compounds, such as amino acids and
proteins, is promoted. This may have a favorable effect on the protein synthesis in grains of cereals and hence improve their baking quality and their nutritional
value. In grains for malting purposes and in particular barley, however, low protein content and high starch content are required. In this case, relatively high N
rates have a detrimental effect on grain quality. An analogous case is the sugar beet, which should be high in sugar and low in N-containing compounds,
especially amino acids. Relatively high N supply favors the synthesis of vitamins of the vitamin B group and the synthesis of carotenes in green plant tissue but
has a negative effect on the content in vitamin C. High N rates may also increase the sensitivity of leaves and culms to fungi attack.

Phosphate and especially K+ have a favorable impact on the energy status of plants. A relatively high supply of both nutrients promotes the synthesis of
carbohydrates and the development of cell wall material, which increases the resistance against fungi attack.

2.5. Nutrient Balance

2.5.1. Gains and Losses of Plant Nutrients
In order to maintain the level of available plant nutrients in soils, the quantity of nutrients lost from the soil must be replenished. Nutrients may be lost by
harvesting of plant material, leaching, transition into a non-available form in the soil, and volatilization. Nutrient gains result from fertilizer application, soil
weathering, rainfall, and microbial dinitrogen fixation (see Section Organic Matter of Soils and Nitrogen Turnover). In most soils, weathering provides enough
of those nutrients that are only required in minor amounts, such as Fe, Mn, Cu, Zn, Mo, and B. Young soils being rich in primary minerals also may weather
appreciable amounts of Mg, K, and phosphate. Generally, the contribution of plant nutrients released by weathering is more important if the yield level is lower.
Up to the mid-1980s, sulfur supply to crops was to a large extent brought about by SO2 in the atmosphere and by SO2 dissolved in precipitation. However, in
the last two decades increased global environmental concern has prompted reductions in SO2 emissions, which in past years were beneficial for crop growth
in many countries [68]. With the reduction in the sulfur supply from atmospheric emissions, the greater use of high-analysis S-free fertilizers, new high-yielding
crop varieties, and declining use of sulfur as a fungicide, sulfur deficiency became widespread in various parts of the world.

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The quantity of nutrients taken up by crops depends mainly on the yield level and on the kind of plant organs. For a rough calculation of nutrient uptake by
crops the following figures may be used:

1 t of grain (cereals) contains

20 – 25 kg N

5 kg K

4 kg P
1 t of dry matter of green plant material (leaves, stems) contains
15 – 30 kg N

15 – 30 kg K

2–4 kg P
1 t of roots (beets) or tubers contains
1.5 – 3 kg N

4–5 kg K

0.3 – 0.6 kg P

Nutrient losses only occur from plant parts removed from the field. For example, if only grain is harvested and the straw remains on the field, only the plant
nutrients present in the grain are lost from the system.

High nutrient losses may occur by leaching. The quantities lost depend much on climate, weather conditions, and soil properties. In Central Europe, with a
rainfall of about 700 mm/a, ca. 25 – 50 % of the precipitation passes through the soil profile to a depth >1 m. Plant nutrients dissolved in this drainage water
are lost from the soil. Table 10 shows maximum and minimum leaching rates obtained during a period of eight years by VÖMEL [69]. Generally, leaching rates
are low if the soil clay content is high. High leaching rates prevail in fallow soils, low rates in soils with a permanent plant cover, e.g., grassland. Phosphate is
effectively not leached. Leaching occurs mainly with the winter or monsoon rainfall. Under such humid conditions plant nutrients present in plant residues
(stubble, straw, roots, leaves) also may be leached.

Table 10. Leaching rates of plant nutrients from soils [69]

Soil Plant nutrient, kg ha–1 a–1

N K Ca Mg

Sand 12 – 52 7 – 17 110 – 300 17 – 34

Sandy loam 0 – 27 0 – 14 0 – 242 0 – 37
Loam 9 – 44 3 – 8 21 – 176 9 – 61
Clay 5 – 44 3 – 8 72 – 341 10 – 54

Volatile losses only play a role for nitrogen, which may be lost in form of NH3, N2, and N2O (see Section Organic Matter of Soils and Nitrogen Turnover).
Nutrient loss by conversion into a non-available form is only relevant for phosphate and in some cases for K+.

2.5.2. Alternative Plant Nutrition

The terms “ecological agriculture” and “biological agriculture” are used as synonyms for “organic agriculture”. One of the main approaches of organic
agriculture is a mixed farm system within a more or less closed nutrient cycle. With regard to plant nutrition the production system can be characterized by the
following principles:

Nearly closed cycles of nutrients and organic matter within the farm
Predominant use of farmyard manure and compost
Slowly soluble P minerals, if necessary
K fertilizers not in the form of chloride

Besides nitrogen, which may be imported with manure, symbiotically bound nitrogen is the main N source. For this reason N2 fixation by legumes is of great
importance. Synthetic fertilizers are renounced. In the last few years major efforts were undertaken to quantify the cycles of nutrients as well as the organic
matter cycles.

Organic agriculture has to deal with limited amounts of nutrients. Nutrient management, defined as systematic target-oriented organization of nutrient flow, is
therefore considered as the optional combination of resources that are restricted or have to be released. Strategies must be adopted that make nutrients in the
system internally available by achieving optimized utilization or which keep nutrients potentially available in the long term. The main nutrient flows in organic
farm are fixed for the long term by organizing and optimizing the site-adapted crop rotation [70].

[Top of Page]

3. Standard Fertilizers
Heinrich Dittmar

Standard fertilizers include the products used in large quantities worldwide. They are applied to agricultural and large-scale garden crops. They can be
classified as solid and liquid fertilizers.

3.1. Solid Fertilizers

Solid fertilizers are the most important group of fertilizers. Worldwide, nearly 90 % of all the nitrogen applied in fertilizers is in solid form (season or fertilizer
year 1996/97). In Germany about 83.5 % of total nitrogen is applied in the solid form, and the corresponding figure in the United States is 44 %. Phosphate
and potash are applied mainly in solid form. Solid fertilizers include granular, prilled, and compacted products (see Chap. Fertilizer Granulation).

A summary of the most important fertilizers can be found in [71].

3.1.1. Straight Fertilizers

Straight fertilizers contain only one nutrient, for instance, urea (N) or triple superphosphate (P2O5). Straight solid fertilizers are listed in Table 11.

Table 11. Straight fertilizers

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Type Production; main Analysis, wt % Remarks Ullmann keyword

constituents

Nitrogen fertilizers
Calcium nitrate [ synthetic 15.5 % N (Ca(NO3)2), fast acting; chiefly for Nitrates and
13477-34-4] NH4 N, max. 1.5 % special crops and Nitrites
refertilizing
Sodium nitrate [ synthetic 16 % N (NaNO3) fast acting; chiefly for Nitrates and
7631-99-4] special crops and Nitrites
refertilizing
Chile saltpeter from caliche; sodium nitrate ≥ 15 % N fast acting; chiefly for
special crops and
refertilizing
Ammonium nitrate synthetic; may contain 34 % N(NH4NO3) special storage provisions Ammonium
[6484-52-2] additives such as ground (see Chap. Storage, Compounds –
limestone, calcium sulfate, Transportation, and Ammonium Nitrate
dolomite, magnesium sulfate, Application)
kieserite
Calcium synthetic; may contain 26 – 28 % N, ≥ 2 % versatile fertilizer, both fast Ammonium
ammonium nitrate additives such as ground CaCO3 and slow acting Compounds
(CAN) limestone, calcium sulfate
dolomite, magnesium sulfate,
kieserite
Ammonium sulfate synthetic added as limestone or versatile fertilizer with both Ammonium
nitrate (ASN) dolomite 26 % N ( fast and slow action Compounds
and (NH4)
2SO4), ≥ 5 % NO3 N
Magnesium synthetic; ammonium nitrate 20 % N (NH4NO3) for soils and crops requiring
ammonium nitrate and magnesium compounds magnesium
(dolomite, magnesium
carbonate, or magnesium
sulfate)
Ammonium sulfate synthetic, often as byproduct ≥ 6 % NO3 N, 5 % slow acting, for soils Ammonium
[7783-20-2] MgO 21 % N ((NH4) containing lime and/or high- Compounds –
precipitation areas Ammonium Sulfate
2SO4)
Ammonium synthetic ≥ 25 % N (NH4Cl) rice fertilization, chiefly in Ammonium
chloride [ Japan and India Compounds –
12125-02-9] Ammonium Chloride
Urea [57-13-6] synthetic 46 % N (CO(NH2)2) optimal only when soil lime, Urea
biuret ≤ 1.2 % heat, and moisture are
appropriate; also suitable
for foliar application; volatile
losses are possible
Calcium synthetic 20 – 22 % N; ≥ 75 % slow acting, special Cyanamides –
cyanamide [ of total N from requirements, also for weed Calcium Cyanamide
156-62-7] cyanamide; ca.40 % control nitrification
CaO 66 % N
Dicyandiamide [ synthetic nitrification inhibitor, added Cyanamides –
461-58-5] pure to liquid manure; also Dicyandiamide
as additive to straight and
compound fertilizers
containing ammonium
Phosphate
fertilizers
Basic slag byproduct of steel production ≥ 12 % P2O5 soluble phosphate containing up to Phosphate
(Thomas from ores containing in mineral acid, 45 % CaO, versatile Fertilizers
phosphate) phosphate; calcium phosphate fertilizer
≥ 75 % soluble in 2 %
silicophosphate
citric acid
Superphosphate digestion of ground 16 – 22 % P2O5 for all soils Phosphate
phosphate rock with sulfuric soluble in neutral Fertilizers
acid; monocalcium phosphate ammonium citrate
with calcium sulfate solution, 93 % water
soluble
Triple digestion of ground 45 % P2O5; soluble in for all soils Phosphate
superphosphate phosphate rock with neutral ammonium Fertilizers
phosphoric acid; citrate solution, 93 %
monocalcium phosphate water soluble
Partly digested partial digestion of ground ≥ 20 % P2O5; soluble for all acidic soils (pH < 7) Phosphate
phosphate rock phosphate rock with sulfuric in mineral acid, 40 % Fertilizers
or phosphoric acid; water soluble
monocalcium phosphate,
tricalcium phosphate, calcium
sulfate
Soft phosphate grinding of soft phosphate ≥ 25 % P2O5 soluble for acidic soils and low- Phosphate
rock rock; tricalcium phosphate in mineral acid, 55 % precipitation areas Fertilizers
and calcium carbonate soluble in 2 % formic
acid
Dicalcium neutralization of phosphoric ≥ 38 % P2O5 soluble for all soils Phosphoric Acid
phosphate [ acid with calcium hydroxide in alkalized and Phosphates
7789-77-7] dicalcium phosphate ammonium citrate; not
dihydrate water-soluble
Thermal (fused) thermal digestion of ground ≥ 25 % P2O5 soluble for all soils and locations

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phosphate phosphate rock with alkali- in alkalized
metal compounds and silicic ammonium citrate
acid; alkali-metal calcium solution and in citric
phosphate and calcium acid
silicate
Aluminum calcium thermal digestion and 29 – 33 % P2O5 for all soils and locations
phosphate grinding; amorphous soluble in mineral
aluminum and calcium acid, 75 % soluble in
phosphates alkalized ammonium
citrate solution
Potassium
fertilizers
Potash ore run-of-mine potash ≥ 10 % K2O, ≥ 5 % for soils and crops where Potassium
MgO, contains sodium Na and Mg are important, Compounds
especially cattle fodder
Beneficiated beneficiation of run-of-mine ≥ 18 % K2O for all soils Potassium
potash ore potash and mixing with Compounds
potassium chloride
Potassium beneficiation of run-of-mine ≥ 37 % K2O (up to for all crops not sensitive to Potassium
chloride [ potash 60 %) chloride Compounds
7447-40-7]
Potassium beneficiation of run-of-mine ≥ 37 % K2O, ≥ 5 % on Mg-deficient soils for all Potassium
chloride with potash and addition of Mg MgO crops not sensitive to Compounds
magnesium salts chloride
Potassium sulfate synthetic ≥ 47 % K2O, ≤ 3 % Cl for all crops sensitive to Potassium
[7778-80-5] chloride Compounds
Potassium sulfate synthetic, from potassium ≥ 22 % K20, ≥ 8 % deficient soils for all crops Potassium
with magnesium sulfate, with addition of Mg sensitive to chloride Compounds
MgO; ≤ 3 % Cl
salts; potassium sulfate and
magnesium sulfate

3.1.2. Multinutrient Fertilizers

Multinutrient or compound fertilizers contain two or more nutrients. The term complex fertilizer refers to a compound fertilizer formed by mixing ingredients that
react chemically. In bulk-blend or blended fertilizers (see Chap. Fertilizer Granulation), two or more granular fertilizers of similar size are mixed to form a
compound fertilizer.

There are several routes for manufacturing fertilizers. An important route is the Odda process, in which phosphate rock is digested with nitric acid. Calcium
nitrate is crystallized by cooling and removed, and the mother liquor is neutralized by addition of gaseous ammonia (see Phosphate Fertilizers –
Compound Fertilizers by the Nitro Route). Other important processes are based on digestion of phosphate rock with sulfuric acid and the so-called mixed-acid
process [355]. For the production of NPK fertilizers, potassium compounds are added in the desired amount to the corresponding slurries. Magnesium (as
kieserite or dolomite) and micronutrients may also be added.

NPK Fertilizers. According to the EEC Guidelines, NPK fertilizers must contain at least 3 % N plus 5 % P2O5 plus 5 % K2O and at least 20 % total nutrients.
The most commonly used grades (N-P2O5-K2O, each in wt %) are

Nutrient ratio 1 : 1 : 1
15–15–15, 16–16–16, 17–17–17
Nutrient ratios 1 : 2 : 3 and 1 : 1.5 : 2
5–10–15, 6–12–18, 10–15–20
Nutrient ratio 1 : 1 : 1.5 – 1.7
13–13–21, 14–14–20, 12–12–17
Nutrient ratios 3 : 1 : 1 and 2 : 1 : 1
24–8-8, 20–10–10
Low-phosphate grades
15–5-20, 15–9-15

If additional numbers are given in a fertilizer grade, the fourth is the wt % MgO and the fifth is wt % S. Micronutrient contents may also be stated. In some
countries the grade is expressed in terms of the elements rather than oxides.

The NPK fertilizers have the important advantage of simplified application, since all the important nutrients can be distributed in one operation. Each grain of
fertilizer has the same content of nutrients. Serious errors are prevented by the harmonic nutrient ratio, provided the metering rate is correct. The nitrogen is
usually present as nitrate and ammonium N in roughly equal parts. The phosphate is 30 – 90 % water-soluble, the rest being soluble in ammonium citrate
solution. Most of the potassium is present as the chloride; the sulfate is used for chloride-sensitive crops.

In bulk-blended products (see Section Bulk Blending), the individual fertilizers are combined in the desired nutrient ratio. The operational advantage is the
same as that of synthetic NPK fertilizers. Because, however, the individual granular products may differ in grain-size spectrum, granule surface characteristics,
and density, segregation may occur during handling, storage, packaging and even during application. These products are therefore suitable for practical use
only when the individual components have similar physical qualities.

NP Fertilizers. The minimum analysis for NP fertilizers under the EEC Guidelines is 3 % N and 5 % P2O5 and at least 18 % total nutrients. Common grades
are 20–20, 22–22, 26–14, 11–52, 16–48, and 18–46. These products are appropriate for potassium-rich soils or where potash is supplied as a separate
fertilizer.

NK Fertilizers. The minimum analysis for NK fertilizers under the EEC Guidelines is 3 % N and 5 % K2O and at least 18 % total nutrients. These products are
suitable for phosphate-rich soils or where phosphate is distributed separately.

PK Fertilizers. In the group of PK fertilizers, all combinations of the straight phosphate and potassium components listed in Table 11 are possible. In general,
the materials are first milled and then mixed and granulated, so that a fairly homogeneous mixture is obtained. Some products are also made by bulk blending.
The EEC Guidelines set forth a minimum analysis of 5 % P2O5, 5 % K2O, and at least 18 % nutrients. Magnesium and micronutrient boron can be added.

3.1.3. Lime Fertilizers

Solid fertilizers also include lime fertilizers. The main purpose of using lime is to optimize soil pH; a secondary purpose is to supply calcium as a plant nutrient.
The use of large amounts of lime to increase the pH is referred to as soil-improvement liming. Use to maintain the present pH is called maintenance liming.

The starting materials for lime fertilizers are limestone [1317-65-3] and dolomite [17069-72-6]. These are marketed in various forms. National fertilizer
regulations (e.g., the type list in the Federal Republic of Germany's fertilizer law, see Chap. Legal Aspects) govern the fineness of grinding. Calcination at

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900 – 1400 °C yields quicklime CaO; hydration with water gives slaked lime Ca(OH)2. The most immediately effective form is finely divided quicklime with a
particle size of ca. 0.15 mm or less. If a lime grade contains at least 15 % MgO or MgCO3, it can be called magnesium lime. The content of MgO depends on
the starting material (proportion of dolomite) and may be up to 40 %.

Calcium carbonates [471-34-1], CaCO3 , act slowly. They are recommended above all for lighter soils. Unslaked and slaked limes are faster acting. They are
suitable mainly for loamy and clayey soils.

Besides these lime products from natural rock, there are also limes from industrial processes. They include smelting lime and converter lime, which are steel-
industry byproducts. Converter lime with phosphate must contain 40 % CaO + MgO and also at least 5 % P2O5. These products must also satisfy minimum
requirements on fineness to ensure sufficiently fast action.

Finally, the refining of beet sugar yields a product containing lime. According to the fertilizer law in the Federal Republic of Germany, this lime form must
contain at least 30 % CaO and 5 % MgO.

3.1.4. Magnesium Fertilizers

The following magnesium fertilizers are offered in commerce: kieserite [14567-64-7] (27 % MgO) for soil application, and Epsom salts [7487-88-9] (17 % MgO)
for foliar application in liquid form.

3.2. Liquid Fertilizers

Only solid fertilizers were produced and used up to ca. 1950: lower production costs, higher nutrient concentrations, and the ease of making compound
fertilizers were for a long time the reasons that development was limited to the solid fertilizers. Since then, liquid fertilizers have also been developed and
supplied to agriculture. Particularly in the United States, liquid fertilizers have come into heavy use. Modern production methods have lowered production
costs, even for liquid fertilizers with high nutrient concentrations.

Homogeneous liquid fertilizers, in contrast to solid fertilizers, present no special problems during application by the farmer. Furthermore the storage of liquid
fertilizers is less difficult than that of solid ones. Small amounts of herbicides and insecticides can be mixed with liquid fertilizers far more easily. Production
plants for solid fertilizers are much more costly than those for liquid fertilizers. Liquid fertilizers have the drawbacks that they usually have lower nutrient
content and are sensitive to impurities, as well as to precipitation and crystallization, especially caused by magnesium and fluorine.

Liquid fertilizers are classified as (1) anhydrous ammonia [7664-41-7] with 82 wt % N at high pressure, (2) aqueous ammonia with up to 24 wt % N, (3)
ammoniates (ammoniated ammonium nitrate and/or urea solutions) with up to 50 wt % N at moderate to atmospheric pressure, and (4) nonpressure urea –
ammonium nitrate solutions with up to 32 wt % N [72]. Compound liquid fertilizers include both clear liquids and suspensions.

The growing interest in liquid fertilizers results in large part from the fact that field spraying can be used for specific, exactly meterable, inexpensive, clean
application with an injector. Even low nitrogen rates of 15 – 30 kg/ha can be exactly and uniformly metered out in liquid form.

Liquid-fertilizer plants are classified according to type of operation as hot mix or cold mix. Hot-mix plants use phosphoric acid and ammonia, whereby hot mix
refers to the heat of reaction. Cold-mix plants mix ammonium phosphate solution with other ingredients; no heat of reaction is evolved. Cold-mix plants are
popular in the United States, because they are simple and inexpensive. They are essentially a blending and mixing operation, the liquid counterpart of the
bulk-blend plants (see Section Bulk Blending).

Table 12 lists the consumption of nitrogen in liquid fertilizers and their share of total nitrogen consumption by countries. In Germany consumption of nitrogen in
liquids has risen since the season 1985/86, but total nitrogen consumption is decreasing [72]. The use of liquid ammonia plays no role in Germany and has
strongly declined in Denmark. In the United States more nitrogen is consumed in liquid than in solid form.

Table 12. Consumption of liquid fertilizers and their share of total nitrogen consumption

Country and fertilizer year * Liquid ammonia direct application Nitrogen solutions Total liquids Total N
103 t N % 103 t N % 103 t N % 103 t N

World
1985/86 5022.2 7.13 3811.1 5.41 8833.3 12.54 70 461.6
1993/94 5052.4 6.97 3801.9 5.24 8854.3 12.21 72 497.7
1994/95 4122.8 5.69 3794.3 5.24 7917.1 10.93 72 454.8
1995/96 4649.2 5.92 4013.6 5.11 8662.8 11.03 78 592.5
1996/97 ** 4688.1 5.67 4097.0 4.96 8785.1 10.63 82 645.6
United States
1985/86 3400.5 35.96 1887.6 19.96 5288.1 55.92 9457.0
1993/94 4116.3 35.89 2543.0 22.17 6659.3 58.06 11 469.4
1994/95 3308.7 31.12 2514.0 23.65 5822.7 54.77 10 632.1
1995/96 3693.6 33.09 2642.8 23.68 6336.4 56.77 11 161.5
1996/97 ** 3651.6 32.65 2651.3 23.71 6302.9 56.36 11 184.5
Germany
1985/86 15.0 0.66 65.0 2.84 80.0 3.50 2285.7
1993/94 0.0 0.00 205.0 12.72 205.0 12.72 1612.0
1994/95 0.0 0.00 226.0 12.65 226.0 12.65 1787.0
1995/96 0.0 0.00 282.0 15.93 282.0 15.93 1770.0
1996/97 ** 0.0 0.00 290.0 16.53 290.0 16.53 1754.0
France
1985/86 31.0 1.29 482.0 20.02 513.0 21.31 2408.0
1993/94 37.0 1.67 560.0 25.20 597.0 26.87 2222.0
1994/95 35.7 1.55 566.4 24.54 602.1 26.09 2308.3
1995/96 42.7 1.79 577.0 24.13 619.7 25.92 2391.7
1996/97 ** 44.8 1.78 643.2 25.48 688.0 27.26 2523.9
Denmark
1985/86 102.0 26.69 0.0 0.00 102.0 26.69 382.1
1993/94 0.0 0.00 4.0 1.23 4.0 1.23 325.0
1994/95 0.0 0.00 6.0 1.90 6.0 1.90 316.0
1995/96 18.0 6.19 7.0 2.41 25.0 8.60 291.0
1996/97 ** 17.0 5.94 7.0 2.45 24.0 8.39 286.0

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* The fertilizer year (season) runs from July 1 to 30 next year.

** Preliminary.

Liquid fertilizers can be easily mixed with a variety of micronutrients and agricultural pesticides. The dissolving of micronutrients in clear liquid fertilizers is
promoted by gelatinizing agents or by complexing with polyphosphates. The pulverized additions such as copper sulfate, sodium molybdate, sodium borate,
zinc oxide, or manganese oxide, which are mixed with suspensions [73], can be suspended in water by stirring.

Nonpressure liquid fertilizers are generally stored in concrete or mild steel tanks [308, p. 129]. A corrosion inhibitor is required in the case of nonpressure
urea – ammonium nitrate solution. Concrete tanks have the shape of vertical cylinders. The tanks should be lined with a film of a durable plastic such as poly
(vinyl chloride). Before lining, the concrete tank must be protectively coated [74]. For pressurized liquid fertilizers, double-walled vessels with leak warning
systems should be employed. When single-walled tanks are used, a retaining basin must be erected.

3.2.1. Nitrogen Liquids

Liquid Ammonia. Since 1950, liquid ammonia has found increasing use as a direct-application fertilizer, especially in the United States, since it can be
produced in large amounts at low cost. Because of its high vapor pressure (6 bar at 10 °C, 9 bar at 20 °C, and 12 bar at 30 °C), anhydrous ammonia must be
stored and transported in pressure vessels and applied with special equipment.

Ammonia is injected into the soil to a depth of roughly 15 cm with injection prongs. In general, the equipment suitable for this purpose deposits the fertilizer in a
pipe whose diameter depends on the soil type and soil moisture content. Figures 12 and 13 show the ammonia loss as a function of the soil type, the soil
water content, and the depth of application [75]. If the soil contains 15 % water, the NH3 loss is virtually independent of depth and, at about the 1 % level, can
be neglected. Despite some advantages, the application of liquid ammonia is too expensive for most farmers in the EC. A publication for farmers on the safe
use of liquid ammonia is available [76]. For storage and transportation, see Ammonia and [308, p. 73]

Figure 12. Ammonia losses as a function of application depth for three types of air-dry soils

Figure 13. Ammonia loss as a function of soil water content for three depths of application

Pressurized Nitrogen Liquids. Together with ammonia, ammonium nitrate and/or urea can be converted into pressurized aqueous nitrogen fertilizers. The
following categories are distinguished: low-pressure solutions (up to 1.3 bar) for direct application in agriculture, medium-pressure solutions (up to 7 bar),
mostly used for ammoniating superphosphates or phosphoric acid, and high-pressure solutions (over 7 bar), used only for ammoniation. Table 13 lists some
nitrogen solutions with their saturation temperatures and vapor pressures at 40 °C (313 K) [77].

Table 13. Nomenclature and physical properties of some nitrogen solutions

% N × 10 Composition * Vapor pressure at 40 °C, Saturation temperature,

bar ** °C

410 22–65–0 0.7 – 6

410 26–56–0 1.2 –32
444 25–55–10 1.5 –29
453 31–0-43 3.4 + 8
454 37–0-33 4.0 – 9
490 33–45–13 3.6 –27
490 34–60–0 3.4 –47
530 49–36–0 7.3 –73
580 50–50–0 10.1 –34

* HN –NH NO –(NH ) CO, wt %.

3 4 3 2 2
** Multiply by 0.1 to convert to MPa.

Nonpressure Nitrogen Liquids. Nitrogen solutions that contain little or no ammonia have no significant vapor pressure at ambient temperatures. The most
common nonpressure liquid nitrogen fertilizers comprise mixtures of ammonium nitrate, urea, and water (UAN), which are the most popular nitrogen fertilizers
in the United States. A commercial solution might have the following composition:

Ammonium nitrate 39.5 % = 14 % N

Urea 30.5 % = 14 % N
Water 30.0 %
UAN 100.0 % = 28 % N

The density at 15 °C is ca. 1.28 g/cm3, corresponding to 36 kg of nitrogen in 100 L of the product.

Figure 14 gives solubility isotherms and phase boundaries for the ammonium nitrate – urea – water system. In order to optimize the amount of UAN as a
function of temperature during transportation and in the field, the UAN composition is adjusted to suit the conditions [77], [79]. This is especially important for
winter application. Among almost-nonpressure nitrogen solutions, mixtures containing added NH3 (see Table 14) should also be mentioned [80].

Table 14. Composition, nitrogen concentration (N), and crystallization temperature (Tc) of nitrogen solutions [80]

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Composition, wt % N, Tc , Pressure at 10 °C,

NH3 NH4NO3 Urea H2O wt % °C bar *

24 56 10 10 44 –26 0.3
20 45 15 20 39.2 –32 0.2
19 58 11 12 41 –14 0.2

* Multiply by 0.1 to convert to MPa.

Figure 14. The ammonium nitrate – urea – water system [77], [78]

Solid lines are solubility isotherms; dotted lines show phase boundaries; dashed lines show constant nitrogen content.

A urea – ammonium nitrate solution can be produced by dissolving solid urea in an ammonium nitrate solution. If the raw materials are solid urea and
ammonium nitrate, UAN can be produced in a slightly modified dissolver. Figure 15 gives a simplified diagram of such a production unit.

Figure 15. Production of urea – ammonium nitrate solution [112]

a) Ratio controller; b) Mixer; c) Cooler; d) Storage tank

The desired ammonium nitrate : urea ratio is obtained by mixing a 75 – 80 % urea solution at 120 °C with an 80 – 85 % ammonium nitrate solution at 40 °C,
the quantities being controlled. After the addition of water, the liquid fertilizer is transferred to a storage tank after passing via a cooler. The mixer and cooler
are made of stainless steel, and the equipment downstream of the cooler are made of carbon steel [94]

Since urea – ammonium nitrate solutions attack ordinary steels, steel storage tanks and tank cars should be coated with Derakane-470, a poly(vinyl ester)
[82], or lined with polypropylene or polyethylene [83]. This practice also prevents stress-corrosion cracking of the steels, especially in the presence of (NH4 )
2CO3 [84]. Poly(vinylidene fluoride) provides excellent corrosion protection up to 120 – 130 °C [83]. The most common inhibitor for these solutions is
anhydrous ammonia, which is used to adjust the pH to 7. Ammonium thiocyanate and ammonium phosphate are also effective [308, p. 129]

In the production and use of UAN, such solutions can explode if they are evaporated to <5 % water and simultaneously heated, especially when the two
components have become segregated [85].

3.2.2. Multinutrient Liquids

Liquid mixed fertilizers consist of aqueous solutions and dispersions of the nutrients nitrogen, phosphate, and potash. These liquid mixed fertilizers are
produced mainly from phosphoric acid, anhydrous ammonia or aqueous ammonia, ammonium nitrate, urea, and potassium salts, chiefly KCl but also K2SO4
(hot mix). In most cases, fine-grained potassium chloride, with a somewhat higher potash content (62 % K2O) than the normal fertilizer salt, is employed
because it dissolves better. If only solid raw materials are used, the N-P-K grade of the liquid mixed fertilizer can be varied only over a narrow range. The
following solid nitrogenous components are mainly employed: ammonium nitrate, urea, monoammonium phosphate, and diammonium phosphate (cold mix).

For intensive field and greenhouse cultivation of vegetables, etc., the nutrients can be introduced into the watering system in the form of a low-percentage
nutrient solution. Because this solution is often delivered directly to the roots through hoses, it should have the lowest possible level of impurities.

3.2.2.1. NP Liquids
In the early 1950s the commercial production of mixed liquid fertilizers was started in the United States. Pure electric-furnace orthophosphoric acid was used
as the phosphate source. The acid was ammoniated to give an 8–24–0 grade liquid which does not salt out at – 8 °C. At mixing plants, this base solution was
mixed with urea – ammonium nitrate solution to give a liquid containing ca. 28 – 32 % nitrogen. An additional potassium content was obtained by dissolving
potassium chloride in the liquid. Maximum-mix grades attainable in this way included 13–13–0 and 7–7-7. A problem was the low concentrations of the 8–24–0
base solution and the final liquid mixes. Moreover, use of the cheaper wet-process orthophosphoric acid was not possible, because on ammoniation of such
acids, iron, aluminum, magnesium and other impurities form voluminous, gelatinous, and crystalline precipitates that are difficult to handle.

In 1957 TVA introduced superphosphoric acid and base solutions made by ammoniation thereof [86]. The superphosphoric acid, initially produced by the
electric-furnace process, contained ca. 76 % P2O5 as compared to 54 % P2O5 in commercial wet-process acid. At this higher P2O5 concentration, ca. 50 % of
the P2O5 is in the form of pyrophosphoric, tripolyphosphoric, and tetrapolyphosphoric acids [88]. Because of higher solubility of the ammonium salts of these
polyphosphoric acids, ammoniation of superphosphoric acid allowed production of higher grade base solution (10–34–0 instead of 8–24–0) and higher grade
mixed fertilizer solutions. A further advantage was that the polyphosphates are effective sequestering agents that prevent precipitation of many metal ions. The
kinetics of formation of ammonium polyphosphates are reported in [87].

Although the introduction of superphosphoric acid was an effective solution to the problem of low-grade liquids, there were still the high costs of the electric-
furnace acid process. Studies were undertaken to produce usable superphosphoric acid by concentration of the cheaper (54 % P2O5) wet-process phosphoric
acid to about 72 % P2O5 and a polyphosphate content of 45 – 50 %. Problems of the wet-process superphosphoric acid of this concentration were its high
viscosity and the poor storage properties of the 10–34–0 base solution derived from it. Although the polyphosphate content of the liquid initially keeps
impurities in solution in complexed form, precipitates may still form during storage if the acid used in ammoniation had too high an impurity level and the
polyphosphate concentration is too low. A frequent problem with NP liquids is the precipitation of insoluble magnesium compounds. If 0.4 wt % magnesium
(calculated as oxide) is present, the storage time before appearance of cloudy precipitates is only about one month. For magnesium oxide concentrations of
0.2 % and 0.1 %, the storage life is about 1 – 2 years [89].

The usual raw material for phosphoric acid productions, apatite, with its impurities and its variable composition, is not a simple raw material. In the production
of phosphoric acid, however, most of the impurities (e.g., aluminum, iron, and magnesium compounds) remain behind in the acid slurry.

The removal of the impurities from the wet-process phosphoric acid (Fe, Al, Mg, Ca, SO3, F) is necessary for storage and application of the liquid fertilizer.
Two typical processes reduce the concentrations of the most troublesome impurities significantly (Table 15) [95]. Process B, which is used in Europe, reduces
the impurity concentrations to lower levels than the U.S. Process A, while not reducing P2O5 concentration as much; however, Process B is more expensive.

Table 15. Purification of wet-process phosphoric acid

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Raw Purified acid

acid Process A Process B

P2O2 52.5 40.4 48.9

Fe 0.6 0.2 0.07
Al 0.9 0.3 0.01
Mg 0.3 0.03 0.001
Fe 0.8 0.3 0.06

The cleaning of the wet-process phosphoric acid by means of continuous extraction with ammonia and acetone has been described for the “green acid” from
North Carolina phosphate rock and the “black acid” from Florida phosphate rock [90]. An extraction process is described in [91]. For the use of chelating
agents, see [92, p. 58].

Addition of ammonium fluoride to aqueous aluminum phosphate-containing slurries precipitates aluminum as (NH4)3 AlF6 and forms ammonium and
diammonium phosphate:

resulting in a filtrate that can be subsequently worked up to give a liquid fertilizer.

Figure 16 shows how the polyphosphate content and the N : P2O5 ratio affect the solubility of ammonium phosphates at 0 °C. The bottom curve represents the
solubility of the orthophosphates. The middle and top curves demonstrate the increase in solubility as the polyphosphate content increases [93].

Figure 16. Effect of polyphosphate content and N : P2 O5 ratio on solubility of ammoniated phosphoric acids at 0 °C

Polyphosphate contents as percent of total P2O5: a) 0; b) 45; c) 70

Crystallizing phases: 1) (NH4)H2PO4; 2) (NH4)2HPO4; 3) (NH4)3HP2O7 · H2O; 4) (NH4)5P3O10 · 2 H2O; 5) (NH4)2HPO4 · 2 H2O; 6) (NH4)4P2O7 · H2O

Table 16 characterizes NP base solutions made from superphosphoric acid. The two solutions are 10 – 34 from wet-process superacid and 11 – 37 from
furnace-grade superacid. The 10 – 34 NP solution is used predominantly [77].

Table 16. Composition of NP base solutions [77]

Grade Phosphoric Percentage composition *

acid, wt % Ortho- Pyro- Tripoly- Tetrapoly- Higher

P2O5 phosphate phosphate phosphate phosphate phosphates

10–34–0 76 49 42 8 1 0
11–37–0 79 – 80 29 42 21 5 3
80 – 81 20 37 23 10 10

* Distribution of P O sources: of the total P O present (34 or 37 wt %), the percentages given in the table are present in the form of orthophosphate,
2 5 2 5
polyphosphate, etc.

A large number of experimental data points were subjected to regression analysis. With the resulting equation, the total nutrient concentration in NP solutions
made from ammonium phosphates and urea at 0 – 50 °C can be calculated with a relative error of 1 % or else determined with a nomograph [80].

Figure 17 shows schematically a plant for producing NP base solutions (tank reactor process).

Figure 17. Plant for producing NP solution from superphosphoric acid [77]

a) Reactor; b, c, and d) Coolers; e) Storage tank

Superphosphoric acid, usually containing 40 to 50 % of the P2O5 as polyphosphates, ammonia, and water are continuously fed to a stirred-tank reactor. A heat
exchanger operating in closed cycle holds the temperature in the reactor at roughly 70 °C. The solution concentration is controlled through density
measurement, and the N : P2O5 ratio is controlled by means of the pH. The NP solution outlet from the reactor is cooled to 35 °C in another heat exchanger (c)
before being transferred to a storage tank. To minimize hydrolysis of polyphosphate to orthophosphate, the product is further cooled to ca. 20 °C and the
storage tank is protected from sunlight. The polyphosphate content of the product is always slightly lower than that of the feed acid. For example, a base
solution containing about 50 % polyphosphate, which is about the minimum polyphosphate content of the product with acceptable storage properties, requires
a feed acid containing 55 % polyphosphate.

Because of the expensive heat-exchange problems — heat must be supplied in the production of superphosphoric acid and removed in the subsequent
ammoniation step — other techniques have been developed for producing ammonium polyphosphate solution from orthophosphoric acid in a direct process,
thereby largely eliminating the expensive heat exchange. Two examples are the Swift process and the Tennessee Valley Authority (TVA) process.

In the Swift process (Swift Agricultural Chemical Corporation), ammonia gas reacts in a jet reactor (Fig. 18) with preheated wet-process phosphoric acid to
produce ammonium polyphosphate. The phosphate melt inlet to the mixing tank is converted to liquid fertilizer by the addition of water; the grade produced is
usually 10–34–0. The extent of polymerization depends on the temperature that prevails in the process reactor. At 300 °C, it is about 60 %. In addition to clear
10–34–0 liquid fertilizer, a 12–40–0 suspension can also be obtained with this process [94].

The TVA process uses a T reactor (Fig. 19) to produce ammonium polyphosphate. Wet-process phosphoric acid (52 – 54 wt % P2O5 ) is preheated and then

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partly neutralized by ammonia in a simple spray washer (spray tower). The solution is then fed into the T reactor, which is also supplied with heated anhydrous
ammonia from the other side. At the adjusted temperature of 232 – 243 °C, the reaction with ammonia goes to completion while the residual water is
simultaneously vaporized and a foamy polyphosphate melt is formed [95]. After the product passes through a rotary separator (disengager), excess ammonia
and steam are removed; the ammonia is scrubbed out, and the steam is discharged. From the melt, with a polyphosphate content of roughly 50 %, either clear
liquid fertilizers such as 10–34–0 or suspensions such as 10–37–0 can be produced [95], [96].

The T reactor process has enabled reasonable equipment costs, process simplicity, and efficiency in the production of high-quality liquid fertilizers. The unique
feature of the process is the conversion of a low-polyphosphate (20 – 35 %) superphosphoric acid to an high-polyphosphate (ca. 80 %) 10–34–0 or 11–37–0
base solution. The high polyphosphate content substantially improves the stability, storage life, and handling properties of the base solutions and NPK liquids.
In contrast to the tank-reactor process the reaction is accomplished in a limited volume of the pipe reactor with minimal heat losses [97].

Figure 18. Swift process for producing NP (or NPK) solution from orthophosphoric acid [94]

a) Acid heater; b) Ammonia vaporizer; c) Cooling tower; d) Cooler; e) Pipe reactor; f) Mixing tank

Figure 19. TVA process for producing NP solution from orthophosphoric acid [94]

a) Acid heater; b) Spray tower; c) T reactor; d) Rotating disengager; e) Ammonia preheater

In the Ugine Kuhlmann process [98], clear NP liquid fertilizers with good storage properties are produced from unpurified wet-process phosphoric acid [90].

The crude acid is first treated with urea to yield urea phosphate, which is crystallized and separated. The mineral impurities remaining in the mother liquor can
be used in the production of solid fertilizers. Thus there is no waste disposal problem. In the second reaction step, the urea phosphate is reacted with
ammonia, yielding a urea – ammonium polyphosphate melt, which is dissolved in water to obtain a 16–30–0 liquid fertilizer.

3.2.2.2. NPK liquids

Liquid NPK fertilizers are produced by adding a potassium component, usually potassium chloride, to UAN and NP solutions. The amount of water needed to
dissolve 100 g of a mixture of UAN, NP solution, and potassium chloride at a specific temperature, as well as the solid phase, can be shown conveniently in
the form of three-component phase diagrams [80]. Other triangular diagrams show the solubility relationships in mixed liquid fertilizer systems [97]. While the
clear NP solutions with polyphosphate have compositions corresponding to those of solid fertilizers, the contents must be kept lower in clear ternary NPK
solutions because potassium nitrate, which is formed from ammonium nitrate and potassium chloride, has a low solubility.

Table 17 presents several three-component liquid fertilizers obtained by mixing a 10–34–0 base solution with potassium chloride powder. The added
component lowers the nutrient content from almost 39 % to ca. 29 – 30 % [99].

Table 17. Three-component liquid fertilizers produced by mixing 10–34–0 base solution with KCl [99]

Fertilizer type Salt composition, wt % Total Freezing

nutrient point,
Ammonium Ammonium Urea NH4NO3 KCl H2O analysis, °C
orthophosphate polyphosphate wt % *

1:1:1 7.93 10.11 7.8 16.3 15.6 42.2 28.85 –21

1:2:2 9.20 12.4 5.0 10.4 18.7 44.4 29.54 –18.5
1 : 1.5 : 1 10.70 13.65 7.3 15.3 14.1 38.4 30.57 –23.5
2:1:1 5.75 7.33 11.9 24.8 10.7 39.5 27.89 –24.5
1:1:0 16.10 20.5 15.9 33.2 0 14.3 38.60 –33

* N + P O + K O.
2 5 2

Production takes place in either cold-mix or hot-mix plants [100], [312, p. 456]. Because cold-mix plants offer low investment costs and are easy to operate,
they are in more widespread use. In a stirred vessel, the appropriate quantities of potassium chloride are added to the base solutions (e.g., 28–0-0 and 10–
34–0) and mixed. Hot-mix plants, especially small-capacity ones, require relatively large investments and, because of their troublesome operation, must have
well-trained personnel.

3.2.2.3. UAS Liquids

The use of high-analysis fertilizers containing little or no sulfur has led to soil sulfur deficiencies in areas far from industries. The critical level for sulfur in soil is
0.1 – 0.3 wt %. Sulfur deficiencies in the soil of Kuwait led to the development of a sulfur-containing liquid fertilizer: 21.2 wt % (NH4 )2SO4 + 37.6 wt %
urea + 41.2 wt % water [101]. The total nitrogen content is 22 wt %, and the saturation temperature is 4 °C.

The reaction of urea with sulfuric acid

yields liquid fertilizers with pH = 1. Because of corrosion, the plant must have polyethylene linings or else use expensive chrome – nickel – molybdenum steel.
The following are typical UAS solutions [102]:

Sulfuric acid, wt % N, wt % S, wt %

28 9 27
17 16 49
15 17 52
10 18 55

Liquid fertilizers can be applied even in winter if ammonium thiosulfate is added in order to lower the salting-out temperature to – 18 °C. From the standpoint of
nutrient content, this compound is better than water. Ammonium thiosulfate itself is a clear liquid fertilizer (12–0-0 + 26S) with a salting-out temperature of – 5 °

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C [102].

3.2.3. Suspensions
Suspension fertilizers contain solid nutrient salts, especially potassium chloride, suspended in a concentrated ammonium phosphate solution. Their
development has made it possible to attain nutrient contents corresponding to those of solid NPK fertilizers:

Solutions Suspensions

8–8-8 15–15–15
3–9-9 7–21–21
2–16–12 5–15–30
10–5-5 20–10–10

What is more, suspension fertilizers have the advantage that low-priced phosphates that are difficult to dissolve in water can also be employed.

The storage and application of suspension fertilizers, however, is more difficult than that of clear liquid fertilizers, since the former tend to undergo
sedimentation. If an easily handled suspension is desired, the product must be stirred vigorously before use. Swellable clays such as palygorskite (attapulgite),
a magnesium silicate-containing clay ( Clays), have proved suitable as suspending agents. Suspensions thus make special demands on technique. The
methods of storage, transportation, and spraying cannot be transferred directly from clear liquid fertilizer solutions. As a rule, substantial changes in equipment
are needed, and these require additional investments. The quality of spray distribution does not match that for clear fertilizer solutions either. For all these
reasons, suspensions have scarcely become established in Europe, despite efforts to introduce them. In the United States, on the other hand, a larger scale of
farming, together with a well-developed distribution service sector, has allowed the successful introduction of suspensions.

A suspension fertilizer can be produced from solid monoammonium phosphate by intensive stirring in water and simultaneous adding of ammonia. The
addition of swellable clay (1 – 2 %) ensures a fairly stable suspension. By dilution, a product of grade 9–27–0 is obtained. Applied in a comparable way, it
behaves much like the commercial 10–30–0 liquid fertilizer [103].

Anhydrous ammonia is used to improve the solubility and mixing of monoammonium phosphate. Ammonium orthophosphate displays the highest solubility at
a molar ratio NH3 : H3PO4 of 1.5. A turbine mixer is suitable for homogenizing the suspension obtained by the addition of KCl and 1 or 2 wt % palygorskite
[104].

A stable suspension is obtained by ammoniating wet-process orthophosphoric acid (54 wt % P2O5 ) at 71 °C and a pH between 7.5 and 8.5. The product is
then adjusted to the desired pH with a small amount of acid. Because of the fineness of the solid particles, the suspension (8–24–0) remains stable. After
cooling, it can be blended with urea – ammonium nitrate solutions (32 % N) and potassium chloride to produce various compositions of liquid fertilizers [105].

A two-step process developed by TVA yields low-priced, high-analysis suspension fertilizers in which the phosphate component is obtained by ammoniating
orthophosphoric acid (Fig. 20). In the first reaction step, the acid is partly ammoniated with ammonia, and the solution is held for about 30 min at 106 °C. In the
second step, ammoniation is completed. Then the product is cooled to 60 °C, and the suspension of fine diammonium phosphate crystals is stabilized with
1.5 wt % clay. A fluid NPK fertilizer of 15–15–15 grade can be produced from the 12–40–0 suspension [106]. Raising the acid concentration from 54 wt % to
70 – 73 wt % P2O5 (wet-process superphosphoric acid) gives useful suspension fertilizers. In general, however, the Mg content is so high that prolonged
storage is excluded because of the precipitation of struvite, MgNH4PO4 · 6 H2O.

Figure 20. Production of orthophosphate suspensions

a) First reaction stage; b) Second reaction stage; c) Cooler; d) Slurry vessel for suspending agent; e) Product tank

This difficulty is avoided if triple superphosphate is employed as the sole phosphate source. Palygorskite is slurried with water in a mixing vessel, aqueous
ammonia and urea – ammonium nitrate solution are added, and then finely-ground triple superphosphate and potassium chloride are incorporated. The
suspensions made by this process have a typical grade of 12–12–12 [107]. The addition of palygorskite can be omitted if part of the triple superphosphate is
first treated with aqueous ammonia to yield a voluminous precipitate, which then acts as a suspending agent for the other solid particles [108].

Suspensions from the Nitrophosphate Process. A low-cost process for producing a suspension fertilizer involves digesting crude phosphate with nitric acid.
The slurry of phosphoric acid and calcium nitrate is inlet to a hot-mix plant and ammoniated to form an NP suspension fertilizer. Such processes have been
developed in the United States, the USSR, and the Federal Republic of Germany [81], [109], [110]. Aside from the cheap raw material, the fixed costs of the
fertilizer are relatively high. Since nitrophosphate processes yield suspension fertilizers with large amounts of calcium, the dilution effect of the calcium holds
the nutrient content relatively low (e.g., 9–9-9 or 6–12–12).

High-Nitrogen Suspension Fertilizer. TVA has devised a promising method for producing a high-nitrogen suspension fertilizer (36 wt % N) [102]. This
product is a mixture of microspray-crystallized urea and ammonium nitrate solution (76 wt % AN) with palygorskite. The composition is 57.5 wt %
urea + 31.5 wt % ammonium nitrate + 10.0 wt % water + 1 wt % palygorskite [105], [108], [111].

Sulfur-Containing Suspensions. In regions where the effects of sulfur deficiency in the soil are pronounced in certain regions, sulfur in fertilizers not only
increases yield but also can improve product quality. TVA has manufactured a 29–0–0–5S urea ammonium sulfate (UAS) suspension fertilizer in a pilot plant.
The feedstocks are urea (70 % aqueous solution), sulfuric acid (93 %), anhydrous ammonia, and water. Clay (ca. 2 %) is added to the UAS solution to give the
final product [102].

[Top of Page]

4. Special Fertilizers
Manfred Drach, Ralf Vosskamp, Martin E. Trenkel, Reinhold Gutser, Günter Steffens

The special fertilizers include water-soluble nutrient salts, foliar fertilizers, micronutrient fertilizers, slow- and controlled-release fertilizers, nitrification inhibitors,
and organic fertilizers, including sewage sludge, compost and manure.

4.1. Water-Soluble Nutrient Salts

Especially for fertilization in commercial horticulture, but also for specialty field crops, water-soluble nutrient salts (e.g., ammonium nitrate, potassium nitrate,
ammonium phosphate, magnesium sulfate) are preferably used with water-saving irrigation systems (drip irrigation/fertigation) and with soilless cultivation
systems. Various crop-specific fertilizer recipes can be formulated with these salts. A convenient form for the consumer are multinutrient fertilizers made by
mixing various water-soluble salts, which generally also include micronutrients. Such salt mixtures are available worldwide from most major fertilizer
manufacturers.

From these salts and salt mixtures, the grower prepares highly concentrated master solutions, which for application are further diluted to render them plant-
compatible and then fed into the irrigation system. By using appropriate automatic fertilizer systems it can be assured that irrigation intervals and concentration
of the nutrient solution are adjusted to the crop's needs.

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A distiction is made between urea-containing and urea-free nutrient salt mixtures. Since the application rate of nutrient salts is frequently monitored by means
of conductivity, products containing urea cause problems as urea has no ionic conductivity and is therefore not detected. Therefore, products containing urea
are mainly used for foliar fertilization (see Section Foliar Fertilizers) where these calibration problems do not exist and because urea nitrogen is the N form with
the best uptake rate via the leaves.

A prerequisite for all nutrient salts is rapid dissolution in water without any residues. This is achieved by producing the salt mixtures from appropriate
ingredients and by properly grinding them. Moreover, for special fields of application in horticulture (flood irrigation and soilless cultivation systems) they are
rated by their nitrogen forms. For these fields of application, nitrate-based nutrient salts are preferred.

In principle, if appropriately diluted, all nutrient salts are suitable both for soil fertilization and for foliar fertilization.

4.2. Foliar Fertilizers

For over 100 years it has been known that nutrients can be taken up through the leaves. However, with some exceptions, plants cannot be provided with
nutrients through the leaves alone, since even leafy plants such as potatoes cannot absorb sufficient nutrients through the leaves. Foliar fertilization, therefore,
is usually a supplement to soil fertilization. However, it is often the case that proper foliar fertilization puts the plants in the position to utilize soil-derived
nutrients better. Recent decades have seen foliar fertilizers come into use not only for special crops or in certain localities, but throughout agriculture.

Foliar fertilizers are substances that contain primary nutrients and/or micronutrients, are applied to the leaves, and are absorbed into the leaves. The most
important foliar fertilizer is urea (46 % N) which is highly soluble in water and rapidly absorbed by plants via the leaves. Therefore, urea is frequently used as a
component of fertilizer suspensions and solutions. In addition to nitrogen, other macro- and micronutrients can be added, frequently in a nutrient ratio tailored
to the demand of specific target crops. Special raw materials and formulations ensure a good plant compatibility and optimum foliar nutrient uptake. Also used
for foliar fertilization are solutions with organic ingredients (e.g., amino acids), readily soluble salts (e.g., potassium nitrate or micronutrients, mostly based on
sulfate) and salt mixtures containing macronutrients and special micronutrient mixtures.

4.2.1. Production
Solid foliar fertilizers are produced by mixing salts that are readily soluble in water. Before application, the salts are dissolved for spraying. Liquid foliar
fertilizers, which are made from readily soluble salts or solutions and adjusted to a given analysis, are also on the market. The production of suspensions for
foliar application involves the use of dispersing agents, and in some cases ionic surfactants, to stabilize the spray.

4.2.2. Application
In order to achieve optimal utilization of nutrient uptake through the leaves, the nutrient salts must remain as long as possible in the dissolved liquid state on
the leaf surface. For this reason, spraying in overcast weather or toward evening (“evening dew”) gives better results than spraying on dry days in bright
sunlight. Depending on the sensitivity of the leaves and the concentration of the spray liquid, application in hot, sunny weather may cause burning. Table 18
gives the time required for 50 % absorption of nutrients applied to the leaves of bean plants [113].

Table 18. Nutrient absorption rates [113]

Nutrient Time for 50 % uptake

Nitrogen 1–6h
Phosphate 2.5 – 6 days
Potash 1 – 4 days
Calcium 1 – 4 days
Sulfur 5 – 10 days
Magnesium 1 h (20 % uptake)
Iron 24 h (8 % uptake)
Manganese 1 – 2 days
Zinc 1 day
Molybdenum 10 – 20 days

Nutrients placed on the leaf surface follow three paths to the leaf cells [114-116]. After the cuticle has been wet by the nutrient spray, the cutin swells, which
increases the distances between the wax plates in the cuticle. As a result, the nutrients are able to diffuse through the cuticle and into the cell wall (Fig. 21).
The nutrients can then diffuse into the space around the epidermal cell and to the cell membranes, where they can be absorbed, or they can diffuse further
along the cell wall of the epidermal cell and adjoining cells, deeper into the leaf, where they can be absorbed by a parenchymal cell. Nutrients that have been
absorbed by an epidermal cell can be transferred to other cells by cytoplasmic strands connecting the cells, the plasmodesmata, a second path. If surfactants
are included in the nutrient spray, a third path becomes available: the nutrients can pass through the stomata into the air spaces of the leaf.

Figure 21. Access and transport paths for nutrients in leaves

Reasons for Using Foliar Fertilizers. Foliar fertilizers are applied to remedy obvious nutrient deficiencies. If a deficiency is recognized, the missing nutrient is
supplied by spraying. If the deficiency is not well defined, complete foliar fertilizers or a mixed micronutrient fertilizer can be employed.

Another reason for foliar application is to remedy hidden (latent) nutrient deficiencies, which can seriously impair crop yield and quality.

Foliar fertilizers are also used to protect yield and quality, to meet peak nutrient demands (i.e., remedy latent deficiencies and stimulate the plants to absorb
more nutrients from the soil), and to improve quality. The last point is especially important for special crops (wine, fruits, vegetables).

Advantages and Drawbacks of Foliar Fertilizers. Foliar application has a number of advantages over soil application: Nutrients act rapidly, nutrient
utilization is high, nutrients are placed where they are needed, the risk of leaching losses and groundwater contamination is reduced. micronutrients are
supplied to meet much of the demand for them, micronutrients are not fixed in the soil, application does not entail extra costs if fertilizers are combined with
agricultural pesticides, and some nutritional problems can be cleared up only through application to the leaves or fruit (bitter pit in apples, stem necrosis in
grapes).

The main disadvantages of foliar fertilization are that the action time is often short, the quantity of primary nutrients delivered is relatively small, and there are
questions of compatibility in relation to concentration and prevailing weather conditions.

4.2.3. Combination with Agricultural Pesticides

Foliar fertilizers are usually applied along with agricultural pesticides for the following reasons [117]: to lower the cost of application, since pesticide spraying is
required anyway; to reduce the stress due to the application of pesticide (e.g., certain herbicides); to improve the quality of pesticide spray liquids (lower the
pH or increase the electrolyte content) and thus stabilize them; to reduce evaporation at low air humidity, so that most of the fine droplets reach the plant in
liquid form; and to lower the surface tension of the water.

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4.3. Micronutrients
The most important micronutrients (trace elements) are iron, manganese, boron, zinc, copper, and molybdenum. The delivery of micronutrients to plants is just
as indispensable today as that of macronutrients or primary nutrients. Diseases resulting from an undersupply of micronutrients are seen more and more often
as agriculture and gardening become more intensive, with a corresponding increase in plant nutrition [118]. For this reason, better and more specific
micronutrient fertilizers have now been developed.

The term micronutrient also signifies that these substances are needed only in small quantities, often just 1 – 100 g per hectare and year. These small
amounts are, however, absolutely necessary. But if the optimal dose is much exceeded, serious crop damage and loss of yield may occur. For boron, in
particular, the difference between an adequate and an excessive amount is slight.

To work in the proper way, the micronutrients must be absorbed by the plants. Uptake is mainly in the form of ions: cations or metal – chelate ions of iron,
manganese, copper, and zinc and anions in the case of boron and molybdenum (borates, molybdates). Absorption is through the leaves (foliar fertilizer) or the
roots (soil solution).

4.3.1. Micronutrient Forms

Micronutrients are used in the following inorganic forms:

1. Various metal salts (sulfates, chlorides, nitrates)

2. Milled oxides
3. Metal flours and metal slags

Table 19 lists only those micronutrient compounds that are in common use. The table also states the nutrient analyses, the solubilities in water, and the
various types of fertilizers in which the compounds appear.

Table 19. Micronutrient fertilizers

Substances and products Formula Analysis, Solubility, Uses

wt % g/100 g H2O

Salts (technical)
Iron(II) sulfate heptahydrate FeSO4 · 7H2O 19.5 62.3 liquid fertilizers,
Manganese(II) sulfate monohydrate MnSO4 · H2O 32 63.0 nutrient-salt
Copper(II) sulfate pentahydrate CuSO4 · 5H2O 25 36.0 mixtures, solid
Zinc(II) sulfate monohydrate ZnSO4 · H2O 35.5 63.7 straight and
Zinc(II) sulfate heptahydrate ZnSO4 · 7H2O 22 165.5 multinutrient
Boric acid H3BO3 17 fertilizers,
Colemanite (boron mineral) Ca2B6O11 · 5H2O 11 micronutrient and

Disodium octaborate tetrahydrate * Na2B8O13 · 4H2O 20.8 9.5 multimicronutrient

Hexammonium heptamolybdate fertilizers
tetrahydrate (NH4)6Mo7O24 · 4H2O 54
Oxides
Manganese dioxide (mineral) MnO2 45 solid straight and
Zinc oxide (residual zinc) ZnO 69 multinutirent
Molybdenum trioxide MoO3 60 fertilizers
Slags
Copper slag flour 2.5 Cu, 0.05 Co micronutrient
fertilizers
Metal flours
Manganese flour 20 Mn, 10 Fe,
0.5 Zn, 0.25 Cu micronutrient
Copper flour 2.6 – 25 Cu fertilizers

* Disodium octaborate is not a homogeneous substance. It has a Na O : B O ratio of 1 : 4 and can be produced as a concentrated solution. It is sold
2 2 3
by US Borax under the trade name Solubor.

In addition to these, the nitrates and chlorides of iron, manganese, copper, and zinc are also used, especially in concentrated liquid fertilizers. The trace-
element nitrates and chlorides have high solubilities (e.g., 268 g per 100 g H2O for Fe(NO3 )2 · 6 H2O or 400 g per 100 g H2O for FeCl3 · 6 H2O; some of the
nitrates and chlorides of manganese, copper, and zinc have still higher values). Because of the price and the handling qualities in the solid state, however, the
sulfates are preferred. Many crops are sensitive to trace-element chlorides in large amounts. At the levels usual in foliar application, however, this is certainly
not a major problem. Trace-element sulfates and nitrates provide two nutrient elements each.

Because soluble iron compounds are fixed as phosphates or oxides in calcareous soils, organic complexes were first developed for this element. One
successful complexing agent is ethylenediamine di(o-hydroxyphenylacetic acid) (EDDHA):

Other compounds of trace metals with N-carboxylalkylamino acids are less effective in the soil, especially with soil pH values > 7, but if applied on the leaves
are superior to the EDDHA compounds and to the simple salt solutions.

The N-carboxylalkylamino acids have also come into wide use today as chelating agents for manganese, copper, and zinc:

EDTA. ethylenediaminetetraacetic acid

HEDTA. hydroxyethylethylenediaminetriacetic acid
DTPA. diethylenetriaminepentaacetic acid
EDDHA. ethylenediamine di(o-hydroxyphenylacetic acid)
EDDHMA. ethylenediamine di(o-hydroxy-p-methylphenylacetic acid)

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For the formulas of the N-carboxylalkylamino acids, see Ethylenediaminetetraacetic Acid and Related Chelating Agents, and the stability constants, see
Ethylenediaminetetraacetic Acid and Related Chelating Agents

Other chelating agents such as lignosulfonates and citric acid have so far been used only to a lesser extent.

4.3.2. Production
The list of fertilizers containing micronutrients comprises straight micronutrient fertilizers, combination micronutrient fertilizers, and ordinary fertilizers with
micronutrients. All these types can be manufactured in either liquid or solid form. Among the solid micronutrient fertilizers, the powdered and fine-crystalline
ones predominate, since nearly all of them can be dissolved in water and applied through the leaves. They generally consist of the several substances in
Table 1 as well as the N-carboxyalkylamino acid chelates cited.

Solid micronutrient fertilizers for soil application include metal flours, metal slags, and micronutrient frits. Metal flours come from fabrication waste in the
manganese production and processing industry and from specially prepared alloys. The source material is ground and granulated to between 0.25 and
1.5 mm. Metal slags such as copper slag flour are also won from waste products. The metal slags are quenched in water and comminuted to fine, powdery
products.

Frits are made by melting glasses and incorporating the desired micronutrients (single-element and multi-element frits). The glasses are then finely milled
[119].

Solid straight micronutrient fertilizers and multi-micronutrient fertilizers with complexing can be produced in various ways. One technique is to grind a metal
sulfate with chelating agents, or several metal sulfates with chelating agents (in many cases borates, molybdates, and magnesium sulfate are added) and
blending [120]. Chelation takes place when the material is dissolved in water before use. A second approach is to stir and thereby dissolve chelating acids and
metal oxides (including magnesium oxide) in water at elevated temperatures; additives that cannot be chelated, such as borates and molybdates, are added;
the product is further stirred, filtered, and spray-dried [121] or crystallized.

Liquid micronutrient fertilizers and combination micronutrient fertilizers can be prepared by the same technique but without the spray-drying step.

In the production of fertilizers with micronutrients, the micronutrients are usually added before granulation; in the case of liquid fertilizers, micronutrient
compounds or chelates are dissolved along with the primary nutrient forms.

4.3.3. Commercial Fertilizers

Several firms in Western Europe manufacture pure micronutrients or combination micronutrient fertilizers, most of them in chelate form. Table 20 lists selected
firms and examples of their products.

Table 20. Commercial fertilizers

Company Products

ABM Chemical Nevanaid Fe, finely powdered solid product with 9 % Fe (HEDTA)
(United Nevanaid Fe, finely powdered solid product with 7 % Fe (DTPA)
Kingdom)
Nevanaid Mn, finely powdered solid product with 10 % Mn (EDTA)
Allied Colloids Librel Fe-Dp, finely powdered solid product with 7 % Fe (DTPA)
(United Librel Mn, finely powdered solid product with 13 % Mn (EDTA)
Kingdom)
BASF Fetrilon 13 %, spray-dried solid fertilizer with 13 % Fe (EDTA)
(Germany) Fetrilon-Combi, spray-dried solid multimicronutrient fertilizer with 9 % MgO,
4 % Fe, 4 % Mn, 1.5 % Cu, 1.5 % Zn, 0.5 % B, 0.1 % Mo (all heavy metals as EDTA, boron as borate, Mo
as molybdate)
Nutribor, crystalline powder with 8 % B, 1 % Mn, 0.1 % Zn, 0.04 % Mo, 6 % N, 5 % MgO, 12 % S (EDTA)
Solubor DF, microgranular with 17.5 % B
Ciba Geigy Sequestrene 138, solid fertilizer with 6 % Fe (EDDHA), soil application
(Switzerland) Ferrogan 330, solid fertilizer with 10 % Fe (DTPA)
Grace Rexoline Rexene 224 Fe, powdered or granular fertilizer with 6 – 7 % Fe (EDDHMA), soil application
(Sweden) Rexenol Cu, powdered solid fertilizer with 9 % Cu (HEDTA)
Rexene Zn, liquid fertilizer with 6.5 % Zn (EDTA)

Urania (Germany) uses metal slags as raw material to produce granular copper fertilizers containing 2.5 % and 5 % Cu, as well as a copper – kieserite
granular fertilizer with 2.5 % Cu and 21 % MgO. Similar micronutrient products and the same chelating agents are made in the United States and marketed as
commercial fertilizers [119, pp. B68 to B83].

There are also fertilizers with micronutrient supplements, namely: granulated straight and multinutrient fertilizers, water-soluble nutrient salts, suspensions and
solutions with micronutrients, which are chosen and added according to crop demand.

4.3.4. Use
In order to combat micronutrient deficiencies, either fertilization far exceeding actual depletion or directed foliar fertilization must be carried out [117, p. 128].
The annual depletion of micronutrients can be partly offset by the use of macronutrient fertilizers with micronutrients. On the basis of average micronutrient
contents and average crops (rotation 70 % cereals, 20 % root crops, 10 % fodder), the following are withdrawn from the topsoil per hectare and year in central
Europe [117, p. 122]: 400 – 700 g manganese, 260 – 400 g zinc, 150 – 200 g boron, 80 – 120 g copper. The amounts for grassland (per hectare and year) are
800 g manganese, 300 g zinc, 80 g copper, 50 g boron, and 0.5 g cobalt. In addition, leaching removes an average of 250 g manganese, 250 g boron, 100 g
zinc, and 30 g copper per hectare and year [117, p. 122].

Normally, fertilization must more than make up for this consumption. Per hectare, boron-deficient soils must receive 1 – 2 kg of boron, and manganese-
deficient soils must receive as much as 12 – 24 kg of manganese.

In order to prevent the development of latent deficiencies, micronutrients are often used in small quantities, especially for foliar application. This applies in
particular to intensive cereal farming, where — even on well-supplied soils — the freely available micronutrients are soon consumed or else the nutrient flux at
peak demand times cannot be covered from soil reserves. If relatively small amounts of a multi-micronutrient fertilizer are used in specific treatments during
tillering and in the shoot and ear phases, latent deficiencies are generally eliminated and the yield potential is fully utilized [122], [123].

4.4. Slow- and Controlled-Release Fertilizers

4.4.1. Introduction
In plant nutrition, soil and plants are two antagonistic systems that compete for the nutrients available in or applied to the soil. This competition is the main
reason why only a portion of nutrients is taken up and used by the plants and crops grown, while another portion is (temporarily) immobilized in the soil or lost
by denitrification/volatilization and leaching (particularly of nitrogen) [124, p. 124]. The fertilizer industry has developed special types of fertilizers and fertilizer

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modifications which avoid or at least reduce such losses, such as:

– Foliar fertilizers
– Slow and controlled-release fertilizers
– Nitrification and urease inhibitors; stabilized fertilizers

The utilization rate of nutrients is improved considerably by leaf application. However, in practice it is impossible to supply all the necessary nutrients via plant
leaves [124, pp. 125 – 127], [125, pp. 14 – 16]. A more practical route is the use of nitrogen fertilizers which release the nutrients according to the plants'
requirements, that is, slow- and controlled-release fertilizers.

Terminology. The Association of American Plant Food Control Officials (AAPFCO) gives the following definition: “Delay of initial availability or extended time
of continued availability may occur by a variety of mechanisms. These include controlled water solubility of the material (by semipermeable coatings,
occlusion, or by inherent water insolubility of polymers, natural nitrogenous organics, protein materials, or other chemical forms), by slow hydrolysis of water-
soluble low molecular weight compounds, or by other unknown means” [126].

There is no official differentiation between slow-release and controlled-release fertilizers. However, the microbially degradable N products, such as urea –
formaldehydes (UFs and other urea – aldehyde compositions), are commonly referred to in the trade as slow-release fertilizers, and coated or encapsulated
products as controlled-release fertilizers [127, p. 12].

Advantages and Disadvantages. Slow- and controlled-release fertilizers reduce toxicity, especially in use with seedlings. The toxicity of conventional soluble
fertilizers is caused by the high ionic concentrations resulting from quick dissolution. Consequently, these slow and controlled-release fertilizers permit the
application of substantially larger fertilizer dressings (depot fertilization). This results in significant savings in labor, time, and energy. They also allow the full
nutrient requirements of crops grown under plastic cover to be met (protected crop cultivation). These fertilizers significantly reduce possible losses of nutrients
due to the gradual nutrient release (particularly losses of nitrate nitrogen). They also reduce evaporative losses of ammonia. They further contribute to a
reduction in environmentally relevant gas emissions (N2O) [127, pp. 15 – 16].

There are no standardized methods for reliable determination of the nutrient release pattern available as yet due to the lack of correlation between laboratory
tests and field conditions. With urea – formaldehyde fertilizers, a proportion of the nitrogen content may be released extremely slowly or not at all. With sulfur-
coated controlled-release fertilizers the initial nutrient release may be too rapid and cause damage to turf or the crop. Repeated use of sulfur-coated urea may
also increase the acidity of the soil. Polymer-coated or encapsulated controlled-release fertilizers can cause an environmental problem since undesirable
residues of the coating material may accumulate in the fields. However, the main disadvantage is that the cost of manufacturing slow- and controlled-release
fertilizers is still considerably higher than that of conventional mineral fertilizers. At present their cost/benefit ratio prevents their wider use in general
agriculture. Consequently, the vast majority is applied in nonagricultural sectors such as nurseries and greenhouses, golf courses, professional lawn care, as
well as by consumers (home and garden) and landscape gardeners [127, pp. 17 – 18]. Total world consumption of slow- and controlled-release fertilizers is
estimated at 562 000 t (1995/96), amounting to only 0.15 % of world total consumption of N + P2O5 + K2O in the form of fertilizer material (ca. 380 × 106 t)
[128].

Types of Slow- and Controlled-Release Fertilizers. The two most important groups are:

1. Condensation products of urea such as urea – formaldehydes (slow-release)

2. Coated or encapsulated fertilizers (controlled-release)

Of lesser importance are other organic chemicals, ion-exchange materials, and supergranules.

4.4.2. Urea – Aldehyde Slow-Release Fertilizers

Three types of urea – aldehyde condensation products (see also Urea – Reaction of Urea and Its Derivatives with Aldehydes) have gained practical
importance:

1. Urea – formaldehyde (UF)

2. Urea – isobutyraldehyde (IBDU/Isodur)
3. Urea – acetaldehyde/crotonaldehyde (CDU/Crotodur)

At pH values below 2, crotonaldehyde and acetaldehyde can form cyclic condensation products [131]. For production of urea – aldehyde condensates, see
[129, pp. 3 – 87], [130, pp. 1 – 137], [132, pp. 153 – 156], [133], [134, pp. 247 – 279].

The urea – formaldehyde products have the largest share of the slow- and controlled-release fertilizer market (40 % of world consumption in 1995/96); IBDU-
and CDU-based products are less widely used (15 % in 1995/96), since their manufacturing costs are even higher than that of urea – formaldehydes [127,
pp. 61 – 63].

4.4.2.1. Urea – Formaldehyde Condensation Products.

Ureaform, as defined by the American Association of Plant Food Control Officials (AAPFCO) is the oldest type of urea – formaldehyde condensate. As early as
1924, Badische Anilin- & Soda-Fabrik (now BASF) registered the first patent (DRP 431 585) on urea – formaldehyde condensation fertilizers [135]. In the
United States they were patented for use as fertilizers in 1947; commercial production began in 1955.

Ureaforms are a mixture of methylene – urea oligomers of various molecular masses, polymer chain lengths, and hence varying water solubilities, such as
methylene diurea (MDU), and dimethylene triurea (DMTU). They also contain a certain amount of unchanged urea.

Manufacture. The manufacture of urea – formaldehyde products is a two step process [136, p.13], [137], [138], [139], [140], [141], [142], [143]:

First, urea and formaldehyde are combined to give the intermediates monomethylol- [1000-82-4] and dimethylolurea [140-95-4]. Under acidic conditions these
methylolureas react with further urea to give various oligomers of methylene urea:

In the production of granular urea – formaldehyde products, water must be removed by evaporation. The main problem in the manufacture of urea –
formaldehyde slow-release fertilizers is the production of condensation oligomers in the desired proportions. A number of processes can be used to meet this
target (e.g., dilute- and concentrated-solution processes). The procedure commonly applied is to use suspensions of methylene urea or solutions of urea and
methylol urea as well as solid product. In this way the condensation reactions take place in the granulator itself (in situ process) [144].

Properties. The urea – formaldehyde products are separated into the following three fractions:

1. Fraction I: cold water (25 °C) soluble (CWS), containing residual urea, methylene diurea (MDU), dimethylene triureas (DMTU), and other soluble
reaction products. Depending on soil temperature the availability of Fraction I nitrogen is slow.
2. Fraction II: hot water (100 °C) soluble (HWS), containing methylene ureas of intermediate chain length: slow-acting nitrogen.
3. Fraction III: hot water insoluble (HWI) containing methylene ureas of very long chain length, insoluble in both cold and hot water; extremely slow-acting
or ineffective in plant nutrition.

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How the proportion of the different methylene ureas affects the release of nitrogen and the nitrogen efficiency are expressed by the activity index (AI). The AI is
calculated from the solubility fractions of the fertilizer under various conditions [127, p. 22]. In the past urea – formaldehydes had an AI of about 40 – 50; more
recent formulations have AI values of 55 – 65.

In general, the nitrogen content of urea – formaldehyde condensation products ranges from 35 to 42 % N. The American Association of Plant Food Control
Officials (AAPFCO) specifies a minimum AI of 40, with at least 60 % of the nitrogen as cold water insoluble nitrogen (CWI N), a total N content of at least 35 %
N, and an unreacted urea nitrogen content of less than 15 % of total nitrogen. In the United States, Western Europe, the Former Soviet Union, and Israel
research has been carried out to reduce the fraction of HWI nitrogen [148]. In the 1980s research resulted in the development of MDU/DMTU compositions
which consist of shorter chain polymers with at least 60 % CWS polymer nitrogen. Although they have higher contents of CWS nitrogen, they still have safer
agronomic and environmental properties than conventional nitrogen fertilizers. Commercial products are white, colorless powders or granules. In wet
granulation, the pH value and temperature must be controlled to avoid hydrolysis and thus losses of formaldehyde. Under normal conditions the finished
products are stable in handling and storage. Typical properties of urea – formaldehyde products are given in Table 21.

Table 21. Properties of typical ureaforms

Property Nitroform* Azolon**

Total N, wt % 37.4 38.0

Insoluble in cold water, wt % 26.9 26.0
Soluble in hot water, wt % 15.4 10.4
Activity index 43 60
Bulk density, t/m3 0.75
Granule size, mm 0.5 – 2.0 1.0 – 4

* Trademark of Nor-AM; BASF product analysis 1980.

** Trademark of Aglukon; analysis from [149].

Application. The release of plant-available nitrogen from urea – formaldehyde products mainly involves decomposition through microbial activity and
dissolution by hydrolysis. Consequently, factors affecting microbial activity, such as higher temperature, moisture, pH value and oxygen availability, also affect
the release of nitrogen. These products are therefore widely used in warmer climates (in the Mediterranean region of Europe and in the southern and
southwestern United States).

4.4.2.2. Other Urea – Aldehyde Condensation Products

Due to the higher costs involved in the combination of urea with higher aldehydes, only two products have gained commercial importance. These are IBDU or
Isodur (urea + isobutyraldehyde) and CDU or Crotodur (urea + acetaldehyde or crotonaldehyde).

IBDU (Isodur). Products derived through the combination of urea and isobutyraldehyde consist of mainly isobutylidene diurea [6104-30-9] (with small
quantities of slow-acting by-products).

Manufacture. Isobutylidene diurea is manufactured by condensation of liquid isobutyraldehyde with urea (either in solution or solid form). In contrast to urea –
formaldehyde, the reaction of urea with isobutyraldehyde results in a single oligomer. To obtain an optimal proportion of IBDU it is important to stop the
reaction by neutralization when the IBDU yield is at a maximum.

Isobutylidene diurea is produced in Japan and Germany [130], [150], [151], [152] (Mitsubishi, BASF). In the BASF process urea reacts with isobutyraldehyde in
an aqueous solution to give a high proportion of slow-release N [153]. A Mitsubishi-developed process is operated by IB Chemicals in Alabama.

Properties and Application. IBDU is a white crystalline solid with a theoretical N content of 32.18 wt % N. The official definition (AAPFCO) requires 30 wt % N,
of which 90 % must be cold water insoluble prior to grinding. Since it is almost completely soluble in hot water, the N content is therefore nearly all slow-
release N. It has a calculated AI of 90 – 99 (ureaform: 55 – 65). Nitrogen is released from IBDU by hydrolysis, which is affected by soil moisture and
temperature. Both urea molecules of IBDU can be liberated. The rate of N release is mainly a function of particle size: the finer the particles, the more rapid the
rate of N release. IBDU is unstable in an acid media, whereby it decomposes into the starting materials. Therefore, it tends to release its nitrogen more rapidly
in strongly acid soils. This can also be counteracted by using larger, well-compacted granules [158], [159].

The safety margin and agronomic response from IBDU is good with turf; occasional phytotoxity has been observed in greenhouse use. Since it is independent
of microbial activity, IBDU is particularly suited to low-temperature application. Properties of IBDU are given in Table 22.

Table 22. Properties of CDU, IBDU, and Isodur

Property CDU IBDU Isodur

mp, °C 245a 207 – 208 203 – 204b

Bulk density, kg/m3 ca. 600 600 – 700 500 – 600
Solubility in water at 25 °C, g/L
fertilizer grade 0.3 – 3.0 2.7

pure substance 1.3 (pH 2); 0.9 (pH 7) 1

Total N, wt % 31 31 31
pH (10 wt % suspension) 4–6 5–8 6–8
LD50 (rat, oral), g/kgb 10.0 10.0

a259 – 260 °C for crotonylidene diurea (BASF).

b236 °C for isobutylidene diurea (BASF).
cToxicological data from BASF.

CDU (Crotodur). Crotonylidene diurea [1129-42-6] is a mixture of 75 – 80 wt % crotonylidene diurea (2 mol urea + 2 mol acetaldehyde) and 15 – 20 wt % 5-
oxyethylcrotonylidene diurea [23048-84-2] (2-oxo-4-methyl-5-oxyethyl-6-ureidohexahydropyridine), 2 mol urea + 3 mol acetaldehyde), [145] and 5 – 7 wt % K
2SO4.

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Manufacture. Crotodur, which was patented as a slow-release fertilizer in 1959 [153], is produced by acid-catalyzed reaction of urea with acetaldehyde (Chisso
Corp., Japan) or crotonaldehyde (BASF, Germany) [154], [155]. The mother liquor is neutralized, and the CDU isolated as a white powder by spray drying or
filtration.

Properties (see Table 22). CDU or Crotodur contains 85 wt % to > 90 wt % pure crotonylidene diurea. It is almost completely insoluble in cold water, but
soluble in hot water with a calculated AI of 90 – 99. In contrast to isobutylidene diurea, N release from crotonylidene diurea depends on hydrolysis and
microbial activity. Only the urea molecule from the side chain (6-position) can be liberated by hydrolysis. The urea which forms part of the ring can only be
released by microbial action [146]. The particle size also influences the N release; with large particles, release is strongly delayed.

Application. In Japan and Europe Crotodur is mainly used on turf and in speciality agriculture, either as a straight N fertilizer or in granulated NPK fertilizers.

4.4.2.3. Further Processing of Urea – Aldehyde Condensates

All commercial urea – aldehyde condensates such as ureaform, IBDU, Isodur, CDU, and Crotodur can be further processed by compaction or moist
granulation with other conventional fertilizers with rapidly available plant nutrients, thus producing straight and compound fertilizers with both slow-release and
rapidly available nitrogen. However, it is necessary to keep the pH between 5.4 and 6.2 [147], or preferably between 5.0 and 5.5 [156], the temperature below
90 °C, and the dwell time as well as the quantity of recycled material as low as possible [130, pp. 1 – 15], [156] to prevent hydrolysis and, particularly in the
case of ureaform, further condensation to higher oligomers.

Commercial Products and Trade Names. There are a large number of various slow-release fertilizers based on ureaform 38–0-0, methylene ureas 40–0-0,
IBDU 31–0-0, and CDU 31–0-0, which are formulated as straight fertilizers and in combination with P, K, and secondary and trace elements in solid form, as
well as in solutions or suspensions: Scotts Granuform, Scotts MU-40, ProGrow, ProTurf (The Scotts Company); Nitroform, Nutralene (Omnicology,
Inc./AgrEvo); Plantosan, Nitroform, Nutralene, Azolon (Aglukon Spezialdünger). Hydroform, Hydrolene (Hydroagri US). Folocron, CoRoN (CoRoN Corp.);
Isodur (Floranid), Crotodur (Triabon) (BASF); Azorit (EniChem); Urea – formaldehyde (Mitsui Toatsu Fertilizers); IBDU (Mitsubishi Kasei); CDU (Chisso).

Analyses of some typical fertilizers containing Isodur or Crotodur are listed in Table 23.

Table 23. Analysis and physical properties of typical fertilizers containing Isodur or Crotodur *

Property Floranid permanent 15 + 9 + 15 (+ 2)** Floranid N 32** Triabon 16 + 8 + 12 (+ 4)**

Nitrogen content, wt %
Total 15 32 16

IBDU 5 29

CDU 11.0

Ammonium 5.8 4.0

Nitrate 4.2

Carbamide 3.0 1.0

Phosphate (P2O5) 9 8
Potassium (K2O) 15 12
Magnesium (MgO) 2 4
Granule size*** 0.7 – 2.8 0.6 – 2.6 1.0 – 3.5
Bulk density, kg/m3 960 600 820

*Floranid and Triabon are trademarks of BASF.

**Floranid Permanent and Triabon also contain trace elements.
***90 % within given range [157].

4.4.3. Other Organic Chemicals

Some other organic compounds such as oxamide, triazones, and melamine have also been used as slow-release fertilizers but have not obtained the
commercial importance of urea – aldehyde products.

Oxamide [471-46-5], the diamide of oxalic acid, N content 31.8 wt %, Mr 88.08, mp 419 °C, 20 1.667 g/cm3, is a nonhygroscopic, colorless compound that
forms needle-shaped crystals.

Its solubility in water is only 0.4 g/L [41, p. 320]. By hydrolysis in the soil, it is transformed first into oxamic acid with liberation of ammonia, and then into oxalic
acid. Oxalic acid is toxic to plants if it is not further converted into carbon dioxide by microbial activity. Because the nitrogen is released by hydrolysis, the slow-
release effect is primarily a function of particle size. Oxamide is manufactured by oxidation of hydrogen cyanide with hydrogen peroxide to give cyanogen,
which is then partially hydrolyzed [161]. It can also be produced directly in one step from hydrogen cyanide, oxygen, and water, with copper nitrate as the
catalyst [162], [163], [164].

In Japan, production of oxamide as a slow-release fertilizer amounts to about 1000 t/a (1995, Ube Industries) [165].

Symmetrical Triazones. Some symmetrical triazones are used as slow-release nitrogen fertilizers [160], particularly in urea – triazone solutions with 28 % N
for application to soil. Triazones are synthesized by condensation reactions of formaldehyde or other aldehydes with urea, organic amines, or ammonia [131,
p. 251].

Commercial Products and Trade Names. Hickson Kerley, United States: N-Sure 28–0-0, N-Sure-Lite 30–0-0, Trisert 13–3-4.

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Melamine, triaminotriazine [108-78-1], is a high-nitrogen (66 wt % N) crystalline powder. It is produced through heating urea under pressure in the presence of
a catalyst. Melamine slow-release fertilizer material is available as a powder (Nitrazine 66 % N). Currently only small amounts are used in the fabrication of
slow-release spikes and stakes for shrubs and trees.

4.4.4. Inorganic Compounds

Some sparingly soluble inorganic compounds such as metal ammonium phosphates and metal potassium phosphates [130, pp. 256 – 284] are also used as
slow-release fertilizers. Their solubility in water at 25 °C is [166], [167]:

MgNH4PO4 · H2O 0.014 g/100 mL

MgNH4PO4 · 6H2O 0.018 g/100 mL
MgKPO4 · H2O 0.21 g/100 mL
MgKPO4 · 6H2O 0.23 g/100 mL

The release of nitrogen, particularly from the two ammonium compounds, again depends on particle size (slow release only with larger particles or granules).

The manufacturing processes for magnesium ammonium and magnesium potassium phosphates are described in [130, pp. 256 – 284], [168], [169].

Other sparingly soluble inorganic compounds which have been used as slow-release fertilizers are based on crystalline ammonium potassium polyphosphates
[170], and on glassy melts of ammonium dihydrogenphosphate, potassium hydrogenphosphate, and dicalcium phosphate [171].

Commercial Products and Trade Names. MagAmp (magnesium ammonium phosphate; Grace Sierra Horticultural Products); EnMag (magnesium ammonium
phosphate + potassium sulfate; ICI).

4.4.5. Coated and Encapsulated Controlled-Release Fertilizers

Coated fertilizers are conventional soluble fertilizer materials whose plant nutrients are rapidly available and which after granulation, prilling, or crystallization
are given a protective coating to control water penetration and hence the rate of dissolution and nutrient release in the soil. The AAPFCO definition is: “A
product containing sources of water soluble nutrients, release of which in the soil is controlled by a coating applied to the fertilizer”.

Coated fertilizers are the fastest growing group of slow- and controlled-release fertilizers in the United States and in Japan. They accounted for 24 % of total
world consumption of slow- and controlled-release fertilizers in 1995/96 [127, pp. 61 – 63]. The growth is due to improved economics in production, the
possibility of controlling the release of nutrients other than nitrogen, and the greater flexibility in determining the nutrient release pattern.

Many condensation polymers, drying oils, waxes, and bitumen were tested for their suitability as coating materials [129, pp. 102 – 263], [172], [173]. However,
only three categories of coated/encapsulated controlled-release fertilizers have gained commercial importance:

1. Sulfur coatings
2. Polymer coatings (e.g., PVDC copolymers, polyolefins, polyurethanes, urea – formaldehyde resins, polyethylene, polyesters, alkyd resins)
3. Sulfur – polymer coatings (hybrid products with a multilayer coating of sulfur and polymer) [174-186]

4.4.5.1. Sulfur-Coated Controlled-Release Fertilizers

The only inorganic coating material which has achieved any importance is sulfur [129, pp. 102 – 263], [132, pp. 151 – 169], [193-196]. The sulfur coating can
be regarded as an impermeable membrane which slowly degrades in the soil through microbial, chemical, and physical processes. Nutrient release depends
on the thickness of the coating in relation to the size of the granule or prill and the quality of the urea substrate. The total N content of sulfur coated ureas
varies with the amount of coating applied; products currently available contain 30 – 42 % N, 6 – 30 % S, and various sealants and conditioners. Commercial
production started in 1972 when ICI commissioned a pilot plant in the United Kingdom.

Manufacture. Most of the modern industrial processes are still based more or less on the technology developed in the 1960s and 1970s by TVA [193], [194],
[197] (now National Fertilizer and Environmental Research Center). Preheated (71 – 82 °C) urea granules (1.7 – 2.9 mm) are introduced into a horizontal
rotating cylindrical drum. Molten sulfur (143 °C) is sprayed onto the urea granules and quickly solidifies on contact. The average target thickness is 40 µm, but
there are various random proportions of granules having thin (< 30 µm), medium (30 – 50 µm) and thick (> 50 µm) sulfur coatings. Any pores and cracks are
closed in a second step by addition of a polymeric hydrocarbon/petroleum-based wax or a high-viscosity polymeric paraffin oil with a polyethylene sealant (2 –
3 % of total weight). A flow conditioner such as diatomaceous earth, talc, clay, or silica (2 – 3 % of total weight) is added to give a dust-free, free-flowing
product with good handling and storage properties.

Other straight and compound fertilizers can also be coated with sulfur. However, ammonium nitrates and fertilizers with high contents of nitrate nitrogen are
excluded due to the risk of explosion.

Agronomic Properties. Generally, sulfur-coated urea products have good slow-release properties. However, resistance of the coating to impact and abrasion
is low. The quality of sulfur-coated urea (SCU) is characterized by the rate of N release into the soil solution within seven days (TVA method). SCU-30
indicates a product that releases 30 % of its nitrogen within seven days, resulting in a rather rapid initial effect. If coated too thickly they may exhibit lock-off,
i.e., no effective nutrient release. These disadvantages of sulfur-coated conventional fertilizers were the reason for the development of sulfur-coated, polymer
encapsulated fertilizers.

Commercial Fertilizers and Trade Names. Sulfur-coated fertilizers are mainly distributed as straight nitrogen grades, e.g., Enspan 39 % N (Hydro Agri, North
America), sulfur-coated urea, and sulfur-coated potassium (Nu-Gro Canada).

4.4.5.2. Sulfur-Coated, Polymer-Encapsulated Controlled-Release Fertilizers

Sulfur – polymer hybrid coatings combine the controlled-release performance of polymer-coated fertilizers with the lower cost of sulfur-coated fertilizers.
Figure 22 [198] shows the flow diagram of the process developed by RLC Technologies. The process yields a sulfur-coated controlled-release granular urea
fertilizer with a uniform, durable polymer coating over the sulfur coating. The hot-melt polymer liquid sealant of the conventional process is replaced by specific
liquid monomers. When applied sequentially onto the surface of the hot sulfur-coated urea granules, they copolymerize to form a firm, tack-free, water-
insoluble polymer coating sealant. The liquid monomers used in this process are diisocyanates, such as MDI (4,4-diphenylmethane diisocyanate), and a polyol
mixture of DEG (diethylene glycol) and TEA (triethanolamine); the TEA acts both as a reactive polyol and a catalyst. The resulting product has improved
impact resistance. The RLC sealant provides a substantial improvement over polymeric wax and solvent-dispersed sealants [198].

Figure 22. Flow diagram of the RLC Technologies process

Commercial Products and Trade Names. The commercial products (in the United States) generally contain 38.5 to 42 % N, 11 to 15 % S and ca. 2 %
polymer sealant: TriKote PCSCU 39–42N (Pursell Technologies), Poly-S PCSCU 38.5–40N (Scotts), and POLY PLUS PCSCU 39N (Lesco).

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4.4.5.3. Polymer-Encapsulated Controlled-Release Fertilizers
Application of controlled-release fertilizers to high-value crops requires precise control of nutrient release geared to plant requirements. Hence, a range of
polymer-coated controlled release fertilizers has been developed, in which the rate of nutrient release can be altered by means of the composition and
thickness of the coating, giving longevities from one to 24 months. The release pattern of these controlled-release fertilizers is significantly more linear than
that of PCSCU.

Polymer coatings can be semipermeable membranes or impermeable membranes with tiny pores. Most polymers used in coating conventional fertilizers
decompose extremely slowly or not at all in the soil and leave residues of up to 50 kg ha–1 a–1). This may be considered as an environmental disadvantage
even though the accumulation of 10 years (500 kg) only represents 200 ppm in dry soil. Nevertheless, extensive research is being carried out into the
development of polymer coatings that are biodegraded after application. In the case of polyethylene, polypropylene, and ethylene copolymers, incorporation of
ethylene – carbon monoxide copolymer promotes photochemical degradation of the coating, and coatings that contain a poly(3-hydroxy-3-alkylpropionic acid)
as active ingredient are biodegradable [178], [179], [185, p. 14].

Manufacture. In the Sierra Process [187] the coating material is a copolymer of dicyclopentadiene with drying or semidrying oils in an organic solvent (glycerol
ester of linseed oil). The granules are coated with at least two layers in a coating drum operating at 65 – 70 °C. Maleic acid, for example, is added to improve
the drying of the oil. Coating weights vary from 10 to 20 wt %; the commercial products are mainly blends of different coating weights.

The Chisso Asahi process [188], [189] produces a particularly smooth coating. The incorporation of finely powdered inorganic materials such as talc and silica
into the coating [185, pp. 15, 16] makes it possible to produce controlled-release fertilizers in which the rate of release of nutrients in the soil varies with
temperature. A hot 5 wt % solution of the coating material in a hydrocarbon or chlorinated hydrocarbon solvent is sprayed onto the warm granules of fertilizer
in a fluidized bed, and the solvents are immediately evaporated with hot air (60 – 70 °C).

Polyolefins, ethylene – vinyl acetate copolymers, poly(vinylidene chloride), and mixtures thereof are used as coating material. The moisture permeability is
modified by means of the ratio of ethylene – vinyl acetate (high permeability) to polyethylene (low permeability) [185, pp. 12 – 16].

The release pattern is determined by a water-leach test at 25 °C; for example, T-180 indicates that the product releases 80 % of its nutrient over 180 d at 25 °
C in water. Products are produced from T-40 to T-360 [185, pp. 19 – 21].

The Pursell Technologies Reactive Layers Coating (RLC) process [190], [191] produces attrition resistant controlled-release fertilizers by coating a plant
nutrient with a coating material that chemically bonds to it. Solvent-free polyols and polyisocyanates are pumped to nozzles, located along the entire length of
a horizontal, cylindrical rotating drum. The two reactive liquids are applied sequentially in ultrathin layers onto the surface of preheated urea granules, where
they polymerize directly to form a continuous polyurethane encapsulating membrane. The first layer of polyisocyanate can also react with the urea granule,
chemically bonding the polymer coating to the surface of the urea granule. The thickness of the layer depends on the number of reactive layers and allows
controllable release durations of up to 6 months to be achieved.

The polyols used in the process are predominantly polyester polyols. The isocyanates used are also a major factor in influencing the properties of the
polyurethane encapsulation. Preferred isocyanate raw materials include polymeric diphenylmethane diisocyanates. Though the process had been primarily
defined for the use of urea, most other plant nutrients/fertilizers can also be utilized.

Commercial Products and Trade Names. The main polymer-coated substrates are urea (40–0-0 and 38–0-0), potassium chloride/potassium sulfate, and
NP, NK, and ammonium nitrate containing NPK fertilizers. Various grades also contain secondary and minor elements.

Trade names: The Scotts Company, US: Osmocote, Osmocote Plus (NPKs + MgO + TEs), High-N, Sierra, and Sierrablen; Prokote, Scottkote. Chisso Corp.,
Japan: Meister (urea, KCl and K2SO4) Lp and Long, Nutricote (NP, NK, NPK). Pursell Technologies Inc., US: POLYON lines (PC-U, PC-SOP, PC-NPK, PC-
MAP, PC-KNO3). Agrium, Canada: Duration and ESN (clay-coated PCU). Aglukon Spezialdünger, Germany (subsidiary of AgrEvo): Plantacote Depot,
Plantacote Control (NPK), and Plantacote Mix. BASF, Germany: Basacote (NPK + TE). Haifa Chemicals, Israel: Multicote 4 (PC-NPK, PC-U, PC-KNO3). Asahi
Chemical Ind., Japan: Nutricote. Mitsubishi Chemical, Japan: M cote (PCU).

4.4.6. Anti-Float Materials

Special controlled-release fertilizers which sink immediately on application have been developed for application to irrigated crops. Diatomaceous earth or
wetting agents such as liquid surfactants are applied to the external surface of the coated fertilizer to achieve this antifloat effect by breaking the surface
tension between the water and the coated fertilizer [192].

Commercial Products and Trade Names. Pursell Technologies Inc. POLYON PCU-AF/AntiFloat, marketed in Japan by Sumitomo; Haifa Chemicals resin-
coated anti-floating urea MULTICOTE.

4.4.7. Controlled-Release Fertilizers on Carriers

Bayer manufactures controlled-release NPK fertilizers based on water-insoluble synthetic ion-exchange resins [199], [200]. The nutrients are released from the
resin granules by reaction with salts in the ground water.

Commercial Products and Trade Names. Bayer AG Lewatit HD 5 NPK 18–7-15 and Lewaterr 80 NPK (31–12–33).

4.4.8. Supergranules
A slow release of nutrients can also be achieved by granulation or compaction of conventional fertilizers with a relatively small surface to volume ratio
(supergranules, briquettes, tablets or sticks or stakes). Some of these formulations also contain urea – formaldehyde or IBDU.

4.4.9. Legislation
In the United States, 50 states regulate their own agricultural policies, including fertilizers. There are some guidelines and Federal EPA regulations which can
be imposed on the individual states (mainly concerning registration of pesticides under RECRA — Resource Conservation And Recovery Act — in the EPA).
However, fertilizers are excluded [201]. In Western Europe there are not as yet general regulations of the EU Commission on slow- and controlled-release
fertilizers, and there are no coated controlled-release fertilizers in the EU type list. There are regulations concerning definitions and classification in the
individual member states. These cover fertilizer types such as coated urea, coated NPK, and partly coated NPK.

In Germany, CDU, IBDU and urea – formaldehydes (UFs) are classified as individual fertilizers. Legislation also includes the group of N, NPK, NP, and NK
fertilizers containing UF, CDU or IBDU; other legislation covers coated and encapsulated fertilizers [202], [203].

To achieve European standardization, a Task Force slow-release fertilizers (TFsrf) has been formed with the aim of defining the conditions under which type of
fertilizer included in the EU fertilizer type list can be newly categorized as a slow- or controlled-release fertilizer [127, p. 11]: A fertilizer may be described as
slow-release if the nutrients declared as slow- (controlled-) release meet, under defined conditions including that of a temperature of 25°C, each of the
following three criteria:

1. No more than 15 % released in 24 h

2. No more than 75 % released in 28 d
3. At least about 75 % released in the stated release time

This European Task Force has close contacts to the Controlled Release Task Force formed in the United States by AAPFCO (Association of American Plant
Food Control Officials) and TFI (The Fertilizer Institute). In Japan registration of slow- or controlled-release fertilizers requires a dissolution test in water under
well defined conditions [204], [127, p. 105].

4.5. Nitrification and Urease Inhibitors

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4.5.1. Introduction
Ammonium ions in the soil — whether from decomposition of organic material or from the application of ammonia-containing mineral fertilizers — are oxidized
to nitrite and nitrate. Bacteria of the species Nitrosomonas spp. are responsible for the transformation into nitrite. The nitrite is relatively rapidly oxidized to
nitrate by Nitrobacter and Nitrosolobus spp., so that there is normally no toxic accumulation of nitrite in the soil [205, pp. 156, 157], [206, pp. 287, 289]. The
process is known as nitrification. The formation of the environmentally relevant gases N2O and NO may be regarded as a side-reaction of the nitrification
process [207].

Nitrate is readily soluble in water and in the aqueous soil medium, and so is completely mobile in the soil, in contrast to ammonia, which is strongly adsorbed in
soil colloids and base-exchange complexes. Therefore, it can be leached readily from the soil [208-212]. Under unfavorable (anaerobic) conditions nitrate can
be reduced by denitrification to N2 [206, p. 289]. This can result in further considerable losses of nitrogen [213, pp. 90 – 95].

Addition of a nitrification inhibitor to ammonia containing fertilizers or urea retards nitrification and minimizes leaching of nitrogen as nitrate and losses of
nitrogen due to denitrification. Furthermore, nitrification inhibitors also suppress methane emissions and lower nitrous oxide emissions [207], [212], [214-218].

On application to the soil, amide nitrogen, as in urea, UAN (urea – ammonium nitrate solution), and some NPK fertilizers, is transformed by the enzyme urease
via the unstable ammonium carbamate (H2NCOONH4) to ammonia, and CO2 [205, p. 156].

This transformation has two major drawbacks:

1. It results in sometimes very high volatilization losses of ammonia when urea is applied to the surface [219], [220] or under flooded conditions.
2. It can produce severe seedling damage by ammonia and nitrite [221].

Urease inhibitors inhibit or reduce the formation of urease, which is ubiquitous in surface soils. This slows down the rate of urea hydrolysis in the soil and
prevents or at least depresses the transformation of amide nitrogen into ammonia.

Definitions. Nitrification inhibitors are compounds that delay bacterial oxidation of the ammonium ion by depressing the activity of Nitrosomonas bacteria in
the soil over a certain period of time. Thus, they control leaching of nitrate by keeping nitrogen in the ammonium form longer, and preventing denitrification of
nitrate [222, p. 12]. Urease inhibitors prevent or depress transformation of the amide nitrogen of urea into ammonium hydroxide and ammonia over a certain
period of time by inhibiting hydrolytic action on urea by urease; thus they avoid or reduce volatilization losses of ammonia.

There is considerable confusion concerning the terms nitrogen stabilizers, nitrification inhibitors, urease inhibitors, and stabilized fertilizers. The terms nitrogen
stabilizers and nitrification inhibitors have been used interchangeably. Strictly speaking, stabilized fertilizers refers only to those which are modified during
production with a nitrification inhibitor, such as ALZON and BASAMMON. In all other cases, fertilizers and nitrification and urease inhibitors are sold separately
[222, p. 12].

Advantages and Disadvantages of Nitrification and Urease Inhibitors. Nitrification inhibitors significantly reduce leaching losses of nitrate by stabilization
of ammonia [219], [220] and reduce emissions of the environmentally relevant gases N2O and NO [207], [214-216], [223]. Nitrification inhibitors indirectly
improve the mobilization and the uptake of phosphate in the rizosphere [224]. Urease inhibitors reduce ammonia volatilization losses, particularly from top-
dressed agricultural fields and under reduced tillage conditions [225, p. 9, 10], [226-228]. Urease inhibitors furthermore reduce seedling damage where seed-
placed levels of urea-containing fertilizers are too high [219], [221].

Possible disadvantages include the fact that fertilizers containing ammonia and a nitrification inhibitor may result in increased ammonia volatilization if they are
not incorporated into the soil immediately after application. Depending on the type of nitrification inhibitor, the activity of soil bacteria may not only be
interrupted for a certain time period, but the soil bacteria may actually be killed. This can be regarded an undesirable interference in a natural soil process
[213, p. 219], [229, pp. 37 – 44].

4.5.2. Types of Nitrification and Urease Inhibitors

Extensive research on nitrification and urease inhibitors has been carried out mainly in Europe, Japan, Russia, and the United States. Various chemical
fumigants and pesticides have also been tested to establish their possible effectiveness in inhibiting nitrification (nematicides; soil-insecticides and herbicides)
[230, pp. 547 – 554].

Until the late 1960s research was carried out in the United States and Japan on N-Serve (2-chloro-6-trichloromethylpyridine; Dow Chemical Company), AM (2-
amino-4-chloro-6-methylpyrimidine; Mitsui Toatsu Chemicals), Terrazole (5-ethylene oxide-3-trichloromethyl-1,2,4-thiodiazole; Olin Mathieson); ASU (1-amide-
2-thiourea; Nitto Chemical Industry), and ATC (4-amino-1,2,4-triazole hydrochloride); substituted phenyl compounds (DCS), and compounds of the s-triazine
line (MAST) [231, pp. 64 – 82]. In Eastern Europe and the former Soviet Union, CMP (1-carbamoyle-3-methylpyrazole) and its main metabolite MP (3-
methylpyrazole) were tested extensively. However, only products based on pyridines, dicyandiamide, pyrazoles have gained practical agronomic importance
as nitrification inhibitors. Terrazole, AM, and ASU (thiourea) had some regional importance, particularly in the United States and in Japan.

Reseach on urease inhibitors has concentrated on phosphoric triamides. Limited research has been carried out with PPD/PPDA (phenyl phosphorodiamidate)
and ATS (ammonium thiosulfate) [222, p. 32].

There are no reliable statistics publicly available on the use of nitrification inhibitors due to the unique production structure. Estimates of the acreage treated
with fertilizers containing nitrification inhibitors for the United States are 1860 × 106 ha (1995/96), 1660 × 106 ha thereof with nitrapyrin and 200 000 ha with
dicyandiamide. For Western Europe a very rough estimate is 200 000 ha of arable cropland treated with fertilizers containing dicyandiamide [222, p. 63, 64].

4.5.3. Pyridines
4.5.3.1. Nitrapyrin
Nitrapyrin consists of 2-chloro-6-trichloromethylpyridine [1929-82-4] and related chlorinated pyridines, such as 4,6-dichloro-2-trichloromethylpyridine [
1129-19-47].

Manufacture. The (trichloromethyl)pyridine compounds are manufactured by photochlorination of methyl-substituted pyridines. The desired amount of chlorine
gas is passed through the appropriate methyl-substituted pyridine, generally in the presence of its hydrochloride. The product is recovered by conventional
procedures such as filtration or distillation [232]. A flow diagram for the production of chlorinated picolines from readily available raw materials such as -
picoline is given in [233].

Nitrapyrin is produced exclusively by DowElanco in the United States and distributed under the trade name N-Serve (NS) [234-236].

Properties. Nitrapyrin is a white crystalline solid with a mild sweetish odor, mp 62 – 63 °C; bp 101 °C at 133 Pa. For use in agriculture nitrapyrin is formulated
as a liquid product.

N-Serve 24 nitrogen stabilizer consists of 22.2 wt % 2-chloro-6-trichloromethylpyridine, 2.5 wt % related chlorinated pyridines including 4,6-dichloro-2-
trichloromethylpyridine, and 75.32 wt % Xylene-range aromatic solvent [64742-96-6].

N-Serve 24E nitrogen stabilizer consists of 21.9 wt % 2-chloro-6-trichloromethylpyridine, 2.4 wt % related chlorinated pyridines, 4,6-dichloro-2-
trichloromethylpyridine, and 75.7 wt % Xylene-range aromatic solvent.

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Both formulations contain 2 lb of active ingredients per gallon (≈ 240 g/L); NS24 is recommended for use with anhydrous ammonia (82 % N) and impregnation
onto urea; NS24E for use with liquid fertilizers (aqueous ammonia, solutions) and with manure (slurry).

Nitrapyrin has a very selective effect on Nitrosomonas bacteria. However, this effect is not only bacteriostatic but also bactericidal, so that part of the
population in treated soil is killed [213, p. 219], [236], [237].

Toxicity. The single dose toxicity of nitrapyrin is low; the technical material has a LD50 of ca. 1000 mg/kg of body weight in laboratory animals. It is slightly
irritating to the eyes and skin and has a low vapor toxicity. The equivalent LD50 (oral, female rat) for the two formulations is 2140 mg/kg (N-Serve 24) and
3300 mg/kg (N-Serve 24E). In soil and in plants, nitrapyrin is chemically and biologically rapidly degraded into 6-chloropicolinic acid, the only significant
chemical residue from its use, and further to N2, Cl–, CO2, and H2O.

Application. The recommended application rate is 1.4 – 5.6 L/ha. In warm soils the nitrification inhibiting period is normally 6 – 8 weeks; it can be 30 weeks or
more in cool soils.

However, in agronomic use this long-term standard nitrification inhibitor has two drawbacks:

1. Loss by volatilization from treated fertilizers during storage

2. The bactericidal effect, which may be regarded as an undesirable interference in a natural soil process

The loss by volatilization restricts it to simultaneous application with anhydrous or aqueous ammonia or fertilizer solutions which are injected directly into the
soil at a depth of at least 5 – 10 cm. This limits acceptance in regions where nitrogen fertilizer is not commonly injected. Therefore, N-Serve is available
commercially only in the United States.

4.5.3.2. Other pyridines

3,6-dichloro-2-trichloromethylpyridine is a proven nitrification inhibitor [238]. However, it is not readily obtained by ring chlorination of a 2-substituted pyridine
because such chlorinations are not sufficiently selective to produce a preponderance of the desired isomer. Hence, 3,6-dichloro-2-methylpyridine is prepared
by the addition reaction 1,1-dichloro-2-propanone and acrylonitrile to give 4,4-dichloro-5-oxohexanenitrile. Subsequent cyclization in the presence of hydrogen
chloride gives 3,6-dichloro-2-methylpyridine, which is chlorinated to obtain 3,6-dichloro-2-trichloromethylpyridine [239].

Commercial Products and Trade Names. N-Serve 24 Nitrogen Stabilizer, N-Serve 24E Nitrogen Stabilizer, DowElanco.

4.5.4. Dicyandiamide
Dicyandiamide [461-58-5] exists in two tautomeric forms ( Cyanamides – Dicyandiamide). Its nitrification-inhibiting property was first reported in 1959 [240].

Manufacture. All large-scale production processes are based on calcium cyanamide. In the first step cyanamide is liberated from calcium cyanamide by
carbonation in aqueous solution at pH 7 – 8. The cyanamide is then dimerized to dicyandiamide at pH 9 – 10.

The dicyandiamide is isolated by filtration or centrifugal crystallization.

The disadvantage of this production process is the high energy input for the production of calcium carbide, the raw material for the production of CaCN2; this is
reflected in the relatively high price for the product as a nitrification inhibitor. There are only three major producers worldwide: SKW Trostberg and SKW
Stickstoffwerke Piesteritz in Germany; Odda Smelteverk in Norway; and Nippon Carbide in Japan. The former Canadian producer, Cyanamid Canada, has
ceased production.

Properties. Dicyandiamide is generally supplied as white or colorless crystals in paper or jute bags. Under dry conditions it can be stored for an unlimited
period. It has low water solubility (3.2 g/100 g water at 20 °C) and contains at least 65 % nitrogen. When applied to the soil it is decomposed (partly abiotically
and partly biotically by specific enzymes) and converted via guanylurea and guanidine to urea, a conventional fertilizer [241-244].

Dicyandiamide has a bacteriostatic effect on the Nitrosomonas bacteria. Depending on the amount of nitrogen applied, soil moisture, and temperature, the
nitrification-inhibiting effect of dicyandiamide lasts 6 – 8 weeks.

Toxicity. With an LD50 of 10 000 mg/kg oral (female rat), dicyandiamide is practically nontoxic. The Ames test did not reveal any mutagenic activity.
Furthermore, long-term studies have shown that dicyandiamide has no cancerogenity. Therefore, any risks for human health can be excluded. This also refers
to its residues [237], [245].

Processing. In Western Europe the majority of ammonium-containing fertilizers are applied in solid form. However, a satisfactory nitrification-inhibiting effect
can not be obtained by simple mechanical mixing of dicyandiamide with the solid fertilizer. Dicyandiamide added to the fertilizer prior to granulation, it
decomposes at the usual granulation temperatures of 100 – 140 °C. When dicyandiamide is spread onto the finished fertilizer granules it does not adhere
firmly to the granule surface. The use of vegetable, animal, or mineral oils as adhesion promoters has drawbacks with regard to storage and spreading. BASF
has developed a process for applying dicyandiamide to ammonium- and sulfate-containing fertilizers without decomposition and with good adherence to the
surface of the granules [246]. The fertilizer granules at 60 – 130 °C are mixed in a rotary drum with 2 – 4 wt % of finely ground dicyandiamide with
simultaneous addition of a 40 – 50 wt % aqueous solution of Ca(NO2). The surface of the fertilizer material is rapidly cooled, thus preventing a decomposition
of the applied dicyandiamide, which adheres well to the fertilizer granules.

Freeport-McMoRan Resource Partners in the United States has developed two processes for incorporating dicyandiamide into urea in combination with other
nitrification- or urease-inhibiting compounds. In the first, dicyandiamide is incorporated into urea in combination with ammonium thiosulfate and a phosphate.
Controlled release of N is claimed [247]. In the second, dicyandiamide is incorporated into urea in combination with N-(n-butyl)thiophosphoric triamide (NBPT)
[248].

Application. Dicyandiamide is applied directly with N or NPK fertilizers and fertilizer solution, in which it is incorporated in correct proportion for the ammonia
content. These stabilized fertilizers are recommended for all agricultural crops, particularly when grown on light-textured soils where heavy precipitation is
expected within 6 – 8 weeks after application or where crops have a relatively slow growth rate during the early growing stages (e.g., potatoes).

Commercial Products and Trade Names. Ensan (BASF technical product); Basammon stabil (27 % total N, of which 1.6 % is dicyandiamide N (Ensan) and
13 % S); Nitrophoska stabil 12–8-17 (12 % total N, of which 1.1 % is dicyandiamide N (Ensan), plus 2 % MgO and 7 % S). Didin (SKW technical product);
Alzon 27 (27 % total of N, of which 1.6 % is dicyandiamide N (Didin) and 31 % S); Alzon 47 [47 % total N, of which 3 % is dicyandiamide N (Didin)]; Piadin
(SKW Stickstoffwerke Piesteritz) liquid mixture of DCD and 3MP (3-methylpyrazole, the main metabolite of CMP) in a proportion of 15 : 1, contained in
Piasin 28/Alzon-flüssig (a urea – ammonium nitrate solution).

4.5.5. Pyrazoles
The group of pyrazole compounds has the largest number of compounds showing a nitrification-inhibiting effect [249], [250]. They include 3-methylpyrazole;
3,4-dimethylpyrazole; 4-chloro-3-methylpyrazole; 3-methylpyrazole phosphate; 3,4-dimethylpyrazole phosphate; 4-chloro-3-methylpyrazole phosphate;
compounds resulting from the addition of polyacrylic acid to 3,4-dimethylpyrazole, 4-chloro-3-methylpyrazole, 3,4-dimethylpyrazole phosphate, 4-chloro-3-
methylpyrazole phosphate; and from the addition of polyphosphoric acid to 3,4-dimethylpyrazole (1:20) and (1:1). In the 1980s and 1990s various
compositions were patented [324], [251-256].

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Properties. The nitrification-inhibiting effect of pyrazole compounds is better than that of dicyandiamide. However, they have one or more of the following
disadvantages: they are liable to hydrolysis, which lowers the stability in storage and the activity period in the soil. They are too toxic and they are highly
volatile. 3-Methylpyrazole is so volatile that significant amounts are lost when it is applied onto the surface of fertilizer granules or on fertilizer storages. Metal
salts and metal complexes of 3-methylpyrazole [257] are also relatively volatile.

The most extensively tested pyrazole is 1-carbamoyl-3-methylpyrazole (CMP; in Russia: KMP). This compound is not as volatile as 3-methylpyrazole, but its
manufacture is difficult and high evaporation losses may still occur when it is applied to fertilizers and on storage.

4.5.5.1. 1-Carbamoyl-3-methylpyrazole
1-Carbamoyl-3-methylpyrazole (and its metabolite 3-methylpyrazole, MP) has the molecular formula C5H7N3O.

CMP was developed by VEB Agrochemie Piesteritz (now SKW Stickstoffwerke Piesteritz, Germany). Further research and practical use was mainly carried out
in the former German Democratic Republic, in Central Eastern Europe, and in the former Soviet Union.

Manufacture. Carbamoyl-3-methylpyrazole (CMP) is produced from 3(5)-methylpyrazole (MP) by carbamoylation with sodium cyanate in aqueous HNO3.
After 1 h, the resulting CMP is removed by filtration, washed with water, and dried in a vacuum dryer. The yield is 90 %.

Properties. Bulk density 630 kg/m3, solubility in water 0.56 g/100 g, mp 123 – 125 °C, evaporation pressure 4.41 × 10–2 Pa (20 °C). Therefore, the technical
solid product has to be transported and stored in closed containers. When mixed with solid or liquid fertilizers, these have to be applied and incorporated into
the soil immediately after preparation of the mixture. CMP has a bacteriostatic but not bactericidal effect on Nitrosomonas bacteria.

Toxicity. CMP has an LD50 of 1580 mg/kg (rat, oral) and its metabolite 3MP and LD50 of 1312 mg/kg (rat, oral).

Application. For use in field testing and agriculture CMP was formulated as a 50 % CMP-preparation for mixing with solid ammonium-containing fertilizers or
solutions. However, because of its liability to hydrolysis and to prevent evaporation losses the CMP formulation could only be added at the time of applying the
fertilizer and, like nitrapyrin, had to be incorporated into the soil immediately.

Commercial Products and Trade Names. At present (1998) there is no registration for 1-carbamoyl-3-methylpyrazole or any other pyrazole compound as a
nitrification inhibitor in Europe. In accordance with German fertilizer law, Stickstoffwerke Piesteritz has registered a 15 : 1 mixture of dicyandiamide with 3MP
under the name Piadin, recommended for use with UAN fertilizer solutions.

4.5.5.2. Outlook
In recent years research has concentrated on overcoming the high evaporation losses on adding pyrazole compounds to fertilizer granules and solutions, on
storing such modified fertilizers, and on applying them onto the soil. BASF [258] has reported a process in which fertilizer granules are covered with salts of 3-
methylpyrazole and made resistant against abraision and evaporation by addition of an inorganic or organic polyacid [259]. This treatment significantly lowers
the volatility of the nitrification inhibitor and allows smaller amounts to be used. The storage stability of fertilizers treated by the BASF process is also improved.
In a test for 4 weeks at 30 °C, 40 – 50 % R. H., and 1.2 m/s air velocity on 3,4-dimethylpyrazole/polyphosphoric acid 1/20 and 1/1 (DMPP), losses of the
applied nitrification inhibitor were 0 and 12 %, respectively. Thus, DMPP is of future interest as a nitrification inhibitor.

4.5.6. Neem/Neem-Coated Urea

The extract from the press cake of the seed of the neem tree (Azadirachta indica) exerts a nitrification-inhibiting effect on Nitrosomonas spp. This effect is
reversible.

The active compound in this biological nitrification inhibitor consists of various terpenes/triterpenes (epinimbin, nimbin, deacetylnimbin, salanin, azadirachtin,
deacetylsalanin).

Toxicity. The formulated product is nontoxic.

Application. For practical use, a product containing 5.0 % active ingredient is to be mixed with urea in a ration of 1 : 100 before application.

Commercial Products and Trade Names. Nimin (5 – 5.5 % active ingredient) produced by Godrej Agrovet, Pirojshanagar (India).

4.5.7. Urease Inhibitors

Although it has long been known that substantial evaporation losses in form of ammonia from urea may occur, it was only in the 1980s that the first chemical
substances with effective urease-inhibiting properties in soils were disclosed, namely the phosphoric triamide compounds. Losses of between 3 and 40 % and
more of applied nitrogen are possible when urea is not incorporated immediately after application and stays on dry soil (particularly on soil with a high pH and
with high temperature). Also if it is applied with conservative tillage, particularly no-till, and on crops which are not tilled, such as bananas, sugar cane, oil
palms, and rubber, as well as on flooded rice [206, p. 290], [213, p. 211], [218], [260-263], [264, pp. 52, 59]. Reference [265] lists 146 triamide compounds, of
which N-(n-butyl)thiophosphoric triamide (NBPT) showed the best inhibition values.

N-(n-butyl)thiophosphoric triamide [94317-64-3], NBPT urease inhibitor is the best developed of the N-alkyl thiophosphoric triamide for commercial
applications.

Manufacture. NBPT is prepared by a two-step synthesis in THF:

The approximate product composition from this manufacturing process is as follows [337]:

– N-n-butylthiophosphoric triamide (NBPT), min. 85 wt %

– N,N-di-n-butylthiophosphoric triamide (DNBPT) 0 – 3 wt %
– N,N,N-tri-(n-butyl)thiophosphoric triamide (TNBPT) 0 – 3 wt %
– Thiophosphoric triamide (TPT) 0 – 3 wt %
– Others 0 – 10 wt %

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– THF 0 – 2 wt %
– Triethylamine 0 – 2 wt %

Properties. Pure NBPT is a white crystalline solid, industrial grade NBPT is a waxy, sticky, heat- and water-sensitive material, which render this material
difficult to handle. This material is susceptible to decomposition during storage and distribution. The vapor pressure is 1.1 kPa at 40 °C. The compound is an
excellent urease inhibitor that inhibits the activity of urease for 12 – 14 d on dry soil. When incorporated into the soil in combination with urea or urea-
containing fertilizers, it significantly reduces seedling damage when seed-placed levels of such fertilizers are too high [219], [221]. For satisfactory use on
flooded crops, further research is needed. N-methyl-pyrrolidone (NMP) is a good carrier for NBPT [268]. However, cheaper formulations with better long-term
stability are obtained with glycols and glycols with a liquid amine cosolvent [269].

Toxicity. The acute oral LD50 of NBPT is 1000 – 4000 mg/kg. The Ames tests were negative [266, p. 23]. The compound poses a very low acute toxicity
hazard to workers and has received EPA approval. Because it inhibits free urease in the soil without affecting bacterial growth, it is not classified as a pesticide
and hence not regulated under TSCA. In the soil, the product degrades into the fertilizer elements nitrogen, phosphorus and sulfur.

Application. For practical use in agriculture NBPT (Agrotain) is formulated as a green clear liquid containing [267] 25 % N-(n-butyl)thiophosphoric triamide, as
active ingredient, 10 % N-methylpyrrolidone, and 60 – 65 % other nonhazardous ingredients. The recommended rate of application depends exclusively on the
quantity of amide-nitrogen applied as urea, UAN, or in the form of NPK-fertilizers (1.4 kg per tonne of urea).

Agrotain is primarily recommended for pre-planting surface application of urea and urea-containing fertilizers, but may be used in pre-emergence, side-dress,
top-dress, or other post-planting applications. It is not recommended for use if rain is imminent [222, pp. 38, 39].

Commercial Products and Trade Names. The only commercial product for use in agriculture is Agrotain (IMC-Agrico).

4.5.8. Environmental Aspects

In assessing the value of nitrification and of urease inhibitors not only must the better utilization of the applied nitrogen be taken into account, but also the
possibility of maintaining clean ground water, as well as reduced emissions of ammonia and other environmentally relevant gases [222]. In Germany, where, in
water catchment areas with restrictions or for other reasons, a reduction in applied nitrogen is required, the recommendation is that nitrogen application can be
reduced by approximately 20 kg/ha without loss of yield.

Of equal importance are the positive environmental properties of nitrification inhibitors in significantly reducing emissions of climatically relevant gases such as
N2O and methane [207].

The application of urea or UAN-solution modified with a urease inhibitor such as NBPT would permit a substantial reduction in nitrogen losses to the
atmosphere, and consequently also in the application rates, without affecting growth and yield of fertilized crops.

4.5.9. Legal Requirements

In Western Europe, there is no uniform regulation for DCD, the leading nitrification inhibitor (urease inhibitors are not yet in use). As in the case of slow- and
controlled release fertilizers, individual countries [270], [271] have established national classification and legislation [272]. The pyrazole compound CMP (in
combination with DCD) also comes under fertilizer legislation.

In the United States only fertilizers, but not additives to fertilizers, are excluded from RECRA (Resource Conservation And Recovery Act) regulations of the
EPA. Therefore nitrapyrin — the active ingredient in N-Serve, the leading nitrification inhibitor in the United States — is classified as a pesticide in the EPA
registration. In 1996 it was decided that all nitrification inhibitors have to be EPA registered as pesticides in the United States [222]. However, in spite of the
new regulation, DCD will not require registration as a pesticide. NBPT, which does not affect soil organisms, is not classified as a biocide, but is regulated
under the TSCA.

4.6. Organic Fertilizers (Secondary Raw Material Fertilizers)

At present an EC catalogue of commercial organic fertilizers is not available. Since these fertilizers mainly contain exploitable plant and animal wastes and in
future will contain more waste of organic origin (with or without pretreatment such as composting, anaerobic fermentation, etc.), comprehensive legal
provisions are in preparation. In Germany these organic fertilizers are designated secondary raw material fertilizers (Sekundärrohstoffdünger). According to the
German Fertilizer Law their main components are organic waste materials for agricultural and horticultural utilization (secondary raw materials). These
fertilizers are also subject to the German Waste Law (analysis of pollutant content, description of subsequent utilization) and the German Fertilizer Law (control
of nutrient content) [273-275]. Depending on the quality standard, monitoring systems varying in analytic sophistication are specified. The main argument for
the application of these fertilizers is the preservation of natural (and therefore limited) nutrient resources (e.g., P) by means of systematic recycling. The
applied amount of these fertilizers is mainly limited by their nutrient content. In the case of low quality, the pollutant load can also determine the applied
quantity. In Germany the permitted pollutant load conforms to the threshold values fixed in the decrees for the utilization ofsewage sludge (AbfKlärV), which
are likely to be lowered substantially for reasons of soil protection [276]. According to the pollutant content or the ratio of nutrients to pollutants, organic wastes
can be ranked as to their applicability as secondary raw material fertilizers (Fig. 23). For fertilizers containing several organic waste materials, each component
must meet the legal requirements for secondary raw material fertilizers. Blending of unapproved material with compounds of low pollutant content is prohibited.

Figure 23. Applicability of wastes for agricultural use [277]

Another group of organic – mineral fertilizers are mixtures of fertilizer salts (N, P, K) with peat, composted bark, lignite dust, or, occasionally, dried slurry. The
difference between these fertilizers and secondary raw material fertilizers is that the primary product of organic origin is not classified as waste. Nevertheless,
threshold values for heavy metal concentrations have been set [e.g., 3 mg Cd/kg dry weight (dw); 750 mg Zn/kg dw]. In the case of peat, different
combinations of fertilizer salts (N, NP, NPK, PK) are added. In the case of composted bark, lignite, or slurry, only mixtures with NPK fertilizers are supplied
[274].

Organic fertilizers are also classified according to their effects:

– Fertilizers with an improving effect on soil condition have a stable organic substance as well as a slow effect on N supply (low concentration of readily
available nitrogen)
– Fertilizers with short-term effects on nutrient supply, especially of nitrogen, have high contents of mineral nitrogen and/or readily available organic N
compounds
Examples for the first category are composts (i.e. biogenic composts, garden composts) and fertilizers based on peat. The second category includes sewage
sludge (high NH4 concentration), blood meal, and potato starch wastewater (readily degradable organic N compounds).

Organic fertilizers with or without the addition of mineral fertilizer salts are classified as follows:

1. Fertilizers based on peat (or materials of similar stability): peat, composted bark, lignite
2. Fertilizers based on waste materials of animal origin: horns, bone meal, blood meal, hide meal, feather meal, guano
3. Fertilizers based on waste materials of plant origin (selected examples of waste materials from the food- and feedstuff industries): castor cake, cacao
waste, brewer's grains, rape (marc), vinasse, spent mash, potato starch wastewater, filtration diatomaceus earth
4. Fertilizers based on municipal waste: sewage sludge, biogenic and garden composts

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4.6.1. Fertilizers Based on Peat or Materials of Similar Stability
Peat ( Peat) is an organic material of stable structure and low nutrient content that has no effect on nutrient supply without the addition of mineral fertilizers,
but improves soil condition (e.g., aeration, water-retention capacity). The raw material for peat fertilizers is mainly highly decomposed upland moor peat (black
peat) or acidic low moor peat (pH < 6). These peats (pH 3 – 5, volume weight 50 – 200 g/L, salt content 50 – 1500 mg/L, ash 2 – 15 %, organic matter 85 –
98 %) have high sorption capacity (cation sorption capacity 300 – 600 mval/L).

Depending on the kind of application, the crop, and the nutrient status of the soil, several mixtures of peat with mineral fertilizers (N, NP, NPK, and PK salts)
are available. The following minimum requirements for nutrient content are specified: 1 % N, 0.5 % P, 0.8 % K, 30 % organic substance [274].

Similar mixtures of organic and mineral fertilizers are based on composted bark or lignite (partial substitute for peat) and other organic materials such as dried
slurry or spent mushroom substrate (SMS). The minimum fraction of organic substance is set at 15 %. The organic substance of composted bark is highly
stable against biological degradation and resembles the organic substance of peat. After complete decomposition, composted bark shows no N immobilization
and is therefore suitable for replacing peat in mixtures with other fertilizers (pH 5 – 7, volume weight 150 – 300 g/L, salt content 100 – 1500 mg/L, ash 12 –
45 %, organic substance 55 – 88 %). Threshold values for heavy metal concentrations are specified for these fertilizers [274], [278].

4.6.2. Fertilizers Based on Waste Materials of Animal Origin

Only waste materials that pose no health risk may be converted into fertilizers. The raw materials arise as byproducts at butchers' shops, slaughterhouses,
and carcass-disposal plants. Horn, bone meal, and blood meal are the most widely used in agriculture. In some cases, the primary products, containing mainly
N and P, are upgraded by the addition of K salts [279], [280], [281], [282].

Horns. Horn materials (e.g., horns, hoofs, claws) consist mainly of the filament protein keratin. Since keratin decomposes slowly, horns represent a slow N
source (22 % of the protein is in the form of cystein). The rate of N release increases with the extent of grinding (chips < grit < meal). Nutrient concentrations
are listed in Table 24.

Table 24. Nutrient concentrations in fertilizers based on animal wastes (% in dry matter)

Fertilizer N P K Ca Mg C/N

Horn 10 – 14 0.4 – 4.0 0.2 – 0.8 1.5 – 7.5 0.5 – 1.0 3 – 4

Blood meal 9 – 13 0.2 – 1.0 0.2 – 1.5 1.5 – 3.0 0.4 2.4
Feather meal 12 0.3 0.2 4
Bone meal 4 – 6 (0.8) 7 – 12 0.2 18 – 25 0.6 4.5
Carcass meal 6 – 11 2.4 – 7.0 0.3 – 0.5 4 – 10 0.2 3.5
Guano 8 – 16 2–7 1–3 18 3–5 3–4

Bone Meal. Bones are ground, partly degreased, and cleaned. The main constituent of bone protein is the filament protein collagen (90 % of bone N is bound
in collagen). By treatment with hot water and steam, collagen is converted into glutine and is removed. Therefore, steamed bone meal contains only 0.8 % N
(untreated bones 4 – 6 % N). Due to the high P content (7 – 12 % P), bone meals are mainly applied as P fertilizers (Table 24). Occasionally, tricalcium
phosphate is converted into monocalcium phosphate by acid treatment.

Blood Meal. Besides blood, blood meals often contain other slaughterhouse wastes such as intestine contents. These mixtures are dried and ground (N
content 9 – 13 %; Table 24). Sometimes, mixtures of fresh blood (3 % N, 0.1 – 0.2 % P, 0.1 % K, 80 % water content) with solid wastes are used. Like meat
meal, blood meal has a short-term effect on N supply.

Hide Meal. The main constituents of hide meal, a waste material from leather production, are skins and hair. The effect on N supply is quite slow (8 – 11 % N
dw, C/N 5). In Germany, the threshold value for Cr3+ is set at 0.3 % in dry matter (for agricultural utilization, Cr6+ is prohibited in hide meal).

Feather Meals. These fertilizers show slow N release, comparable to that of horns. The N content of 13 – 14 % (Table 24) is mainly bound as keratin.

Meat and Carcass Meal. Occasionally, meat meal and carcass meal are converted into organic fertilizers. These slaughterhouse wastes have a high
proportion of protein and hence a short-term effect on N supply (meat meal: 11 % N, 2.4 % P; meat-and-bone meal: 10 % N, 2.5 – 7 % P; carcass meal 6 –
10 % N; Table 24).

Guano consists of partially mineralized excrements of seabirds and can also contain feathers and carcasses. It is obtained from deposits in arid coastal
regions of South America. Guano is converted to guano fertilizers by acid treatment. Guano fertilizers consist mainly of inorganic substances and contain 8 –
16 % N, 2 – 7 % P (ammonium and calcium phosphates) and 1 – 3 % K (Table 24). Since up to 50 % is in the form of ammonium, guano has a short-term
effect on N supply.

4.6.3. Fertilizers Based on Wastes of Plant Origin

Provided the waste materials do not pose any health risk, conversion into fertilizers can be performed without special pretreatment. Both aerobic (composting)
and anaerobic methods (fermentation, generation of biogas) are suitable for the treatment of plant wastes. The pretreatment and conditioning of some wastes
are regulated. All substances described have low pollutant contents. Therefore, the applied quantities are only limited by nutrient contents [274], [281], [282].
The nutrient concentrations in these fertilizers are summarized in Table 25.

Table 25. Nutrient concentrations (% dw) in fertilizers based on wastes of plant origin

Fertilizer N P K Ca Mg org. S C/N

Castor cake 5.5 0.8 0.8 – 1.6 0.4 0.3 80 8

Cacao waste 2.3 – 3 0.4 – 0.5 2.5 – 3.0 0.6 0.5 90 17 – 24
Brewers grains 4 0.4 – 0.7 0.5 – 1.0 0.3 0.2 65 – 75 10 – 12
Fruit pulp 1.0 0.3 1.3 0.8 0.1 85 – 95 40 – 50
Rape 1.5 – 2.5 0.4 – 0.8 3 – 3.5 1.0 – 1.8 0.2 75 20 – 30
Vinasse 3–4 0.15 6–7 0.6 – 1.2 0.3 50 8
Pulp 5–6 0.7 – 1.0 0.8 – 6.0 75 – 85 8 – 10
Potato starch wastewater 4–8* 0.7 – 0.9 * 10 * – 12 5*–7
Filtration diatomaceus earth 0.7 < 0.1 < 0.1 0.2 < 0.1 6 4–8

* In fresh potato starch wastewater.

Castor cake is the residue of castor beans after oil has been pressed. Owing to its high protein concentration, castor cake contains 5 – 6 % N, which is
ammonified in soil quite rapidly and thus becomes plant-available. The fertilizers are only traded in sealed packages due to their allergenic properties.
Furthermore, the toxic substances ricin and ricinin must be destroyed by steam treatment at 120 °C for several hours, and dust has to be absorbed by treating

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the castor cake with linseed oil.

Cacao waste is a residue of cocoa production and has a lower N and P content and higher K content than castor cake.

Brewers' grains (water content 75 %) and rape (water content 40 – 60 %) result as waste from brewing and from production of fruit juices and wine. They are
used as fertilizers in fresh and composted form and have only a minor short-term effect on N supply.

Vinasse. Sugar-containing molasses is a waste material of sugar production from sugar beet. It is used for alcohol, yeast, and glutamate-production. The
remaining sugar-free molasses is concentrated to 60 – 70 % and is then used as sugar-beet vinasse, an organic N and especially K fertilizer. Vinasse has a
medium-term effect on N supply.

Pulp remains after alcohol production (distillery) from corn or potatoes (5 – 7 % dry matter). Potato pulp contains more K than corn pulp. Pulp has a medium-
term effect on N supply, because potato and corn protein must first be decomposed by microorganisms. Ten cubic meters of pulp is equivalent to 30 – 40 kg
N, 4 – 6 kg P, 5 – 40 kg K, and 200 – 300 kg C. Pulp is applied for fertilization as fresh material. Storage without addition of preservatives leads to unpleasant
odors [283].

Potato Starch Wastewater. The production of potato starch generates large quantities of potato starch wastewater, which is used as a fertilizer. Depending
on the production technique, 3 – 50 % of the total N is present in the ammonium form. Furthermore, the protein N is mineralized rapidly. Therefore, potato
starch wastewater has a short-term effect on N supply. It also has a high K concentration. Potato starch wastewater is classified as follows:

– Fresh potato starch wastewater (ca. 6 % dry matter; 1 L is equivalent to 60 g dry matter, 5 g N, 025 g P, 6 g K)
– Treated potato starch wastewater (e.g., protein precipitation, evaporation, partly mixed with wastewater), 1 – 5 % dry matter (in the case of storable syrup,
up to 55 % dry matter [284], [285])

Filtration diatomaceous earth is the filtration residue in breweries (75 % water content). Yeast proteins are the main N-containing substances. Owing to the
narrow C/N ratio, this waste material has a short-term effect on N supply.

4.6.4. Fertilizers Based on Municipal Waste

This group is represented by biogenic and garden composts as well as by sewage sludge. In Germany the produced nutrient quantity of secondary raw
material fertilizers is estimated at 270 000 t N per annum and 90 000 t P per annum, of which sewage sludge accounted for 60 % of N and 75 % of P.
Composts accounted for 20 – 25 % of N and P. This demonstrates the importance of nutrient recycling by utilizing these waste materials as fertilizers. The
precondition for recycling these wastes in agriculture and horticulture is a high quality standard, which strongly depends on the content of pollutants, especially
heavy metals, dioxines, and furans. In Germany legal provisions for the utilization of sewage sludge and biocomposts have already been set or are in
preparation (Waste Law, Fertilizer Law). These rules are likely to reduce environmental risks to a tolerable minimum and to promote the acceptance of the
secondary raw material fertilizers [275], [281], [282]. Lately, sewage sludge and biocomposts have been classified as organic NPK fertilizers in the group of
secondary raw material fertilizers [274].

Sewage sludge is mainly produced in municipal purification plants. Sewage sludge is classified into primary (residue after mechanical purification, deposits in
settling tanks) and into secondary sludge (residue after biological purification by biomass and chemical purification by precipitation). Generally, the two kinds of
sewage sludge are mixed and are subjected to various treatments. A precondition for the utilization of sewage sludge as fertilizer is an acceptable health
standard. In Germany pollutant concentrations of sewage sludge have been considerably reduced over the last 20 years (e.g., Cd, Figure 24). At present, the
average Cd concentration is 80 % lower than the threshold value specified in the decrees (AbfKlärV) for the utilization of sewage sludge (10 mg Cd/ kg dry
matter) [276]. In 1993 dioxin and furan concentrations averaged 27 ng/kg, well below the threshold value of 100 ng/kg dry matter. Adjustment of the threshold
values to the present quality standard is in preparation. In 1994 the average concentrations of heavy metals in sewage sludge applied in agriculture (in mg/kg
dry matter) were Pb 84, Cd 1.8, Cr 56, Cu 251, Ni 32, Hg 1.6, Zn 977, all well below the permitted maximum loads set in the decrees for the utilization of
sewage sludge (AbfKlärV) [276], [286].

Figure 24. Cadmium concentration in sewage sludge from 1977 to 1994 [286] (the dashed line marks the threshold value for agricultural use [276])

Depending on the pretreatment (dewatering; precipitation of P with Ca, Fe, Al salts; lime addition) nutrient concentrations in sewage sludge vary considerably
(Table 26). Therefore, the nutrient contents of these fertilizers must be routinely monitored and adjusted if necessary. The short-term effect on N supply
depends on the NH4 content (fraction of total N). The effect on P supply depends mainly on prior precipitation and pretreatment (lime addition, drying). The
applied amount of these fertilizers is determined by nutrient concentrations. For example, the input of P should correspond to the P removed by harvest. Thus
the applied quantity remains under the maximum amount of 5 t dry weight of sewage sludge per hectare in three years.

Table 26. Dry matter and nutrient contents of sewage sludge (in wt %) [275]

Dry matter N P K Mg CaO

Range 6 – 23 2 – 6 1.5 – 7.0 0.2 – 0.5 0.4 – 0.7 0 – 15

Maximum 75 25 15 40
Average 12 3.8 1.6 0.3 0.6

Biogenic and Garden Composts. Biogenic compost originates from biologically degradable waste, separated and collected in households. The portion of
biologically usable waste in total domestic waste is 30 – 40 wt %. Garden compost consists of waste materials of plant origin such as litter or remains from
pruning, collected in gardens, parks, and embankments and in National Parks. Composts represent the final product of a controlled rotting process in piles or
bioreactors. According to the extent of rotting, composts are characterized as fresh or mature composts. Biogenic wastes are subjected to biogas production
and subsequent composting.

As a result of the separate collection of the organic wastes, biogenic composts have lower pollutant concentrations than composts based on total domestic
wastes (Table 27). Heavy metal concentrations of biogenic and especially garden composts remain under the threshold values set in the decrees for the
utilization of biogenic composts (BioAbfV, in preparation). Average concentrations of organic pollutants (e.g., dioxins, furans) of 10 – 15 ng TE/kg dry weight lie
within the range of the unavoidable natural background load from the atmosphere. Nutrient concentrations of composts vary less than those of sewage sludge
but still have to be routinely monitored (Table 28). Garden composts have lower nutrient contents than biogenic composts. Compared to sewage sludge (high
N and P levels) composts have high K contents and mainly a soil-meliorating effect. The short-term effect on N supply is quite low (only 10 % of total N is
represented by mineral N). An effect on N supply is barely detectable after applications for several years. The maximum quantity of compost application is
likely to be restricted to 20 t (30 t in case of high quality , i.e., minor contents of heavy metals) dry weight over three years per hectare [i.e., 100 (150) kg ha
–1 a–1 of N) [287], [289], [275].

Table 27. Heavy metal concentrations in composts originated from domestic, biogenic and garden wastes (mg/kg dry matter) [287], [288]

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Element Domestic waste Biogenic waste Garden waste Maximum concentration (BioabfV *)

Pb 286 55 59 100 (150) **

Cd 3.9 0.4 0.4 1 (1.5)
Cr 60 27 28 70 (100)
Cu 261 50 36 70 (100)
Ni 40 15 14 35 (50)
Hg 2.6 0.3 0.2 0.7 (1)
Zn 1020 201 133 300 (400)

* BioabfV: Bioabfallverordnung (German Biowaste Regulations), August 1998.

** Maximum quantity of compost application: 30 (20) t dry weight over three years per hectare.

Table 28. Nutrient concentrations in composts (% dry matter) [275]

Compost from N P K Mg CaO Salts (g/L)

Biogenic wastes 1 – 1.8 0.2 – 0.5 0.5 – 1.3 0.3 – 1.6 1.7 – 9.5 3 – 9

Garden wastes 1.0 0.2 0.6 0.5 8.5 (1 – 6)

4.7. Manure
There are four types of animal manures: solid manure, liquid manure, slurry, and dry manure from poultry. Solid manure consists of feces, urine, and bedding.
Usually, solid manure contains 100 % of the feces; the fraction of the urine retained depends on amount and kind of bedding material, animal type, and the
way of housing. The most widely used bedding material is straw, but it can also be peat litter or sawdust. Liquid manure contains the urine of the animal
together with some rain water and cleaning water and small amounts of feces and bedding material. Slurry is a mixture of feces and urine with some additional
water and some bedding and feed material. Layer dry manure consists of the excrement layers from battery farming.

Solid manure production is the most frequent animal manure handling system for raising young layers, broilers, turkeys, and cattle, the latter especially on
smaller farms. For fattening pigs and cattle on larger farms, slurry systems have been favored in the last 30 years because production costs, especially labor
costs, are lower.

4.7.1. Composition [290-296]

A major fraction of the nutrients consumed by animals is excreted with the feces and urine. For nitrogen, this is ca. 70 – 80 % of the intake, for phosphorus ca.
80 %, and for potassium 90 – 95 %. Table 29 lists the nutrient amounts produced per year by various animals.

Table 29. Nutrient amounts excreted per year from various animals

Animal Nutrient amount, kg

N* P2O5 K 2O

Milking cow (6000 kg/a milk yield) 110 38 140

Fattening cattle (125 – 600 kg live weight) 42 18 44
Sow with piglets 36 19 16
Fattening pig 13 6 6
Laying hens (100) 74 41 33
Fryers (100) 29 16 16
Turkeys (100) 164 81 71

*Excluding gaseous losses from storage or application.

The nutrient contents of manures are affected by type of feed, kind and amount of bedding material, amount of water supply, and kind and length of storage.
Even for the same type of manure, the nutrient content can therefore show a wide range; deviations of more than ± 50 % from the average contents are
possible. Table 30 lists the average content of organic matter, nitrogen, phosphorus, and potassium in various types of manures.

Table 30. Contents of organic matter and nutrients in various manures

Manure type and amount Organic Nutrient amount, kg

matter, t N P2O5 K2 O

Solid manure, cattle, 10 t 2 54 32 70

Solid manure, pig, 10 t 2 80 80 60
Solid manure, fryer, 1 t 0.2 28 21 23
Solid manure, turkey, 1 t 0.2 23 17 16
Dry poultry manure, 1 t (50 wt % solids) 0.4 28 21 15
Slurry, cattle, 10 m3 (10 wt % solids) 0.7 47 19 62
Slurry, pig, 10 m3 (6 wt % solids) 0.5 56 31 30
Slurry, poultry, 10 m3 (14 wt % solids) 0.9 98 83 48

4.7.2. Manure Nutrient Efficiency[291], [294], [297-303]

Availability of Nutrients. In animal manures, phosphorus, potassium, magnesium, calcium, and the micronutrients are predominantly present as inorganic
compounds. Their plant availability is comparable to that of mineral fertilizers. The fraction of inorganic nitrogen depends on the type of manure (Table 31).

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The organic nitrogen becomes partly available to the crop after mineralization in the soil. In the long run and under optimal conditions, liquid manure reaches a
nitrogen fertilizer equivalent of up to 100 %, slurry 70 – 90 %, poultry excrement 60 – 70 %, and solid manure 50 – 60 %.

Table 31. Percentage of ammonium N and organic N in various manures

Type of animal Type of manure Percentage nitrogen as

Ammonium Organic

Various animals solid manure 15 85

Poultry dried feces 30 70
Poultry fresh feces 45 55
Cattle slurry 55 45
Poultry slurry 60 40
Pigs slurry 70 30

As for all fertilizers, especially with regard to nitrogen, the nutrient efficiency of manures is highly dependent on the application conditions. Especially for slurry
and liquid manure, spring application usually results in a much better nitrogen efficiency than autumn or winter application, especially in areas where nitrate
leaching occurs over winter. Ammonia losses can be kept low if slurry is incorporated into the soil as soon as possible after application.

Humus Effect. As shown in Table 30, animal manures contain an considerable amount of organic matter. This organic matter may increase the organic matter
content of the soil, depending on the application rate and the cropping system. Application of solid organic manures usually leads to a larger increase in
organic matter content than slurry due to the bedding material, which is low in N and hence less readily decomposable. The application of organic matter
improves soil quality in terms of water-retention capacity, turnover nutrient availability, and nutrient pore volume, and resistance to soil erosion.

4.7.3. Environmental Aspects [294], [295], [298], [304-307]

Environmental problems may result from inappropriate application of animal manures, especially at times when the crop does not require nutrients, at rates
which exceed the nutrient demand, or if animal manures are not incorporated into the soil immediately after application. The consequences can be:

– Nitrate losses due to leaching after nitrification of ammonium N or mineralization of organic N

– Ammonia losses from the soil or crop surface
– Potassium losses due to leaching on light soils
– Phosphorous accumulation in the top soil and in the subsoil; phosphorus leaching from peat soils

With the aim of decreasing nitrate leaching into ground water, some countries have established legal regulations that restrict the amount of manure and/or
timing of application (see Chap. Environmental Aspects of Fertilizer Application). A regulation to reduce ammonia losses from manure application and storage
has been implemented in the Netherlands.

[Top of Page]

5. Fertilizer Granulation
Heinrich Dittmar

5.1. Introduction
The granulation of fertilizers was one of the most significant advances in fertilizer technology, affording considerable advantages to both manufacturer and
user. Today, a well-defined grain size distribution is specified just as nutrient contents and good application properties are. Although the first granular fertilizers
came on the market between 1920 and 1930, a stronger trend toward granulation developed — especially in the United States — only after the end of World
War II.

In 1976, both granular fertilizers and bulk blends enjoyed shares of somewhat more than 40 % in the U.S. mixed-fertilizer market. Granular fertilizers were
losing ground against bulk-blend products and liquid fertilizers [313]. In 1990, the corresponding figures are about 63 % for bulk blends, 22 % for liquid
fertilizers and 15 % for granular fertilizers. In Europe, Africa, and Asia, granular fertilizers are the most frequently used form, far ahead of bulk blends and
fluids.

Advantages of Granular Fertilizers. Forming and subsequent conditioning are indispensable for the production of fertilizers suitable for use. It was
recognized at an early stage that fertilizers in powdered or finely divided form readily cake during storage. This is less of a problem with low-surface-area
granules. Only free-flowing materials allow mechanized handling and distribution. Granules often require less storage space because of their greater bulk
density: they are stored and transported more economically. A further advantage of granular fertilizers over powdered and crystalline products is that they tend
to produce less dust, so that product losses are reduced. A granular product with a definite grain-size spectrum is a prerequisite for uniform mechanical
application with field equipment (see Section Application): granules with diameters between 1 and 5 mm are most suitable. At the same time, losses caused by
the wind, and the accompanying environmental problems, are dramatically reduced. Moreover, granules produced from various feedstocks (solids, slurries,
melts) by granulation do not segregate, in contrast to bulk-blended products (Section Bulk Blending).

The use of granular instead of powdered fertilizers delays nutrient delivery to the plant until the granules have disintegrated completely (controlled delivery to
the plant, diminished leaching losses). In the case of some controlled-release fertilizers, larger granules release nitrogen more slowly (see Section Slow- and
Controlled-Release Fertilizers). Field studies in Swedish soils have shown that granular superphosphate with a grain diameter of 1 – 3.5 mm was twice as
effective as finely-divided fertilizers [314], since the granular form retards phosphate fixation in the soil [315]. This reported effect varies with the soil type, the
pH, the proportion of water-soluble P2O5 and the type of plant [316]. In the case of mineral fertilizers not containing P2O5 (N, NK, and NMg fertilizers),
however, the grain size has only a slight effect.

Definitions [312, Chap. 1].

– Straight fertilizer: a fertilizer containing only one nutrient.

– Compound fertilizer: a fertilizer containing two or more nutrients.
– Complex fertilizer: a compound fertilizer formed by mixing ingredients that react chemically.
– Granular fertilizer: a fertilizer in the form of particles between two screen sizes usually within the range of 1 – 4 mm.
– Prilled fertilizer: a granular fertilizer of near-spherical form made by solidification of free-falling droplets in air or other fluid medium (e.g., oil).
– Coated fertilizer: a granular fertilizer that has been coated with a thin layer of some substance to prevent caking or to control dissolution rate.
– Conditioned fertilizer: a fertilizer treated with an additive to improve physical condition or prevent caking. The conditioning agent may be applied as a
coating or incorporated in the granule.
– Bulk-blend fertilizer: two or more granular fertilizers of similar size mixed together to form a compound fertilizer.

Granulation Loop Granulation may be coupled with a production step, such as the manufacture of ammoniated triple superphosphate, or on the other hand it
may be only a forming step in a production process, for example, granulation in the nitrophosphate process [317]. But other production operations also come

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under the heading of granulation: the preparation of feed materials and, after forming, the steps of drying (Fig. 26), cooling, screening, comminution of material
with too large a grain diameter (oversize), recycling of this comminuted material and of material with too small a grain diameter (undersize) to the granulator,
and finally conditioning of the particles with the desired grain size (product fraction). The processing steps, linked into a loop by the recycle, are called the
granulation loop (Fig. 25).

Recycling is carried out for the following reasons:

1. The size distribution leaving the granulator differs from the required distribution
2. The ratio of liquids to solids in the available feed is in excess of the requirements for the desired size enlargement
3. Granulated material is recycled to provide nuclei for the granulation process

Processes which correspond to (1) may be described as granulation efficiency limited; an example is the agglomeration of low-solubility fertilizers. Condition
(2) is generally encountered where readily soluble or high water content feeds are agglomerated and can be described as liquid phase balance limited. Liquid
phase balance frequently leads to high recycle rates with consequently high processing costs (Chap. Costs of Agglomeration). For the control of granulation
see [318, p. 280]

Figure 25. Granulation loop

Figure 26. Drying drum, showing granulated product

Courtesy of BASF Aktiengesellschaft

The granulation efficiency often is defined as the mass fraction of particulate material that leaves the granulator as finished product, that is, with grain sizes in
the desired range (assuming 100 % sieve efficiency) [317]. It is also possible, however, to state the granulation efficiency as the mass fraction of finished
product at the dryer outlet [319]. This definition allows for some regranulation in the dryer. The mass ratio of material not withdrawn (recycled material) to
product is often referred to as the recycle ratio. For example, a 20 % granulation efficiency implies a recycle ratio of 4 : 1 if other losses are disregarded.

The recycle ratio is important to the process of granulation. Recycle is necessary because, after the product has passed once through the granulator, a certain
quantity of particles lies outside the desired region of the grain-size spectrum (off-size material) and must be run through again. For a given mixture and a
given temperature, optimal granulation takes place only within a narrow range of the solid-to-liquid ratio. The quantity of recycled fines depends not only on the
chemical properties of the materials but also on the water content of the slurry and on the granulation device [320]. Recycle is also needed to generate nuclei
for agglomeration and to stabilize the granulation conditions in the granulator.

The quality of the granules is influenced by the following factors:

– Type and fineness of the feedstock

– Moisture content of the granules
– Surface tension of the wetting liquid and wettability of the particles
– Mode of motion in the granulator
– Inclination and speed of the granulator
– Type and properties of the binder

Granulation Processes. Granulation processes can be classified by the nature of the feed materials to be granulated (i.e., granulation of solids, slurries, melts
[308, pp. 250 – 260], [313] ) and by the type of granulation equipment used. The most important types of equipment for granulating fertilizers are shown
schematically in Figure 27. For the most important fertilizer materials, both straight and multinutrient, Table 32 offers an overview of the main commercial
granulation processes, along with further possibilities.

Table 32. Equipment for granulation of fertilizer materials * [317]

Fertilizer material Granulation equipment: main commercial techniques are in boldface, while possibilities are in
normal typeface

Calcium nitrate prilling, flaking, pan granulator [322], drum granulator, compaction, pugmill/blunger [320]
Ammonium nitrate prilling [308, p. 103], [323], cold spherodizer [323], [324], pan granulator [322], [323], [325], [326],
drum granulator, fluidized-bed granulation [327], [328], spouted-bed granulation, TVA falling-curtain
drum granulation
Calcium ammonium prilling [309, p. 195], pugmill/blunger [308, p. 104], [309, p. 196], drum granulator, pan granulator
nitrate [322], [329], hot spherodizer, cold spherodizer, fluidized-bed granulation [327], [330], spouted-bed
granulation, TVA falling-curtain drum granulation
Ammonium sulfate pugmill/blunger [309, p. 205], drum granulator [331], prilling [309, p. 205], pan granulator [332]
nitrate
Ammonium sulfate crystallization, hot spherodizer, compaction, pipe reactor-drum [333]
Urea prilling [323], [328], [334] cold spherodizer [323], [324], pan granulator [322], [323], [325], [326],
[335], crystallization, drum granulator [336], [337], compaction [338], fluidized-bed granulation [328],
spouted-bed granulation [339], TVA falling-curtain drum granulation
Urea with ammonium prilling [341, pp. 71 – 73], cold spherodizer, pan granulator [342], fluidized-bed granulation [340],
sulfate spouted-bed granulation, TVA falling-curtain drum granulation
Superphosphate drum granulator [343], pan granulator [309, p. 234], pugmill/blunger
Triple superphosphate drum granulator [308, p. 191], [344], pan granulator [309, p. 348], pugmill/blunger [308, p. 191],
[344], compaction
Monoammonium drum/ammoniator-granulator [311, pp. 6 – 8], [345], [346], pugmill/blunger [311, p. 30], [347], prilling
phosphate [311, p. 8], [347], crystallization, compaction
Diammonium ammoniator-granulator [311, pp. 6 – 8], [345], [346], [348], crystallization, pugmill/blunger [346],

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phosphate [347], [348], compaction
Ammonium ammoniator-granulator[311, p. 217], pugmill/blunger [311, p. 217]
polyphosphate
Nitrophosphate (NP) hot spherodizer, prilling [349], [350], pugmill/blunger [320], [351], pan granulator [332], [351], drum
granulator [351], [352], fluidized-bed granulation
Potash compaction [353], crystallization
PK drum granulator [343], pan granulator, pugmill/blunger, fluidized-bed granulation [354]
Nitrophosphate (NPK) hot spherodizer [324], [355], [356], prilling [349], [350],
pugmill/blunger [320], [346], [355], [356], pan granulator [357], drum granulator [345], [346], [351],
[355], [356], fluidized-bed granulation, compaction [317]
Compounds on drum/ammoniator-granulator, pugmill/blunger, hot spherodizer, prilling
ammoniacal base
Compounds with ammoniator-granulator, pugmill/blunger, hot spherodizer, drum granulator, prilling
ammonium nitrate
Compounds with urea drum/ammoniator-granulator, pugmill/blunger, hot spherodizer, compaction, prilling
Compounds with ammoniator-granulator, pugmill/blunger, hot spherodizer, drum granulator, compaction
micronutrients

* Compaction is illustrated in Figure 34. The equipment for the other processes is illustrated in Figure 27.

Figure 27. Granulation equipment [321]

A) Pugmill (blunger); B) Rotary drum; C) TVA ammoniator – granulator drum; D) Spherodizer process; E) SAI-R drum granulator; F) Inclined pan granulator; G)
Fluidized-bed granulator/drier; H) Air-cooled prilling tower

5.2. Granulator Feedstocks

Granulation of Solids with Water or Aqueous Solutions. A solid phase (dry mixed nongranular or powdered material) and a liquid phase or steam
(granulation aid) are required. Steam is discharged under the bed of material at the feed end, and water is sprayed on the bed through spray nozzles. For
each mixture there is a percentage of liquid phase at which granulator efficiency is optimum. The higher the temperature, the less water and hence less drying
is required [308, p. 251]. The system is granulation-efficiency controlled. Granulation takes place by agglomeration of the particles. The granulation efficiency
is high and the recycle ratio is low (roughly 1 : 1). Examples are the granulation of superphosphate (with and without simultaneous ammoniation), the
granulation of superphosphate in the presence of (NH4 )2SO4 and K2SO4, and the granulation of monoammonium phosphate together with other nutrients
[313] to yield high-analysis formulations. While the granulation of solids has proved to be a flexible and economical process, it has the drawbacks of
diminished quality as to physical properties and appearance. What is more, the P2O5 component (monoammonium phosphate or superphosphate) has to be
prepared in a separate plant [313]. For an example of granulation with a solid P2O5 component, see [358], [359]; for granulation of NPK fertilizers containing
urea, see [360].

Slurry Granulation. The materials to be granulated are in the form of a slurry, usually derived from reaction of sulfuric, nitric, or phosphoric acid with
ammonia, phosphate rock, or a combination thereof. In some process modifications, solid materials may be added to the slurry before or during granulation
(Fig. 28). Slurry granulation is liquid-phase controlled. Usually a thin film of a slurry having the fertilizer composition is sprayed onto small solid particles. The
granules are built up in layers (layering process). The process is mainly controlled through the recycle and the slurry water content (the recycle ratio may be
5 : 1 or more [313]). Granulation is aided by various impurities (Al/Fe compounds, organic substances); see [320]. Drying can be combined with granulation
into one processing step. A modification of the slurry process is the Spherodizer process developed by C & I Girdler (Section Drum Granulator). Slurry
granulation is widely practiced in Europe for the production of N, NP, and NPK fertilizers. In the United States, the process has been modified so that acids,
phosphoric and/or sulfuric, or partly neutralized acids are completely ammoniated in the granulator (ammoniator – granulator, Section Drum Granulator) [361].
For example, (NH4 )2SO4 can be granulated in a drum by this method [414].

Figure 28. Slurry granulation process [317, p. 23]

Granulation with solutions or slurries includes fluid-bed spray granulation (mechanism of agglomeration [362], [363]) and spray drying. In the continuous fluid-
bed spray granulation process, solutions, suspensions, or melts can be converted to a granular product in a single step [364]. In contrast to spray (flash)
drying, this process can be made to yield granules with a particle size of up to 5 mm [365]. The liquid for granulation is sprayed through nozzles located in or
above the fluid bed onto the particles, which comprise comminuted oversize or undersize from the cyclone separator. Warm air in the fluid bed promotes the
drying of the particles, and the sprayed particles increase in size. If melts are sprayed into the bed, cold fluidizing air carries off the heat of solidification.
Fluidization is accomplished by blowing air through a plenum with a grid. Agglomeration with urea, NH4NO3, and K3PO4 has been reported [362].

Spray or flash drying represents a direct path from the liquid product to granules. The end product ranges from a powder to a fine grit. The feed liquid is
atomized hydraulically, through feed nozzles, or pneumatically, with two-fluid nozzles or atomizer disks. The solution is sprayed into a tower-like vessel with a
hot air stream and thus solidified into the fine granules. The dry product is removed pneumatically and collected in a cyclone system, or it can be removed with
a bucket wheel at the bottom of the tower [366]. A few special fertilizer products are made by spray drying.

Fluidized-bed methods include the NSM process (Fig. 29) [327], [328], [370, pp. 277 – 288]. The granulator is a rectangular vessel with a perforated plate at
the bottom to provide a uniform distribution of air. The fluid bed, which is initially made up of fines, has a height of 0.5 – 2 m and an area of several square
meters. It is subdivided into chambers to obtain a narrow gradation in the end product. The granulation liquid or melt is sprayed into the fluid bed in each
section by air. Heavier particles, which remain in the bottom portion of the fluid bed, can pass into the next section or to the outlet. In this way, the granular
product migrates through the fluid bed from the first to the last section. The NSM plant has a capacity of 800 t/d for urea, and the production costs are less
than those for prilling. For the properties of slurry granulation processes, see [367], [368]; for studies on the layering process, [369]. For fluid-bed granulation,
see [363].

Figure 29. NSM fluidized-bed granulator [327, p. 7]

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A modification combining granulation and drying in a variant of the fluid-bed process is the “spouting-bed granulator” [313], [371], [372]. The conical vessel
stands on end, with a Venturi tube at the bottom, the narrowest section; into this section, either hot air propels a hot saturated solution or cold air propels a
melt. The fluid bed is set up in the cone. The fast-moving particles require no perforated distributor plate. Drying or cooling takes place rapidly, and the material
builds up in onion fashion. The dust collected in the cyclone is recycled (2 : 1 recycle ratio) [313]. Granulation tests on ammonium sulfate in the spouted bed
have been reported [373]. Despite successful pilot tests, no full-scale unit has yet been built [371].

Melt Granulation. Spherical agglomerates produced from the melt (e.g., urea and ammonium nitrate) are called prills. These are usually obtained by spraying
a salt melt or a highly concentrated solution into the top of a tower. The melt should have a very low viscosity (< 5 cP) but a high surface tension at
temperatures just a few degrees above the melting point [374]. The liquid jet breaks up into droplets in the free air space. As they fall in contact with
counterflowing cool air, the droplets solidify. The tower height (and thus the falling distance) and the velocity of the cool air are adjusted so that the prills are
sufficiently hard when they strike the bottom of the tower [329]; tower heights are typically 45 – 55 m for ammonium nitrate [396]. The prills can be removed
with scrapers or belt conveyers, or they can be cooled in a fluid-bed cooler located at the bottom end of the prilling tower [375]. Alternatively, the heat of
crystallization can be carried away by spraying the droplets of melt into an oil bath. This is done, for example, with calcium nitrate [376], which is subsequently
centrifuged and screened [377].

The recycle ratio in prilling is ca. 0.1 – 0.2 [315]. The prill, with a diameter of 1 – 3 mm, is usually smaller and rounder than the particle obtained by granulation.
Because of the high air throughputs in the prilling space and the resulting off-gas problems, and also because of the smaller particle size, prilling has lost
importance [315]. For small capacities, such as 250 t/d, granulation is economically superior to prilling; for high capacities, from 1000 t/d up, conditions
determine which process is more economical [315], [378]. SCHOEMAKER and SMIT present a comparison between granulation and prilling in the manufacture of
fertilizers [379]. For the prilling of NPK mixtures consisting of NH4NO3, NH4H2PO4, and KCl, see [374].

For tests of oil prilling of a urea – ammonium sulfate mixture (34–0–0–9S), see [341, pp. 71 – 73], [342]; for tests of oil prilling of urea – ammonium
polyphosphate mixtures, see [382]. Monoammonium phosphate can be obtained in melt form with a pipe reactor and sprayed into a prilling tower (Swift
process) [347].

Multinutrient fertilizers mostly have high melting points and are very viscous [313]. One exception is a mixture of monoammonium phosphate and ammonium
nitrate, which melts at a low temperature and has a low viscosity. The melt is granulated in a drum (recycle ratio 1 : 1). Depending on whether KCl is added in
the granulator, formulations such as 24–24–0 and 17–17–17 are obtained. In a TVA process [380], phosphoric acid and NH3 are reacted in a T reactor to yield
an anhydrous melt; this can be granulated by itself to an ammonium phosphate/ammonium polyphosphate mixture (from 11–55–0 to 12–57–0) [313], or urea
can be added to obtain a 35–17–0 or 28–28–0 granular product. If KCl is added, 19–19–19 can be produced [313], [381]. Granulation takes place in a drum or
a pug mill (cf. Sections Pug Mill and Drum Granulator).

Melt-granulation processes have the advantage that a dryer, which is otherwise the largest and most expensive unit in granulation plant, can be dispensed
with [308, p. 256]

5.3. Granulation Equipment

The condition for granulation is that a bed of solid particles moves, with simultaneous intensive mixing, in the presence of a liquid phase. This motion provides
the particle collisions and bonding needed for granule growth. There are many types and models of granulating equipment, most of which use one of three
basic intensive mixing mechanisms [321]:

1. Rotation of one or more shafts carrying staggered paddles in a fixed trough (pug mill, blunger).
2. Rotation of the whole device, such as drum or pan.
3. Movement of particles by a third phase, as by blown air in a fluid-bed granulator. In slurry granulation the third phase is usually hot air or hot combustion
off-gases, which can serve as a drying medium at the same time. In this way, two processing steps in the granulation loop can be carried out in a single
apparatus [365].

In order to improve pelleting conditions or pellet qualities, binding agents can be added along with the granulation liquid. The binding agents may be solid or
liquid, may form films, crusts, or crystals, and may harden at standard temperature or at higher temperature [383].

Because granules can also be obtained by dry compaction, the compactor should be considered as a granulator here.

Various authors have reported data on granulators [309], [317], [321], [352], [384-388]. RIES has attempted to classify granulating equipment and processes
[366], [389-391].

The granulating devices used most often in the fertilizer industry are drums, pans, and pug mills. While fluid-bed granulation has come into use in the fertilizer
field, mixer – granulators and compactors are more frequently employed to form fertilizer granules. Spray drying and extrusion processes are used only for
special fertilizer products.

5.3.1. Pug Mill

A pug mill (Fig. 27 A) consists of a U-shaped trough and, inside it, one or two shafts bearing strong paddles staggered in a screw-thread fashion. In frequency
of use, two-shaft pug mills are dominant [317]. The shafts rotate at equal speeds in opposite directions in the horizontal or slightly inclined trough. The solid
particles (fresh feed plus recycle) are fed in at one end of the trough and are thrown up in the middle of the trough, where they are wetted with the granulation
liquid. In the trough, the paddles move, knead, and transport the moistened particles toward the discharge end. The particles can be given a better-rounded
external shape either in a downstream tumbling drum or in the feed zone of the drying drum. Placement of a perforated NH3 inlet pipe (sparger) at the bottom
of the trough makes it possible to ammoniate and agglomerate the fertilizer at the same time. The pug mill is sturdy and can adapt to variable service
conditions; it produces hard granules of uniform composition [321]. If the angle between the paddles and the shafts is optimized, the energy consumption can
be reduced. The paddles are usually provided with a wear-resistant coating to prevent abrasion [320]. Processes have been described for granulating in a pug
mill an ammonium polyphosphate melt (12–57–0), and the same melt with urea (28–28–0) [380], and the same with KCl (19–19–19) [341]. For tests on 35–
17–0, see [392]. The combination of a pipe reactor with a pug mill for the granulation of NPK has been reported [393].

5.3.2. Drum Granulator

The drum granulator (Fig. 27 B and Fig. 30), which is the type of granulator in widest use for fertilizers, is an inclined rotating cylinder. The rotation speed is
usually adjustable. For a given drum and a given granular product, there is an optimal peripheral speed that gives the highest yield of granules.

Figure 30. Drum granulator

Courtesy of BASF Aktiengesellschaft

An inclination of up to 10° from the horizontal ensures adequate movement of product toward the discharge end. Because, however, this inclination is not
enough to effect classification, the discharged product has a fairly broad grain-size distribution, in contrast to the pan-granulator product (Fig. 31A).

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Figure 31. Schematic representation of granule development in the drum granulator (A) and pan granulator (B) [394]

Drums in which the lengthwise axis is inclined upward from the feed end to the discharge [395] give a narrower particle-size spectrum. Such an upward
inclination also increases the drum fillage.

In drums currently used in the fertilizer industry, the length-to-diameter ratio is ≥1 and may reach 6 : 1. The feed end may have empirically designed
distributing elements on the inside wall to spread the feed material. In the adjacent part of the drum, where the granulation liquid is fed in, a good tumbling
motion should be ensured. This can be achieved with light lifting flights, but they must not lift the granulate too high. In the remainder of the drum, the
pregranulated material should be tumbled to a round shape and further compacted. This is also achieved with light flights on the wall and an appropriate
fillage. The fillage in the spray and tumbling areas can be controlled by means of internal ring dams. The cylinder may be either open ended or fitted with ring
dams at the ends [396] to prevent overflowing at the feed end and to control the bed depth and thus residence time. Fixed or movable scrapers inside the
drum or hammers or other rapping devices outside on the drum can be used to remove or reduce excessive product caking inside the drum. Some material
buildup on the drum wall may promote granulation [397]. Cylindrical drums are used for continuous granulation with and without internals.

As in the case of the pug mill, recycled product (undersize) generates a moving bed of material in the drum; a slurry containing, say, 3 – 8 % water can be
sprayed onto the bed [309].

Powdered feed materials (mixed and wetted in an upstream mixer if necessary to provide granule nuclei) can be granulated in the drum through spraying with
water, solutions, suspensions, and highly concentrated slurries, or through blowing with steam. The bed volume should be 20 – 30 % of the cylinder capacity
[398]. The recycle ratios for drum granulation are generally between 1 : 3 and 1 : 6. Optimization of these plant parameters for each product class is done by
trial and error.

The drum granules are better rounded but less dense than the pug-mill granules [321]. Drums 4.5 m in diameter and 16 m long are in use in the fertilizer
industry.

An important modification of drum granulation is the TVA ammoniator – granulator (Fig. 27C and Fig. 32) [308, pp. 250 –260], [399-401]. This is a drum
roughly equal in length and diameter, with ring dams at the ends but no lifting flights. Ammonia reacts with phosphoric and sulfuric acids below the surface of
the tumbling bed of fresh feed and recycle. The reaction generates heat, which vaporizes the water at the same time that granulation takes place. The heat is
removed by injected air. The ammonia and the acids are supplied to the bed through perforated distribution pipes mounted parallel to the drum axis. The
requisite bed depth is ensured by the ring dam at the drum discharge. In a modern process, a mixture of phosphoric and sulfuric acids and ammonia is
neutralized in a pipe-cross reactor situated upstream of the granulating drum (Fig. 33). The slurry is then fed to the drum along with recycle. While more
phosphoric acid is sprayed onto the tumbling bed, ammonia is fed into the bed [313]. In this way, NPK fertilizers can also be produced [335, pp. 44 – 48]. In
the SA CROS process for monoammonium phosphate production, phosphoric acid and ammonia are mixed and reacted in a pipe reactor. The slurry is
distributed over the tumbling bed together with the steam generated; no subsequent ammoniation takes place in the bed [402]. For granule improvement with
an interstage pan, see [403]. The use of the pipe reactor in combination with the granulating drum for the manufacture of granular ammonium phosphates was
introduced by TVA in 1973 [311, p. 45] and was later incorporated in many plants [404]. A possible improvement in the drum granulator is represented by the
double-pipe granulator, which is especially well-suited to fertilizer mixtures with a high proportion of recycle (Scottish Agricultural Industries system, Fig. 27 E)
[309], [405]. For example, by virtue of the high recycle ratio with corresponding residence times, a hard ammonium nitrate – ammonium phosphate mixture can
be granulated.

Figure 32. Ammoniator – granulator plant for NPK mixtures [317, p. 23]

Figure 33. Location of pipe-cross reactor and spargers in ammoniator – granulator [313, p. 87]

a) Ammonia sparger; b) Phosphoric acid sparger; c) Pipe-cross reactor; d) Scrubber liquor

Reprinted by permission of John Wiley & Sons, Inc.

Another modification of the drum granulation process described is the spray-drum process (Spherodizer, Fig. 27D). In a rotating drum, preneutralized slurry is
sprayed onto a dense curtain of granules cascading from baffles inside the drum. The water content of the slurry must be, say, 12 – 18 % to allow good spray
dispersion [309]. During granulation, hot combustion gases flow through the drum in cocurrent [406], so that drying takes place at the same time. The dried
particles are then sprayed again, redried, and so forth. The grains grow in shell fashion with an onion structure and are very hard. Spherodizer units are built in
capacities of up to 650 t/d. Such an apparatus has a diameter of 4.5 m and a length of 12 m [309]. The Spherodizer, developed by C & I Girdler [407], [408],
was first used on an industrial scale in 1959. The cold and hot used for the versions of the Spherodizer describe the condition of the air that flows through the
drum. The cold version is used with melt feeds, especially ammonium nitrate and urea, while the hot version serves for granulation and spraying with slurries
(NPK fertilizers, nitrophosphates, ammonium phosphate – nitrate, urea – ammonium phosphate) [317]. Granulation and drying thus take place in the same
device. Under optimal service conditions, the recycle ratio is approximately 1 : 1.

A combination of drum granulation and fluid-bed technology is embodied in the Kaltenbach-Thuring Fluidized Drum Granulation (FDG) process [325, p. 39],
[409], [410]. The technique is suitable for both melt and slurry granulation (e.g., size enlargement for urea and ammonium nitrate prills).

In a drum, the best granulation takes place at 25 – 45 % of the critical rotation speed [361], which is the rotation speed at which the weight of the granules and
the centrifugal forces are in balance [386], [318, p. 204]:

D = drum diameter, m
= drum inclination
Ncrit = critical rotation speed, rpm

5.3.3. Pan Granulator

The tumbling motion of granules during agglomeration can also take place on a rotating inclined pan (Figs. 27 and 31 B).

For a given pan size, if the inclination of the pan axis to the horizontal is increased, the granules roll upward less steeply but have a longer residence time in

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the pan. The granulation nuclei and the small granules initially move in the vicinity of the pan bottom. During granulation, the rotation of the pan and the force
of gravity cause them to take up a spiral path. The particles grow and eventually reach the bed surface. The spiral diameter decreases continuously until the
granules, finally becoming large enough, run over the rim of the pan (Fig. 31 B). Melts or slurries are often sprayed onto the bed, but water or solutions can
also be used as granulation aids, and steam can be injected into the bed. If water is employed, it should be applied in the region of the largest spiral diameter
[320]. Experience has shown that the spray liquid must be dispersed more finely, the finer the solids for granulation [413]. Because the overflow product has a
rather uniform grain size, downstream classification can often be dispensed with. By means of an advancing and retreating scraper blade, the pan bottom can
be kept fairly clean and the formation of crusts can be avoided. Here, as in the drum, some material coating the pan prevents wear and promotes the correct
tumbling action [396]. The pan can also be made in the shape of a truncated cone or can have at its periphery a tumbling ring, onto which the granules fall
from the pan rim; surface coating agents can be applied. Pan granulators are manufactured with diameters of up to 7.5 m [317]. Typically, the height of the rim
is one-fifth of the diameter.

Concentrated salt melts of urea, ammonium nitrate, or calcium nitrate can be processed in the pan granulator; the products are easily applied fertilizer pellets,
and an alternative to prills [322], [323], [383], [415].

For the production of granular triple superphosphate, phosphoric acid is added to digest finely milled crude phosphate in a granulator – mixer; this step yields a
moist, crumbly product, which is directly processed in a subsequent pan to the required pellet size with the injection of steam and the addition of hot
phosphoric acid [383]. For the pan granulation of urea – ammonium sulfate mixtures, see [342].

The relationship between the critical rotation speed and the pan diameter and inclination is the same as for the drum granulator [396].

In general, pan rotation speeds are n ≈ 0.6 – 0.75ncrit, where ncrit is the critical rotation speed; the pan axis is usually inclined at 45 – 55 ° to the horizontal
[411]. According to the TVA [412], the optimal angle is ca. 65 °. The throughput of a pan granulator can be calculated roughly as follows [386]:

= throughput, t/h
k = factor ca. 0.95 – 1.1 for mixed fertilizers
D = pan diameter, m

5.3.4. The Granulator – Mixer

While the pan granulator must be fed with powdered or pre-pelleted material, the granulator – mixer can accept friable, plastic, pasty, or crumbly feeds. If the
mixing elements move at the proper speed, the material is comminuted to the desired grain sizes [383]. The disintegration of hard agglomerates is made
possible by cutter rotors mounted at the sides of the mixing space [416]. Granulator – mixers are often used in batch operation, while pan granulators are run
continuously. Process engineers in the fertilizer industry have also combined the two kinds of apparatus with the mixer upstream to improve product quality.
The mixing vessel itself either has a fixed position or may rotate, while the movable mixing elements (e.g., mixing stars, spirals, shafts with attached vanes,
plowshare mixing elements) effect intimate mixing and thus granulation by virtue of their rotation. The shape and rotation speed of the mixing elements are
usually variable and can be adapted to a range of mixing and granulation jobs. Wear of the mixing elements must be expected. The mixing vessel proper can
have a variety of shapes: smooth pipe, zigzag rotary pipe, pan, cone, Y, tub, and so forth. The mixer is often provided with external auxiliary heating. The liquid
used for granulation can be fed to the mixing space and distributed by means of a hollow shaft [385], but suitable openings and feed pipes on the vessel can
also feed in the liquid. For granulation – mixing of fertilizers, the device has a specific energy consumption of 2 – 6 kW per 100 kg of product [417]. The
granulation time can be taken as 5 – 10 min. Grain sizes between 0.1 and 5 mm are achievable. The capacity is up to 30 000 kg/h per mixer [366]. RIES
compares the grain-size distribution curves of fertilizer granules from granulator – mixers with those of the starting fineness [418].

5.3.5. Roll Presses

The size enlargement of a finely dispersed charge material by external compression is implemented in press agglomeration (Fig. 34). The charge is gripped by
two counterrotating rolls, nipped in the gap, and compressed. As the void volume decreases, the material generally undergoes a two- to threefold compaction.
While a charge hopper is adequate for a free-flowing material, a material that is not sufficiently free-flowing can be transported to the nip by screw feeders, with
some precompaction. If the rolls are smooth, the material exiting from the nip (“shell”) has a smooth surface. If the rolls have mating depressions, briquetts are
produced. The shells are next reduced to the desired grain size (in a crusher or mill) and screened. The fines and oversize are recycled (Fig. 35). Rolls are
manufactured in diameters up to 1.4 m and widths up to 1.5 m [390]. They may be mounted side-by-side or over-and-under.

Figure 34. Press agglomeration with smooth rolls [386, p. 215]

a) Rolls; b) Crusher; c) Screen

Figure 35. Compacting of a multinutrient fertilizer [419, p. 34]

For the specific compressive forces for urea, KCl, and (NH4 )2SO4, see [353]; for data on the compaction of special fertilizers, [420], [421]; of K2SO4, [320]; of
calcium cyanamide, [422]. For a general description of fertilizer compaction, see [423], [424]; for a monograph on roll pressing, [425]; for the principles of
pressure agglomeration, [419].

5.4. Costs of Agglomeration

The costs incurred for granulation depend not just on the agglomeration properties, but — for equal or nearly equal agglomeration properties — on the size
and type of equipment used in the process. For equipment and investment costs for pan granulators, drums, mixers, and roll-compaction equipment, and on
hourly operating costs versus equipment size, see [426]. With regard to personnel, mixers and roll presses are considered to require one-half man (year-
round, rotating shifts), while pans and drums are figured at one man each. In contrast to dry compaction (roll presses), drying costs have to be added in for
mixer granulation. Up to a certain moisture content, mixer granulation with drying is quite competitive with dry compaction. For processes and costs of
agglomeration, see also [427]. In comparing the granulation of solids and slurries, the investment costs are one-third higher for slurry granulation, and the
operating and utility costs are likewise greater [313].

For production costs with various granulating equipment, see [428], [429]. For a cost and process comparison between prilling and granulating, see [378],
[430]; for the costs of granulating monoammonium phosphate and diammonium phosphate, [311]; for the costs of NPK granulation in the Norsk Hydro
nitrophosphate process, [349]; for the costs of fertilizer compaction, [431]. For economic aspects and comparative estimates of manufacturing costs, see [308,
pp. 138, 266].

5.5. Bulk Blending

The mechanical mixing of single components in granular form, called bulk blending, is a special way of producing multinutrient fertilizers. Bulk blending was
introduced in the USA at the beginning of the fertilizer industry [447]; it is not nearly so widespread in Europe. In the process, several of the usual starting

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components, such as superphosphate, triple superphosphate, monoammonium phosphate, diammonium phosphate, urea, and potassium chloride, are
combined in an uncomplicated device such as a rotating drum. The nutrient ratio can be adjusted as desired. The components are briefly mixed (up to 15 t/h)
and made available to the farmer in batches that are usually loaded directly into the distributor.

The precondition for this process is that the components in the mixture be physically and chemically compatible [317], [448]. For example, urea and
ammonium nitrate must not be present together, since a mixture of these is very hygroscopic and tends to deliquesce. Further, stoichiometric mixtures of urea
and ammonium nitrate are sensitive to impact, and even a solution of the two can form an explosive mixture [449]. Mixtures of urea or diammonium phosphate
with normal or triple superphosphate have only limited compatibility. If an aqueous salt mixture has a somewhat elevated pH and simultaneously contains
ion, NH3 may be liberated.

Bulk blending has the drawback that segregation can occur during silo filling, packaging, transportation, and application. A uniform grain size or grain-size
distribution is essential for reducing segregation, even if the particles differ in density. Design measures at the silo inlets and inside the silos can prevent
segregation [335, pp. 37 – 39]. Drum mixing generates dust, which may necessitate cleanup measures depending on the amount of dust and the size of the
mixing equipment.

The process has the advantages that the N : P2O5 : K2O ratio desired by the farmer can easily be obtained; micronutrients, insecticides, and herbicides can
easily be metered in, and the dealer requires less storage space.

For the production of bulk-blended urea with an appropriate gradation, see [370, pp. 277 – 288]. For the bulk-blending system in the United States, see [447],
[450-452]; for the use of mechanical fertilizer mixing in Germany, see [453].

5.6. Quality Inspection

For successful handling and application, certain ranges of physical properties must be specified for the fertilizer particles. Quality control, which includes
chemical analysis as well, is performed by the fertilizer manufacturer. For the determination of the physical properties of mineral fertilizers, see [308], [432-
434].

Grain Shape. Fertilizer particles should have the least possible surface area, since irregular shapes lead to increased abrasion and a tendency to cake.

Grain-Size Spectrum. The diameter of ordinary commercial fertilizer grains is in the range of 0.5 – 6 mm. U.S. products generally have a somewhat finer size
spectrum (primarily 1 – 3.35 mm) [317] than European products (primarily 2 – 5 mm). In exceptional cases, the product grains may be coarser, as in the case
of a woodland fertilizer applied from the air (6 – 12 mm), or finer, as in the case of ammonium sulfate and crystalline mixed-salt fertilizers (< 2 mm) and other
special fertilizers. The grain-size distribution is important for the intended application, for example to ensure uniform distribution of fertilizer nutrients by field
equipment. The grain-size spectrum is determined by screen analysis (ISO 8397 standard screening). For the grading curves of granular fertilizers in
comparison to the starting fineness, see [418].

Settled Density. The settled density is important for the sizing of packaging equipment and storage areas. For a given fertilizer grade, it should fluctuate as
little as possible. The settled densities of granular fertilizers can be determined in accordance with ISO 3944; those of finely divided fertilizers (with a high
content of <0.5 mm), in accordance with ISO 7837.

Compacted Density. The compacted density is generally as much as 10 % higher than the settled density. It represents the maximum bulk density that can
be achieved through vigorous shaking. The compacted density can be measured in accordance with ISO 5311.

Dumping Angle. The dumping angle (angle of slope) of a fertilizer is important for the design of storage areas and for transportation. The dumping angle
should be as large as possible and can be measured in accordance with ISO 8398.

Grain Hardness. The grain hardness is a measure of the fracture strength of fertilizer grains and their mechanical stability in storage. As a rule it is measured
by placing grains of a definite size between two parallel plates and compressing [435].

Abrasion Resistance. The abrasion resistance is a measure of the mechanical stability of fertilizer grains moving against one another and of their stability in
free fall (wear due to tumbling and dropping). Abrasion causes dusting of the fertilizers during storage operations, transportation, and application. The abrasion
resistance should be as great as possible and can be determined with, for example, the TVA method [308].

Caking Tendency. One of the most important properties of a fertilizer is its storability, which can be determined through measurement of its tendency to cake.
By careful drying and effective surface treatment (see Section Fertilizer Conditioning), the caking tendency can be significantly reduced and thus the storage
qualities improved. This property is measured by, for example, a shear test on caked fertilizer.

Hygroscopicity. The hygroscopicity of a fertilizer characterizes its sensitivity to atmospheric humidity. Grains of a highly hygroscopic fertilizer exposed to
sufficiently high air humidity take up moisture, which impairs their initial grain hardness and abrasion resistance. The hygroscopicity of a fertilizer is assessed
from the water-vapor adsorption isotherm. The rate of water uptake and the critical relative humidity of the salt system can also be determined [434], [436].
Critical humidities are listed in [437]. Corresponding to the critical relative humidity is the partial pressure of water vapor over a saturated salt solution forming a
very thin skin of liquid over the salt surface. If the humidity of the ambient air is less than critical, the liquid skin gives up water; if greater, the product gains
moisture.

5.7. Fertilizer Conditioning

A conditioner is a material added to a fertilizer to promote the maintenance of good physical condition (flowability) during storage and handling. The use of
conditioners is essential with many products, but is not required with all fertilizers. It is preferable to use other means, such as good drying, to avoid caking.
Even if the fertilizer grains are dried adequately from an economic standpoint, caking may occur and impede storage, transportation, and field application.

Hardening and caking result from the crystallization of water-soluble salts and the formation of bridges between the grain surfaces during storage. The
surfaces also suffer plastic deformation under pressure, and the reduction of the water vapor pressure in the joint between the new contact surfaces causes
the particles to adhere to one another [438]. The reaction

during storage may also be indirectly important in poor storage qualities [315, p. 370], [439].

The internal conditioning of fertilizers means incorporating additives in the granules before or during granulation to improve the physical properties and the
anticaking qualities. Internal conditioners usually act as hardeners or crystal modifiers, for example to improve the storage properties of ammonium nitrate
fertilizers. Internal conditioners inhibit or modify the effects of crystal phase inversions due to temperature changes during storage. The inversion at 32 °C can
cause uninhibited ammonium nitrate granules and prills to shatter and cake. In the case of urea prills and granules, 0.2 – 0.5 % of formaldehyde or urea –
formaldehyde is added to the urea melt as a hardener and anticaking additive [308, p. 301]. The addition of 1.8 % Mg (NO3)2 protects ammonium nitrate from
caking. The destructure effect of the phase change at about 32 °C is avoided [440, p. 200].

External conditioning, also called coating and surface treatment, means applying to the granule surface a thin layer of powders or surfactants to reduce the
caking tendency. The addition of wax and/or oil enhances the action by suppressing dust formation. This process step is carried out in a rotating drum or a
fluid bed. Although coating with a fine, inert powder (kieselguhr, talcum, lime, kaolin) has long been practiced as an external form of inorganic conditioning,
surface treatment with nonionic organic sealants (polyethylene waxes, paraffins, urea – aldehyde resins) and coating with surfactants to make the grain
surface hydrophobic came into use later. The surfactants employed are, above all, fatty amines and sulfonates. These are also used [315] in combination with
powders and waxes and/or oils [370, pp. 289 – 303]. For the use of special oils as anticaking agents, see [441]; for an example of a surfactant, [442]. For
special coatings to prevent caking, see [443]. Because of the many anticaking agents and fertilizers in production, no overall recommendation can be made as
to special additives for general use [438].

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Intentional aging of fertilizer in a storage pile prior to bagging or bulk shipment is referred to as curing. In products that benefit from curing, chemical reactions
that cause caking bonds apparently proceed to near completion during the curing period. The heat of reaction retained in the curing pile speeds the completion
of the reactions. After curing there is reduced tendency for additional bonds to develop [308, p. 302]. In the manufacture of superphosphates, pile curing for
about 30 d frequently is employed to improve physical properties.

5.8. Environmental Aspects

In fertilizer plants, the gaseous effluents from all equipment handling solid materials, including screens, have to be cleaned owing to their content of fine dust
(and harmful gases). Although the most serious dusting occurs during the drying of granular fertilizers, dust is also formed in the granulators. These units are
therefore operated under a partial vacuum. The dust in the off-gas is usually collected in cyclones and recycled. When dry dust collection is inadequate, wet
separation in scrubbers, which also absorb gases like NH3, is employed. Recycling of the scrub waters is implemented in the AZF process [444]. For NPK
fertilizers, experience has shown that a soft granular product has a stronger dusting tendency than a hard one. For certain fertilizer formulations, less dust is
produced from the drum than from the pug mill [445].

Gaseous effluents like ammonia, nitrogen oxides, and fluorine compounds are evolved in the production of NPK fertilizers and feedstocks. Normally these
exhaust gases are scrubbed, and the resulting scrubber liquors are recycled to the process.

Liquid or aqueous effluents from fertilizer plants are usually of smaller volume compared to those vented to the atmosphere [308, p. 322]. They generally result
from scrubbing equipment and can be concentrated and recycled. Spills and washings are usually collected in floor sumps and also concentrated and
recycled.

For the removal of emissions from fluid-bed granulators, see [370, pp. 277 – 288]; for fluorine emission in triple superphosphate production, [446]; for a
summary of environmental practices in the fertilizer industry, [308, pp. 319 – 328].

[Top of Page]

6. Analysis
Vilmos Czikkely and Titus Niedermaier

The point and purpose of fertilizer analysis is to check the declared fertilizer grade and confirm that the contents of grade-determining components, nutrients,
nutrient forms, nutrient solubilities, and incidental components are as printed on the bag. In the Western countries, all fertilizers are subject to official
inspection, and the laws permit only small deviations within given limits.

In nearly every country, only products with established compositions and analyses are allowed in trade; therefore, inspections must be performed during
production, and factory laboratories must use testing methods in compliance with the established official techniques of analysis (Table 33)

Table 33. National and international standards for fertilizer analysis

Method European Federal Republic International United States (AOAC)

Economic of Germany [455] Organization for [457]
Community [454] Standardization [456]

Sampling and sample No. L 213 on pp. 2 – No. 1.1, 1.2, 1.3 ISO 3963; ISO 5306; No. 2.1.01 – 2.1.05
4
preparation (see Section EN 1482 DIN/EN 1482 ISO 7410; ISO/DIS 7742
Sampling and Sample
Preparation)
Nitrogen analysis (see Section
Determination of Nitrogen)
Total nitrogen No. 2.3; § 7.1 in No. 3.5 (3.5.1 – ISO 5315 No. 2.4.02 – 2.4.06
No. 2.6.1; § 7.2 in 3.5.5)
No. 2.6.2
Ammonia and nitrate N 2.2 (2.2.1 – 2.2.3) No. 3.3 (3.3.2 – ISO 11 742 No. 2.4.09 and 2.4.10
3.3.4)
Ammonia N No. 2.1; § 7.2.5 in No. 3.2.1 – 3.2.6 ISO 5314, ISO 7408 No. 2.4.07 and 2.4.08
No. 2.6.1 and § 7.5
in No. 2.6.2
Nitrate N § 7.2.4 in No. 2.6.1 No. 3.4.1 and ISO 4176 No. 2.4.11 and 2.4.12
and § 7.4 in 3.4.2
No. 2.6.2
Urea N § 7.2.6 in No. 2.6.1, No. 3.8 (3.8.1 – ISO 8603 No. 2.4.20
§ 7.6 in No. 2.6.2 3.8.5)
Controlled-release N EN 13 266 No. 3.10 in preparation
Phosphate analysis (see
Section Determination of
Phosphate)
Extraction No. 3.1.1 – 3.1.6 No. 4.1.1 – 4.1.7 ISO 5316, ISO/DIS 7497 No. 2.3.01, 2.3.06,
2.3.11, 2.3.14,
Dissolved phosphate No. 3.2 No. 4.2, 4.3 ISO/DIS 6598 No. 2.3.02 – 2.3.05,
2.3.07 – 2.3.09, 2.3.12 –
2.3.14
Potassium analyses (see No. 4.1 No. 5.1, 5.2 ISO 5317, ISO 7407, No. 2.5.01 – 2.5.08
Section Determination of ISO 5310
Potassium)
Other analyses (see Section
Analysis of Calcium,
Magnesium, and Trace
Elements)
Calcium No. 6.1 and 6.2 ISO/CD 10 151 No. 2.6.01, 2.6.05 –
2.6.07
Magnesium No. 8.1, 8.3, 8.6, 8.7 No. 7.1 and 7.2 ISO/CD 10 152 No. 2.6.01, 2.6.17 –
2.6.21
Sulfur No. 8.1, 8.2, 8.4, ISO 10 084 No. 2.6.28
8.5, 8.9
Micronutrients No. 9.1 – 9.11 Chap. 8 (8.1.1 – No. 2.6.01 – 2.6.04,
8.9.2) 2.6.10 – 2.6.16, 2.6.22 –
2.6.25, 2.6.29 – 2.6.32

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6.1. Sampling and Sample Preparation

Sampling must produce a sample that corresponds to an exact, representative average of a large product batch. The most appropriate time for fertilizer
sampling is during bagging or when the bulk product is being loaded into conveyances. Only when sampling at this time is impossible should samples be taken
from closed bags or from a bulk product stockpile. As a rule, the sample taken should make up at least 0.1 % by weight of a batch for delivery. Fertilizer
regulations also contain provisions for sampling methods. A minimum requirement is given in EN 1482.

A suitable sample divider is next used to reduce the sample quantity to some 1 – 2 kg. The final sample must be prepared for analysis by comminution,
screening, and homogenizing. The smallest portion called for by the analytical technique must still be representative of the whole final sample. At the same
time, this preparation must not alter the gradation of the fertilizer in such a way as to have a marked effect on typical properties such as the solubility in
extractants.

6.2. Determination of Nitrogen

The most important nitrogen compounds are nitrates, ammonium salts, urea, urea – aldehyde condensates, and cyanamide. Farm-produced fertilizers (e.g.,
liquid manure) have most of their nitrogen in organic form (protein).

Total Nitrogen. The analytical method for determining total nitrogen is dictated by the components present in the fertilizer. For straight N fertilizers that contain
only ammonia nitrogen, e.g., ammonium sulfate, it is sufficient to alkalize the sample solution and distill the liberated ammonia into an acid of known
concentration in the receiving flask. For samples containing nitrate, on the other hand, the nitrate content must be reduced first. Examples of ways to reduce
the nitrate are with iron or chromium powder in an acid solution, with ARND alloy in a neutral solution, or with DEVARDA alloy in an alkaline solution. Nascent
hydrogen reacts with the nitrate to give ammonia in quantitative yield. Distillation from the alkalized reaction solution gives the sum of ammonia N and nitrate
N.

For fertilizers that contain other forms of N besides ammonia and nitrate, the reduction step must be followed by the conversion of the other N forms (urea,
cyanamide, protein) to ammonia by Kjeldahl digestion.

The final determination of total N in every case is by distillation of ammonia from the alkalized pretreated solution into a receiving flask with an acid standard
solution and backtitration of the residual acid excess.

Ammonia Nitrogen Apart from Other N Compounds. In theory, the ammonia component is easily isolated from commercial mixed-salt fertilizers by
distillation from sample solutions alkalized with NaOH or KOH. Urea and other organic N forms readily give additional ammonia in alkaline solution. If such
compounds are present, the distillation conditions must be kept as mild as possible. The solutions are alkalized with soda, calcined magnesium oxide, or
freshly precipitated calcium carbonate, and the ammonia liberated is distilled under reduced pressure at room temperature or with the help of a strong air
purge.

For pure ammonium salts of strong acids, the formaldehyde method offers a quick procedure for ammonia determination. The reaction of ammonium ion with
formaldehyde

liberates protons equivalent to the ammonium ions present; these can be directly titrated with sodium hydroxide standard solution.

Nitrate Nitrogen Apart from Other N Compounds. In many cases, nitrate N is determined as total N minus ammonia and urea N. The most versatile direct
method is precipitation of the nitrate with nitron and final determination by gravimetry. Another sensitive method, recommended for specially formulated mixed
fertilizers with low nitrate contents, is a colorimetric technique based on the nitration reactions with 2,4- or 3,4-xylenol. The nitration products give intensely
colored compounds in alkaline solution.

Urea Apart from Other N Compounds. Three different methods are available for the selective determination of urea:

1. Separation of urea by precipitation with xanthydrol(9-hydroxyxanthene), yielding dixanthylurea; gravimetric final determination
2. Enzymatic hydrolysis of urea, controlled by ureases; distillation of produced ammonia into a receiving flask with acid standard solution, where it is
absorbed
3. Colorimetric method (for low urea contents) based on the reaction of urea with p-dimethylaminobenzaldehyde

Nitrogen Fertilizers with Controlled-Release Urea – Aldehyde Condensates. Ureaform, Isodur, and Crotodur are nitrogen compounds that are only slightly
soluble in cold water but are nonetheless effective as fertilizers. The delayed water solubility provides a basis for the analytical characterization of these
compounds: extraction with cold water isolates the readily available N components (ammonium, nitrate, free urea). Only when the extraction residue is treated
with hot water do isobutylidene diurea, crotonylidene diurea, and the short-chain components of the urea – formaldehyde condensates go into solution.

In an acid medium, especially at high temperature, condensates of urea with formaldehyde and with isobutyraldehyde tend to hydrolyze to urea and the
aldehyde. In mixed fertilizers with an inherent acid tendency, there is thus a danger of altering the solubility characteristics in the course of the analysis. For
this reason, the separations are carried out in buffered solutions of pH 7.5 [455].

To calculate the percent N contents, either the total N is determined in the extraction solutions or else the AOAC procedures for urea – formaldehyde
condensates are carried out and a nitrogen activity index is determined.

where CWIN is cold-water-insoluble nitrogen and HWIN is hot-water-insoluble nitrogen.

The nitrogen activity index for urea – formaldehyde condensates is around 50; crotonylidene diurea and isobutylidene diurea have values of more than 90.

6.3. Determination of Phosphate

Because phosphorus fertilizers are rated by their contents of phosphate available to plants, various extraction methods have been devised.

Extraction with Water. Most countries define water-soluble phosphates as those components that go into solution at room temperature when an aqueous
suspension is made with 1 g of sample to 50 mL of suspension volume (in the USA, 1 g of sample to 250 mL).

Extraction with Citrate Solution. The technique of citrate extraction determines phosphates, such as CaHPO4, that are insoluble in water but soluble in
complex-forming salt solutions.

The most common methods in Europe use ammonium citrate solutions with a prescribed citrate concentration. The officially approved extraction processes
differ in the choice of pH. Extraction is performed in a strong alkaline medium with an ammoniacal ammonium citrate solution, or in a neutral ammonium citrate
solution. Most often, extraction is carried on for 30 min at room temperature and is followed by a treatment at 40 °C; for the EEC process with neutral
ammonium citrate solution, 65 °C is prescribed.

Extraction with Citric Acid Solution. Originally, the citric acid solubility was stated only for Thomas phosphate, but the lack of agreement between the plant
availability of P2O5 and the solubility in ammoniacal citrate solution led to other straight and mixed phosphate fertilizers being rated by citric acid solubility.
Treatment with 2 wt % citric acid solution (5 g of sample is agitated in 500 mL of citric acid solution for 30 min at 20 °C) dissolves phosphorus – silicon

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heteropolyacids, which are hardly soluble in complex-forming salt solutions.

Extraction with Formic Acid Solution. Soft and hard phosphate rock can be distinguished by their behavior in 2 % formic acid. A 5-g ground rock sample is
shaken at 20 °C for 30 min with 500 mL of the formic acid solution. In the case of soft phosphate rock, 50 – 70 % of the total phosphate dissolves; in the case
of hard phosphate rock, only ca. 25 % dissolves.

Extraction for Total Phosphate Determination. A technique applicable to all fertilizers as well as crude phosphates is digestion with sulfuric acid, nitric acid,
and copper sulfate. Mixtures of hydrochloric and nitric acids or nitric and perchloric acids have also been proposed for quantitative extraction.

Determination of Phosphate. After hydrolysis of polyphosphates in acid solution, if necessary, phosphate is precipitated as quinolinium molybdatophosphate
and weighed. Possible substitutes for the gravimetric final determination are methods in which the precipitate, washed acid-free, is dissolved with an excess of
sodium hydroxide standard solution and back-titrated with nitric acid standard solution. Reaction of the dissolved phosphate with a molybdate – vanadate
solution yields a soluble, colored heteropolyacid complex, which can be determined by colorimetry.

6.4. Determination of Potassium

For almost all fertilizers that contain potassium, this component is dissolved in water. In complete fertilizers, it is advisable to perform the extraction in acid
solution so that, if gypsum is present, none of the potassium will take part in double salt formation and remain undissolved as syngenite. For the determination,
the potassium is precipitated with sodium tetraphenylborate from a weakly alkaline or acidic solution; the product, slightly soluble potassium tetraphenylborate,
is weighed. Another proposal, mainly in the USA, is to precipitate the potassium as the chloroplatinate (AOAC). Flame photometry is also recognized as an
official test method.

6.5. Analysis of Calcium, Magnesium, and Trace Elements

Complexometric methods with EDTA have come into widespread use for determining calcium and magnesium. Photometric techniques for the determination
of other metal ions effective in growth (Cu, Fe, Mn, Zn, Co, Mo) have been described. To an increasing extent, however, atomic absorption spectrophotometry
has gained in importance. Emission spectral analysis with plasma excitation is also used in fertilizer analysis. But this procedure is new, and as yet no official
analytical specifications exist for it.

Boron must be isolated by distillation in the form of methyl borate before it can be determined. The boric acid is reacted with 1,1-dianthrimide or azomethine H,
and the colored product is determined by photometry. For boron contents of 0.1 % and higher, boric acid and polyhydric alcohol (usually mannitol) are reacted
to give didiolboric acid, which is determined volumetrically.

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7. Synthetic Soil Conditioners

Reinhardt Hähndel and Hans Prün

Soil conditioners are substances with which the soil and substrate properties, seldom ideal for the growth of plants, can be optimized and stabilized. Their
purpose is to exert biotic, chemical, or physical influences on soils in such way as to improve the soil structure and water regime [462]. Synthetic soil
conditioners have well-defined composition, stable quality, and properties suited to the requirements they must meet. They may, for example, supplement or
replace natural substances that are unsuitable from an environmental and ecological standpoint, are in scant supply, or must be conserved.

7.1. Foams
Foamed polystyrene and foamed urea – formaldehyde resin are used as soil conditioners; foamed phenolic and polyurethane resins are used as florists'
mounting media or plant growth media [458].

7.1.1. Closed-Cell Expandable Polystyrene Foam

Expandable polystyrene (PS) foams consist of polystyrene pre-expanded by blowing agents at temperatures of about 100 °C and, after holding, expanded with
steam. The forms used for soil conditioners are flakes, beads, or raspings [458-460], [463], [464].

Physical and Chemical Properties. Expandable PS foams have closed cells. They contain 98 % air by volume and can hold 1 – 2 % water on their surface
[465], [466]. They do not, however, absorb water. Air exchange does take place [467]. Styromull foam flakes are 4 – 16 mm in diameter with a loose density of
12 – 20 kg/m3 [459]. The permeability to water between expandable PS flakes without compression is roughly the same as that of fine gravel; under 25 %
compression, it matches that of coarse sand; at 75 % compression, that of fine sand.

Expandable PS foams are largely resistant to attack by acids and alkalies; they are odorless, chemically neutral, and unobjectionable to plants. These foams
have been considered resistant to degradation by soil bacteria. Physical degradation takes place under the action of ultraviolet radiation, and biodegradation,
especially by soil fungi, yields carbon dioxide and water [467]. This process is slow, however, so that the foams are effective soil conditioners with a relatively
long lifetime.

Raw Materials. Styrene.

Use. Expandable PS foams in comminuted form for soil application have been described [468], [469]. Uses range from incorporation into soils and garden
substrates to the conditioning of weak-structured peat [470].

Incorporated, they have soil-loosening, aerating, and draining actions. Foams are also employed as soil conditioners in crop farming and landscaping, and
they have proved useful as drainage aids in slit drainage and as filter materials for covering drain pipes [458], [471], [472].

For soil aeration and structural stabilization around the roots of urban trees, expandable PS foam beads (1 – 2 mm diameter) are recommended for use with
soil aeration equipment (e.g., Terralift) [473], [474].

Trade Names. Hygropor, Styromull (BASF, Ludwigshafen, Germany); Styrofoam (Dow Chemical, Midland, Mich.).

7.1.2. Primarily Open-Cell Urea – Formaldehyde Resin Foams

Urea – formaldehyde foams consist of condensates of urea with formaldehyde in a well-defined molar ratio. They are solid foams with rigid walls and little
flexibility. The materials used as soil conditioners are mainly urea – formaldehyde foams modified for plant compatibility.

Physical Properties. Urea – formaldehyde foams can be produced with densities of 2 – 50 kg/m3 (as water-free uncomminuted material); foams with a
density of 22 kg/m3 are used for mixing into soils and substrates. Packed moist from processing, urea – formaldehyde flakes (trade name Hygromull) weigh
approximately 35 – 40 kg/m3.

The cell walls are partly open. They are thicker, and the cell volumes smaller, the higher the density. Cell diameters lie between 100 and 300 µm [460], [475],
[476]. The capillarity is low (1 – 2.5 %); the capillary elevation is 300 – 400 mm [460]. The capillary elevation for a garden substrate treated with foam is
described as advantageous [477].

The grades used as soil conditioners are made water-absorbing by modification of the condensate resin and comminution to flakes measuring 4 – 20 mm.
Under vacuum, the water capacity is more than 90 vol % [478]; for Hygromull flakes having a density of 22 kg/m3, this corresponds to 4100 wt %. The water
capacity can be determined appropriately by the method of DIN 11542 (1967). At atmospheric pressure, the initial water uptake is slow but rewetting is very
fast [478].

Water release is uniform and goes to completion without losses due to evaporation, so that the water stored in the foam flakes can be economically utilized by

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plants. The water is held in place by suction forces of pF 1.2 – 2.54 (cf. Section Soil Water – Plant Relationships; see Ceramics, General Survey, for
definition of pF). Urea – formaldehyde foams in a loose bed have the permeability of moderately fine sand; under 25 – 35 % compression, that of fine sand
[479].

Chemical Properties. As the condensation product of urea and formaldehyde, the foams are synthetic organic substances. Incorporated into moist soils and
substrates in flake form, they are known to be biodegradable. At pH 6 – 7, the process goes at 3 – 5 % per year [480]; at pH 3.9 – 4.1, degradation is speeded
up (15 – 20 %), especially at temperatures over 40 °C. The stability falls off rapidly above 80 °C. In horticultural substrates, steam sterilization is tolerated up to
a maximum of 1 h.

The components of the urea – formaldehyde foams are readily biodegradable: The urea component mineralizes to ammonium and is then converted
microbially to nitrate. The formaldehyde component is liberated upon mineralization; it undergoes microbial degradation in 48 – 72 h in soil or water, even
more quickly in air. Bioaccumulation does not occur [481].

A theoretical effective lifetime of some 20 – 30 years is desirable for soil conditioning [462], [482].

Raw Materials and Manufacture. A process, part of which has been patented, is used to produce foams from modified urea – formaldehyde condensation
products with compressed air, foaming agents, and hardeners in fixed or mobile equipment [483].

In Germany, the maximum allowable workplace concentration (MAK) in production is 1 ppm formaldehyde; this level may be exceeded only for short periods
and within limits. In the United States, the absolute MAK is 3 ppm.

Use. The use of urea – formaldehyde foams as soil conditioners has been described by DOEHLER [484]. BAUMANN advanced their use (1953 – 1968) and
developed the Plastopanik technique [459]. Foams were brought into reproducible use through extensive research [458], [460], [462], [470], [485], [486].

For reasons of cost, applications cluster in the areas of garden crops, such as pot and container plants, cut flowers (e.g., carnations, chrysanthemums), flower
bulbs, fruits (including strawberries), vegetables, and eucalyptus, and in landscaping, where foams are used in newly seeded lawns and woods, in the
transplanting of large trees, and in sports areas and golf courses.

In terms of soil physics, urea – formaldehyde foams optimize the air and water regimes in soils and substrates. They enhance the pore volumes, the
maximum, minimum, and plant-available water capacity, and the aeration, and they lower the soil density. Plants respond with improved shoot and root growth,
better early growth and development rates, and increased crop yields and qualities [462].

Trade Names. Hygromull, Hygropor (mixtures of Hygromull with Styromull) (BASF Aktiengesellschaft, Ludwigshafen); Agricon (Intrinco, Vaduz, Liechtenstein).

Official licenses have been issued for Hygromull and Hygropor in Austria, Belgium, France, Luxembourg, the Netherlands, Norway, Spain, and Switzerland
and also for Agricon in Saudi Arabia and other Middle Eastern countries.

7.2. Colloidal Silicates

Colloidal silicates include compounds of polysilicic acid, produced and stabilized mainly by synthetic means, with a high content of reversibly soluble silicic
acid and added flocculating electrolytes [460], [462], [487-489].

Agrosil colloidal silicate consists of (1) partly dehydrated sodium silicate, precipitated (neutralized) with acids, (2) electrolytes (phosphate, sulfate), and (3) an
organic additive to retard aging. Official licenses have been issued for it in Austria, Belgium, Denmark, France, Luxembourg, the Netherlands, Norway, Spain,
Sweden, Switzerland, and some Middle Eastern countries.

Physical and Chemical Properties. Colloidal silicates are solid, fine-grained, and thus easily distributed substances that can be dispersed with water to form
silica gels and silica sols. Silica gels, examined under the electron microscope, are described as porous; they exhibit surface activity for the addition and
inclusion of water and nutrients [490], [491]. Incorporated into soils, they fill the voids between soil particles [492] and bind these together with organic and
inorganic complexing agents to form water-stable crumbs [462], [493-496]. Pore redistribution takes place in this process [490], [497]. Sorptive salt buffering
has been described in soil mixtures [488], [491], [498].

The chemical activity is ascribed in particular to the low-molecular-mass silica sols. In the soil, they enable the holding of phosphate in solution or its activation
by desorption [490]; depending on the pH, they can irreversibly fix heavy metals [461], [462], [499-504].

Raw Materials and Manufacture. Raw materials for the production of Agrosil colloidal silicate are spray-dried and liquid sodium silicate, phosphoric and
sulfuric acids, and an organic aging retardant such as urea, humic substances, pectins, or proteins. The manufacturing process is patented [505], [506].

Use. Colloidal silicates are conceived as soil supplements or soil conditioners [462], [488], [493]. To a certain extent, they make it possible to return soils
affected by salts and heavy metals to agricultural use [462].

Their action as soil conditioners depends on their incorporation in the soil and their ability to take up water (precipitation, irrigation). Quantities used per are
(= 102 m2 ) are 7 – 20 kg, preferably 10 – 15 kg. In gardening and landscaping, they have an effective lifetime of 3 – 5 years; aftereffects in unworked soils
have been seen for 10 and 14 years.

Direct effects due to soil conditioning include improved water and sorption capacities, the activation of plant nutrients in the soil, physical improvement of soil
structure through pore redistribution and crumb formation; and the fixing of heavy metals (such as Cd, Cu, Pb, and Zn) in the presence of alkaline earths.
Indirect effects include improved soil life (respiratory activity and nodule bacteria), the release of excess water (a consequence of crumb formation), and
enhanced phosphate mobility. The growth of new shoots and roots is encouraged, both organic and inorganic substances are accumulated in the vegetation in
greater quantities, less water is needed, wilting of grass is reduced, and fungus and bacteria resistance is increased [462], [507].

In the Swiss classification, the product is not classed as toxic.

Trade Names. Agrosil (Guano-Werke AG, BASF).

7.3. Polymer Dispersions and Polymer Emulsions

Poly(vinyl acetate), poly(vinyl propionate), butadiene – styrene copolymer, cis-butadiene, and various acrylic acid polymers have been described and
employed as soil conditioners with actions in and on the soil [460].

Physical and Chemical Properties. The products are mainly applied to the soil surface in aqueous solutions. They cross-link the particles of the uppermost
soil layer and, depending on the concentration of the active agent, form a closed film or networklike coatings. These are permeable to precipitation but
diminish evaporation. Incorporated into the soil, they promote crumb formation [494].

As organic substances with a relatively high dilution, polymer dispersions are degraded relatively quickly by UV radiation when on the surface of the soil and
by microbial action when in the soil. Their action is therefore limited in time, and their stability depends on ambient conditions such as cold and heat.

Raw Materials. Polyacrylamides and Poly(Acrylic Acids); Polyacrylates; Poly(Vinyl Esters); Rubber, 3. Synthetic

Use. Polymer dispersions are employed chiefly for seed protection in landscaping, and also in vegetable and flower-bulb growing. They are applied at planting
time by spraying, usually along with fertilizers and soil conditioners (e.g., Agrosil) or mulches (cellulose, straw). They can also be applied after planting by area
spraying or, in the case of vegetables planted in rows, by stripe spraying [508].

The quantities used depend on the product and vary between 10 and 50 g/m2 ; the dilution with water depends on the purpose and varies between 1 : 1 and

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1 : 60 (product : water).

The duration of the structure-stabilizing or protective action depends on the quantity used [509] and on environmental conditions such as weathering and
insolation.

Polyacrylates and polyacrylamides are recommended for use alone or with, e.g., starch to promote water storage in soils [460], [510-515]. The waterholding
effect is, however, greatly diminished by pH values higher or lower than 7.0, water hardness, and dissolved substances such as urine or soil nutrients. No
satisfactory practical solution has been found for these limitations [516], but more recent generations of these so called superabsorbers are claimed to be more
tolerant towards dissolved salts. Various applications to gardening substrates and flower-growing soils have been described [517].

Polymer formulations are used for protection against erosion, especially in conjunction with the sprouting of seeds. They perform an environmental function by
offering limited protection to the seeds or small plants against wind and rain erosion until the plants are large enough to protect themselves. They are of
increasing importance in furrow irrigation systems in North America for preventing soil erosion and increasing water infiltration into the soil. A concentration of
10 ppm in the irrigation water is necessary to achieve the desired effects [518]. Biodegradability is a prerequisite for the soil and plant application of selected
polymers. Biodegradability is not assured in the case of some polyacrylates.

Trade Names. Curasol for poly(vinyl acetate) (Hoechst Aktiengesellschaft, Frankfurt); Hüls 801 for cis-butadiene (Chemische Werke Hüls, Marl); Aqua-Gel for
polyacrylate plus starch (Miller Chemical and Fertilizer Corp.); Hydrogel Viterra for poly(ethylene oxide) (Union Carbide Corp., New York); SGP Absorbent for
sodium polyacrylate plus starch (General Mills Chemicals, Inc., Minneapolis, Minn.); Soiltex G1 for polyacrylamides (Allied Colloids).

7.4. Tensides
Many tensides have been tested as soil conditioners, including ammonium laureth sulfate, ethoxylated alkyl phenols, polyoxyethylene esters of alkylated
phenols, polyoxyalkylene glycols and their polymers, polyoxyethylene, polypropoxypropanol glycol butylesters, alkyl polyglycosides, sulfosuccinates, and poly
(propylene oxide)s. The hydrophobic ends of the molecules of the these so-called wetting agents are adsorbed by water-repellent organic matter, and the
hydrophil ends link the soil particles with water.

Use. In turfgrass culture thatch accumulation may occur due to reduced decay of the organic matter of the grass sward. Under dry conditions, this material
becomes hydrophobic, and irrigation results in water losses because of poor infiltration rates and run-off [519], [520]. Spraying of wetting agents onto the
affected areas at a rate of 10 – 20 L/ha increases water absorption and efficiency. Solid formulations are also available.

Trade Names. Primer (Aquatrols, USA); wetx'tra (Rhône Poulenc, France); Turf Ex (Service Chemicals, UK), Saturaid (Debco, Australia).

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8. Storage, Transportation, and Application

Karl-Heinz Ullrich and Hermann Mühlfeld

Fertilizers are produced continuously, year-round, in large capital-intensive plants, but they are sold only in a few months at the beginning of and during the
vegetation period. Large quantities must therefore be stored for long times. The logistic of delivering the product to the user at the proper time leads to a
subdivision of storage into plant storage, dealer storage, and user storage. In this way, loading and transport are spread evenly through the year, with
additional control by seasonally varied sales rebates.

The construction and operation of storage facilities depend on the size, the location, the type of fertilizer, and the danger level, all of which are dictated by the
product.

8.1. General Storage Requirements

Fertilizers are classified as follows by danger level:

– Group A. Explosive fertilizers, such as those with a high ammonium nitrate content or with a low ammonium nitrate content and > 0.4 wt % organic
matter.
– Group B. Fertilizers in which self-sustaining, progressive thermal decomposition (low-temperature decomposition) is possible. In the past this group
comprised mainly multinutrient fertilizers which contain ammonium nitrate. Today, the ammonium nitrate based multinutrient fertilizers which are marketed
are almost exclusively rated Group C.
– Groups C and D. Fertilizers that do not explode and are not susceptible to self-sustaining, progressive thermal decomposition.

The precise classification is set forth by law [521]. With its technical regulations, the German regulation concerning hazardous substances
(Gefahrstoffverordnung) prescribes in detail how to construct and to operate storage facilities for ammonium nitrate based fertilizers. How many regulations
have to be observed depends on the classification of the fertilizer. The strictest standards apply for Group A, followed by Group B. For nonflammable fertilizers
(Groups C and D), the normal storage conditions for bulk materials apply.

Most fertilizers come in granular form and readily absorb moisture. As a result, they experience caking or granule disintegration; either effect makes application
more difficult. The storage areas must therefore be dry. Not only the roof and walls must be tight, but the floor must be safe against rising moisture. Care must
also be taken that moisture does not get into the storage building because of too much air circulation. Doors and windows must be kept closed when the
relative humidity is over 65 %. The surface : volume ratio in storage should be as small as possible.

Fertilizers containing ammonium nitrate, especially calcium ammonium nitrate, must be protected from direct sunlight and from repeated temperature changes
at 32 °C, because otherwise repeated recrystallization leads to granule disintegration.

When ammonium nitrate fertilizers are heated above 130 °C, low-temperature decomposition sets in, generating gases that may be toxic, depending on
concentration. Practices must therefore be employed that safely prevent the action of fire or external heating. Such practices include general fire-protection
measures such as no smoking, no use of fire or open light, and no unauthorized entry. Ammonium nitrate fertilizers must not be mixed with flammable
materials (sawdust, coal dust, sulfur, petroleum, etc.) or with acidic or basic substances (lime, basic slag phosphate, acid salts, etc.). Welding and burning
work may be carried out only with the most stringent safety precautions. Electrical equipment must be located outside the fertilizer pile. Cables and wiring must
be located at least 0.5 m above the highest possible pile level. Special care should be taken that the pile does not cover up lights, especially portable lights
connected by cable to the power supply.

With regard to moving mechanical parts (belt, screw, and bucket conveyors, etc.), care must be taken that these devices cannot run hot or experience fertilizer
buildup at critical points. Diesel and gasoline trucks that go directly into the storage area represent a danger due to hot exhaust gases and hot mufflers.
Hardened fertilizers must be loosened mechanically, not with explosives.

Low-temperature decomposition can be detected by white or brown smoke or a piercing smell. If this process develops and is recognized promptly, the
sintered reaction zone can be separated from the unreacted fertilizer. Good access is needed, and precautions are needed to keep the sizable amounts of gas
evolved from being a health hazard. If safe access is not possible, the decomposition must be brought to a stop by cooling with water. If any low-temperature
decomposition takes place, an alarm must immediately be sent to the fire-fighting service.

Fertilizers affect most of the conventional building materials, especially when wet. Steel, aluminum, and zinc suffer more rapid corrosion and must be protected
by several coats of paint (total thickness > 180 µm). Fertilizer dust can cause brittle fracture at welds in steel. Subsequent welding must be carried out with
special care.

Mineral fertilizers attack concrete more or less severely, causing scaling and corrosion of the steel reinforcement. For this reason, concrete floors contacted by
fertilizer should be protected by filled coal-tar pitch or epoxy-based plastic.

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Wood, especially in the new form of glued lamellae, is a suitable material. Care should be taken to use corrosion-resistant fasteners.

Plant Storage. Storage at the fertilizer plant is almost always in bulk form. Large warehouses, with capacities of up to and beyond 50 000 t for one or more
grades, are employed. The total storage capacity is usually several months' production. The size, shape, and outfitting of the warehouses depend on the
frequency of shipping, the number of grades, the required loading capacity, and the area available. In order to reduce the risk, some grades are limited as to
amount stored in a single warehouse, which may be accomplished by dividing the building. Large quantities are stored in elevators (tower silos) only under
some restrictions, because of the risk of caking and the resulting high reclaiming cost.

If enough space is available and shipments are not frequent, a flat-floor warehouse in which material can be piled more or less high against the walls is the
most economical design. Trough-shaped or basin-shaped storage structures with appropriate reclaiming equipment are used when space is limited and
intervals between shipments are short.

The material used for the foundation and walls is usually reinforced concrete; the roof is most often made of wood. Glued lamellar wood construction makes it
possible to span wide buildings without posts. Fertilizer can be piled against the walls to a height of 10 m or more. However, if the pile is too high, the material
can segregate during placement. Slides during reclaiming are also a problem if material is piled too deep. The plant warehouses generally need not be heated,
since the fertilizer leaves the production facility at a temperature of 35 – 45 °C (not over 50 °C). On the other hand, overhead conveyors and loading apparatus
spanning moderate distances should be heated to keep them dry.

Piling is done mainly with overhead belts at the center or side, with transverse distribution by belts, chutes, or discharge pipes. Newer facilities have a
distribution control room with closed-circuit television units.

Reclaiming capacity must be several times piling capacity. Because requirements vary, several methods have been devised. For high capacity and short
shipment intervals, track-borne scrapers capable of automation are used. Bridge cranes are also employed. Many wheeled tractor loaders are in service; these
can be shifted from one location to another, easily replaced if damaged, and reinforced if necessary. All warehouse equipment moves material by way of
transfer hoppers to conveyor belts, troughs, or bucket conveyors, which carry the material to the loading point. Crucial factors in the choice of equipment are
the loading capacity required, the storage qualities of the fertilizer, the cost of structures and equipment, the safety of the operation, and the expected
operating costs.

Warehouses are not usually operated on the first in, first out principle. For practical reasons, however, the warehouse should be emptied completely from time
to time, since varying raw materials may result in slight color variations, while going to zero aids precise inventorying, and for other reasons.

Shipping from the Plant. Fertilizers at present are usually shipped in bulk, in self-discharging railroad cars, trucks, silo cars with pneumatic loading of
elevators, and canal boats and barges.

Before shipping, many plants screen the fertilizer again to remove dust, lumps, and impurities.

Shipment of fertilizers in bags is declining. The product is usually put in 50-kg open bags (pillow bags), which are then sewed or welded shut, or in valve bags.
Valve bags are better suited to stacking on pallets because of their boxlike shape. Most bags are made of plastic — extruded polyethylene tubing or woven
polypropylene strips coated or lined with polyethylene. Paper and jute bags are now rarely used. The machinery industry has developed largely automated
equipment for bagging and loading or palleting, and much work is still under way to improve these devices and adapt them to various requirements. Because
of the associated high investment costs, bagging takes place mostly at the fertilizer plant. Palleting, which simplifies subsequent transfer of the bagged
product, has gained in importance. In many countries, fertilizers are shipped in large 500 – 1000-kg bags, likewise made of woven polyethylene or
polypropylene.

Dealer Storage. Fertilizer is stored chiefly in buildings, which are usually divided boxwise. Because of the caking tendency and the resulting problems with
reclaiming, especially in the case of ammonium nitrate fertilizers, elevators find use only for free-flowing grades, for a limited span of time, and for quantities up
to 30 t.

In building storage, special care should be taken to protect against moisture, since the fertilizer no longer has its heat from production, and it often sits for
several months under cool, moist conditions. Before receiving material, the warehouse must be completely dry. Fertilizer should be placed continuously,
without long breaks. The pile height should not exceed 5 m. Immediately after placement, the fertilizer surface must be carefully covered with film not less than
25 µm thick, because of the mechanical stress. Joints in the film must have an ample overlap, usually 1 m. A tight seal should be made at the walls (e.g., with
wood lath). Air circulation should be minimized (closed windows and doors, airtight roof). If product is reclaimed in stages, the cover must be restored each
time.

A belt conveyor is suitable for placement of fertilizer. Mechanical abrasion restricts the use of screw conveyors (not over 5 – 6 m, 100 rpm).

User Storage. The interim storage of mineral fertilizers by the consumer is declining to the same extent that the dealers become more willing to undertake this
kind of storage. Bulk fertilizer is kept mainly in flat storage boxes, just as in the trade, and the boxes are similar to those used for dealer storage. Elevator
storage is practiced on a very limited basis.

Bagged product can be stored by the user without major precautions. To simplify transfer operations, between 20 and 30 50-kg bags are assembled on a
pallet, with or without shrink-wrap; in some countries, large bags (0.5 – 1.0 t) are also employed. Bagged fertilizer can be stored outdoors for a limited time
under certain conditions (no temperatures over 32 °C, white UV-stabilized covers).

Transportation. Group B fertilizers can generally be transported without special precautions. Only in exceptional cases are they considered hazardous goods
as defined in the transportation regulations. Specific provisions for Group B, as well as Group A fertilizers, are set forth in international regulations for various
kinds of carriers. The most important rules are recognized by nearly every industrial nation and have been incorporated into the national regulations.

Sea transport: IMDG (International Maritime Dangerous Goods Code)

Rail transport: CIM (International Convention on the Transport of Merchandise by Rail)
Road: ADR (European agreement concerning the international transportation of dangerous goods by road)
Air: IATA-RAR (IATA Restricted Articles Regulations)

The CFR contains rules for all modes of transportation in the USA.

8.2. Application
Solid mineral fertilizers are generally applied to agricultural sites in the form of granules, coarse or fine crystals, and powders. Fine crystals and powders are
becoming less and less important, with the exception of lime which is used almost exclusively in powdered form.

To achieve a good nutrient efficiency and to avoid environmental pollution, the equipment used for the application of mineral fertilizers has to meet the
following requirements:

1. Exact calibration of the amount of fertilizer applied and uniform distribution, both in the direction of travel and in the transverse direction, and
independent of traveling speed and application rate.
2. In order to attain a high area of application, the effective band must be wide and the distributor design must permit a high rate of operation. The rate
must be variable between 50 and 1000 kg/ha. Special distributors for liming must offer rates of up to 5000 kg/ha.

The uniformity of fertilizer application can be determined exactly on a test stand. Boxes with areas of 0.25 m2 catch the fertilizer over the whole application
width, and the product is then weighed. The mean is calculated from the individual values. The smaller the mean deviation from the average value, the more
uniform the fertilizer distribution. Internationally, the test method is largely unified, so that the results are also easily comparable from country to country.

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Application Equipment. Mineral fertilizers in the form of granules or coarse crystals are generally applied by broadcasting-type fertilizer distributors. Spreader
rigs with pneumatic transverse distribution are also utilized, but their use is of declining importance. Powdered fertilizers such as lime are preferably applied by
fixed-width fertilizer spreaders with mechanical transverse distribution to avoid dust formation during operation.

Broadcasting fertilizer spreaders, also called spinner spreaders, operate with working widths of 6 – 36 m. They are characterized by simple construction and
easy handling, together with a high area performance. They constitute the absolute majority of all fertilizer distributors. Broadcasting fertilizer spreaders
distribute the fertilizer over a semicircular to semi-elliptical area around the spreading device. The spreading width is greater than the effective working width.
As the amount of fertilizer which is applied per unit area decreases towards the borders of the spreading swath, overlapping of adjacent swaths is necessary
for uniform transverse distribution of the fertilizer (Fig. 36). Modern broadcasting spreaders have broadcasting patterns with extremely flat sides, so that the
risk of distribution errors in the overlap zone is minimized.

Figure 36. Broadcasting pattern for spinner spreaders

Three types of broadcasting spreaders with different spreading devices exist: single-disk, twin-disk, and oscillating spout (pendulum) spreaders (Fig. 37). The
twin-disk spreader is gaining importance over the single-disk and oscillating-spout spreaders, since its basic concept is better suited for further technical
development. Consequently, the spreading quality of twin-disk spreaders has been raised to a level almost matching that of pneumatic spreaders.

Figure 37. Broadcasting spreaders: single-disk centrifugal distributor (A), twin-disk centrifugal distributors with side-by-side (B) and over-and-under spinners (C),
oscillating-spout distributor (D)

The spreading device in oscillating-spout spreaders is a pendulum tube that moves to and fro. Since this spreading technique allows working widths of only 6 –
15 m, whereas the large fields of modern agriculture require increasingly greater swath widths, the importance of oscillating spout spreaders is also
diminishing.

Fixed-Width Fertilizer Spreaders. With fixed-width spreaders the transverse distribution of the fertilizer is achieved by means of booms, either pneumatically or
mechanically. Unlike spinner spreaders, only one working width is possible.

In pneumatic fertilizer spreaders, the fertilizer is metered at the hopper by cam wheels, fed into distributor tubes, and transported by blast air to discharge
outlets along the spreader booms, which are provided with deflectors (Fig. 38). Depending on the boom length, working widths of up to 24 m are possible.
When working with a pneumatic spreader, overlapping of adjacent swaths is required, as with a spinner spreader. However, due to the steep flanks of the
broadcasting pattern, the required overlap is much smaller (Fig. 39). Pneumatic spreaders can be used for the application of granulated and crystalline mineral
fertilizers, if possible free of dust.

Figure 38. Schematic of a pneumatic fertilizer spreader

Figure 39. Broadcasting pattern for pneumatic spreaders

Spreaders with mechanical transverse distribution are generally equipped with a screw or auger (auger-type spreaders) Fertilizer flowing from the hopper is
conveyed to the driven auger by various means and is then transported to the spreader tubes with adjustable discharge spouts (Fig. 40). Depending on the
boom length, working widths of 6 – 8 m are possible. Auger-type spreaders are preferably used for the application of powdered fertilizers. Boom length and
working width are identical. For uniform fertilizer distribution, exact driving in parallel runs is indispensable (Fig. 41).

Figure 40. Schematic of a spreader with mechanical transverse distribution

a) Supply hopper; b) Elevator belt; c) Slide valve; d) Feed auger; r) Outlet

Figure 41. Broadcasting pattern of a spreader with mechanical transverse distribution

Electronically Controlled Spreading Equipment. Electronic control units are increasingly being used to monitor and to improve the metering and distribution of
mineral fertilizers. Thus, the correct amount of fertilizer can be automatically discharged when the traveling speed of the spreader is changed, and the amount
of applied fertilizer can be displayed, based on permanent monitoring of the fertilizer discharge.

Site-Specific Fertilizer Application Guided by GPS. Until now farmers' fields generally received a uniform fertilizer rate. With the steadily increasing size of
individual fields this practice is bound to change, as increasing field size also implies increasing heterogeneity of the soil and thus of the crop yield. For
economical and environmental reasons, a future development towards the site-specific management of large-sized fields is imminent. Under this aspect, the
global positioning system (GPS) is currently being tested under practical conditions for its suitability for crop management, including fertilizer application. GPS
allows the exact position in the field to be determined and relocated, regardless of weather, location, and time. On this basis, it should be possible to apply
fertilizers site-specifically in accordance with the existing soil and crop variations within a field. The complete technology, from yield recording by the harvester
to nutrient application with the fertilizer spreader, has yet to be further developed. This will probably take another 5 to 10 years.

[Top of Page]

9. Environmental Aspects of Fertilizer Application

Wilfried Werner

Fertilizers are used to enhance soil productivity or fertility (amelioration fertilization) or to maintain it at an economically and ecologically acceptable level
(maintenance fertilization). The task of fertilizers is to replace the nutrients lost through the harvest and by other causes: irreversible fixation in the soil,

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leaching, escape in gas form, etc. Along with the positive effect of fertilizer application, there are also negative effects, especially with improper use.

Up to the beginning and middle of the 1970s, environmental problems triggered by fertilization practices were subject to local discussion only; examples were
the buildup of heavy metals in soils and crops when sewage sludge was applied, the buildup of nitrates in the groundwater where vegetables were raised in
the catchment areas, and the eutrophication of surface waters due to phosphates. Only later was the partly regional character of local environmental problems
acknowledged.

From the early 1990s onwards, increasing emphasis was also placed on global aspects of the impact of fertilization on the environment, i.e., the influence of
agricultural production in general and fertilization in particular on the increased emission of greenhouse gases. The awareness of the mutual relationship
between surplus production of agricultural products and environmental problems within the EU has continuously grown over recent decades. In particular the
interest in mineral emissions from agriculture has increased substantially, both in policy making and research and in practical farming.

9.1. Nitrogen
Of all plant nutrients, nitrogen is the most effective in economic terms, but in ecological terms the most problematic. The plant absorbs nitrogen mainly as
nitrate but partly as ammonium . The plant's ability to assimilate larger molecules with organically bound nitrogen is limited.

Problems with nitrogen arise from a local or regional excess of nitrogen, regardless of its origin. Several cases, which are mostly of a regional character, are
described first, then solutions are listed. Figure 42 summarizes the environmental aspects of nitrogen.

Figure 42. Agricultural nitrogen as an environmental factor

9.1.1. Ground Water

Various sectors of the economy — agriculture, forestry, water resources and wastewater management, transport, energy, and industry — are involved in
ground water and surface water problems having to do with nitrogen. With regard to ground water, the quality of drinking water is the prime concern. A
reduction in the maximum allowable nitrate content in drinking water within the EU, from 90 mg/L to 50 mg/L, has made the nitrogen problem more acute.

Until 1970 – 1975, virtually the only negative aspects considered with respect to nitrate were methemoglobinemia and the nitrate – nitrite – nitrosamine
problem. Later, a number of other reactions triggered by nitrate and sulfate in the aquifer or during transport to it have come under discussion. Depending on
the presence of aerobic or anaerobic conditions, the intensity of (and ) application, and the reserves of microbially available carbon sources, the
reactions listed in Table 34 can yield the following compounds:

or Ca(HCO3)2 water hardness

N2 O stratospheric ozone break-
down
; undesirable, toxic, or
H2S; foul-smelling

Fe2+, Mn2+
Fe(OH)3 ferric incrustation of wells

If available carbon sources are not present, or exhausted, nitrate (or sulfate) can break through into the ground water.

From around 1980 up to now increasing emphasis was placed on ground water as prime source of diffuse nitrogen pollution of surface waters [525], [526].

Table 34. Sequence of environmental problems in the presence of excessive nitrate and sulfate in the pedosphere and hydrosphere

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Causes of Nitrate (and Sulfate) Damage. The following cases have been described in the Federal Republic of Germany:

1. Ground water lowering, plowing of pastureland, intensive cropping with N fertilization [527]
2. Intensive cropping with vegetables and/or intensive stockbreeding with appropriate N fertilization (Fig. 44) [528-532]
3. Intensive agricultural land use — commercial gardening, animal husbandry — with appropriate N fertilization [533]
4. Commercial gardening, intensive white asparagus cultivation, overuse of mineral fertilizers (Fig. 45) [534], [535]
5. In the Netherlands, the ground water in regions with intensive stockbreeding (the provinces of Geldern and Brabant) displays not only elevated nitrate
levels but often high ammonium values at depths between 10 and 25 m [536]

Recent surveys on the nitrate concentration of the ground water in Germany resulted in quite different frequency distributions for a representative overall set of
measurement points and a special set of measurement points restricted to agricultural “loading areas” according to EU Directive 91/676. In the representative
survey, only 10 % of the samples exceeded the EU threshold concentration for drinking water, whereas in the near-surface groundwater of so-called
agricultural-loading areas this was the case in more than 60 % of the samples (Fig. 43).

Figure 43. Frequency distribution of concentration in ground water in Germany [537], [538]

Figure 44. Nitrate and sulfate in the raw drinking water of Mussum, North Rhine-Westphalia, Federal Republic of Germany, 1910 – 1996 [532], [539].

Figure 45. Nitrate concentration in water from three wells of Bruchsal Waterworks, 1973 – 1983 [540]

The insert shows the location of wells no. I – III.

A distinction should be made between acute and chronic nitrate problems. Extreme overfertilization or pastureland plowing can cause sudden, acute nitrate
damage in soils threatened by leaching (sandy soils, high water table, low or declining denitrification capacity). For example, years of overapplication of N
(mainly for asparagus, with more then ten times the N depletion by the crop) in the drinking-water catchment area of the Bruchsal (Federal Republic of
Germany) waterworks overloaded the denitrification capacity and caused a jump in nitrate in well waters (Table 35, Fig. 45) [535], [540].

Table 35. Denitrification potential and nitrate nitrogen concentration 2 – 3 m and 3 – 4 m under the surface of forest (pine or alder) and farmed land
(cereals or asparagus) at Bruchsal (Federal Republic of Germany) in February, 1986

Forest near well number I Intensively cropped land near well number III

Pine Alder Cereals Asparagus

2 – 3 m under the surface

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Denitrification potential *, kg/ha 427 583 67 21
Nitrate nitrogen, kg/ha 6 18 23 56
3 – 4 m under the surface
Denitrification potential *, kg/ha 238 258 50 17
Nitrate nitrogen, kg/ha 4 3 50 60

* The denitrification potential is the concentration of water-soluble carbon, as glucose, multiplied by 10/27, which corresponds to the stoichiometry 5 C

6H12O6 + 24 (see Table 34).

Over a long period, an acute nitrate problem may become chronic. Even under economically optimal fertilization matched to base outputs, elevated ground
water nitrate levels can come about [535], [541], [542]. The base outputs arise through leaching of water-soluble nitrogen-bearing substances. The
unavoidable nitrogen base outputs, primarily in winter, are between 20 and 40 kg ha–1 a–1 [543-545]. A chronic nitrate problem is much more severe than an
acute one with respect to detection and propagation, as well as the cost and the success of rehabilitation measures.

The causes of damage can be classified as follows:

1. Plowing of pastureland, forced in part by prior ground water lowering. In three to four years, this process robs light soils of 6 – 7 t of organic nitrogen
through mineralization and leaching out of the root zone [546], [547]. In heavy soils, the process takes much longer. The nitrate formed by
mineralization is first denitrified by microorganisms, with the simultaneous degradation of the microbially available carbohydrates. The denitrification of
6 – 7 t of nitrate N requires 16 – 19 t of such carbohydrates. In this way, the available organic matter soon becomes the limiting factor, and the
denitrification capacity of the soil is exhausted. In soils with shallow foundation, there is thus a danger that the N output of a nearby intensive farming
operation will appear almost quantitatively in the ground water. Depending on how close the wells are, the raw water may show elevated nitrate levels
for decades [548].
2. Inappropriate crop rotation. Examples of poor crop rotation include high fractions of fallow or semifallow land (e.g., corn [maize] or sunflowers), summer
grains without or with inadequate (winter) intercrops, and large fractions of legumes, especially if they are plowed in too soon [545], [549]. These
practices usually result in high leaching losses, chiefly in winter.
3. Corn rotation with excessive liquid manure. In regions of large-scale stockbreeding, for example, in parts of the Netherlands, Belgium, Germany, and
France, excessive amounts of liquid manure were formerly — and in many forms are still — applied.
4. Incorrect nitrogen fertilization. The problem is usually excessive fertilization, poor timing, and unsuitable fertilizer form, usually not an inappropriate
application method.

The danger of overfertilization with mineral fertilizers is especially great in commercial gardening and in single crops with low N depletion (orchards,
vineyards). Vegetables are usually harvested in the principal growth period of the vegetative phase. Leafy vegetables, above all, offer good market quality only
if a good nitrogen supply is available at the time of harvesting. Thus high residual levels of readily soluble nitrogen remain in the soil. Here again, it often
happens that too much fertilizer is applied. The same holds for vinegrowing, especially over permeable limestone. In sugar beet farming, fertilizer nitrogen was
formerly applied far in excess of the depletion. However, from 1980 until 1994 there was already a continuous decrease from 250 to 125 kg N per hectare in
German sugar beet growing, on average [550].

In general, the danger of overapplication is less for mineral fertilizers than for organic fertilizers, since the nitrogen content in the mineral fertilizer, unlike that in
manure, is known and constant. What is more, the mineral fertilizer can be applied more precisely with respect to both quantity and schedule. Finally, cost is
an important factor in determining the rate of mineral fertilization.

Overapplication of organic fertilizers is a problem chiefly in heavily stock-oriented farming with liquid manure fertilization and in pasturage with grazing. Despite
overapplication of organic fertilizers by a factor of one or two, compared to the residual nitrogen loss, mineral fertilizer N is often supplied in addition to improve
yields. This is demonstrated by the total nitrogen balances of different farming types in Germany. The mean nitrogen surpluses were estimated for the financial
year 1995/96 at 19 kg N per hectare for arable farms, 107 kg N per hectare for cattle farms, and 166 kg N per hectare for special pig and poultry farms [551].

9.1.2. Surface Waters

In common with the groundwater situation, many Western European rivers have shown a strong tendency towards increasing levels of dissolved nitrogen. As
an example, in the period between 1954 and 1995 the nitrogen load, mainly as nitrate, from diffuse sources of the Rhine at the Lobith control station increased
from 95 000 to 185 000 t N per hectare per annum [552].

The present share of diffuse sources in the total nitrogen input into surface waters in Germany is estimated at about 60 % [526], [553], [554], because the N
input from point sources was drastically reduced since the mid-1980s due to the introduction of nitrification and denitrification treatments in sewage plants. Of
the diffuse sources, the pathway via groundwater is highly dominant, accounting for roughly two-thirds. Drain water was responsible for an average input share
of about 10 % of the diffuse nitrogen pollution of surface water in Germany. Hence, about three-quarters of total diffuse nitrogen input was due to leaching of
nitrogen from upper soil layers, and nitrogen fertilization with both mineral and farm-produced fertilizers has an important impact on the level of leaching
losses.

In connection with the nitrate N (and phosphorus) loading of rivers and wetlands, special attention should be paid to the drainage system in the agricultural
area of the northern European lowland plains, with their intensive stockbreeding and liquid manure disposal. The danger of eutrophication not only by
increasing phosphate inputs but also by rising nitrogen inputs into estuaries, coastal zones, and especially the tidal mud flats of the North and Baltic Sea
coasts has come under discussion [555-557]. Sediments in these areas since about 1950 – 1960 display increasing contents of both P and N [558], [559].

9.1.3. Atmosphere
Agriculture is one source of problematic N compounds in the atmosphere: N2O from nitrification and denitrification processes in the soil and, chiefly in
stockbreeding areas, ammonia (Fig. 42).

N2O Emissions. N2O [10024-97-2], with an atmospheric residence time of 100 – 200 years, serves as a source of NO [10102-43-9]. In the upper stratosphere
NO, along with HO radicals and halogenated hydrocarbons, contributes to the breakdown of ozone, which is associated with the danger of increased short-
wavelength radiation on the earth and a correspondingly increased susceptibility to skin cancer in humans [560].

Soil management is the most important agricultural N2O source [561]; denitrification and nitrification are the responsible microbial processes [562], [563].
Intensive studies on N2O emissions from agricultural soils carried out from the beginning of the 1990s gave average emission rates of 2 – 5 kg N2O per
hectare per annum for temporate zones [564], [565], [566], but much higher for tropical soils [567].

The total N2O emission in Germany in 1990 was estimated by the Federal Environment Agency (UBA) at 143 × 103 t N per annum, with an agricultural
contribution of 34 % [553].

The quantity of N2O emitted from soils is determined by the content of available nitrogen, that is, by the level of N fertilization. Nitrogen fertilization was

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responsible for 50 – 80 % of the emissions, and between 1 and 3 % of the fertilized N was lost as N2O [568-571].

A worldwide estimate of direct and indirect emissions of N2O from nitrogen fertilization and nitrogen fixation is given in Table 36. The direct emissions of N2O
are estimated at 1.25 ± 1 % of the applied N. The indirect emissions are ascribed to N from past years' fertilization, crop residues, from subsurface aquifers,
and from recent atmospheric depositions [571]. An additional 0.75 % of the applied N will eventually be evolved from these indirect sources [572]. With
increasing nitrate levels in the soil, the denitrification ratio N2O/N2 shifts in favor of N2O [573]. The average share of N2O in the total denitrification loss was
assessed at 8.5 % [574].

Table 36. Estimates of direct and indirect global emissions of N2O from application of fertilizer N (synthetic or animal waste) to agricultural soils
and from soils growing biological N-fixing crops (106 t/a N2O N) [577]

Region Mineral N Animal waste N fixation Total Range

Africa 0.04 0.21 0.05 0.30 0.15 – 0.45

North and Central America 0.26 0.11 0.11 0.48 0.24 – 0.72
South America 0.03 0.22 0.09 0.34 0.17 – 0.51
Asia 0.75 0.52 0.19 1.46 0.73 – 2.19
Europe 0.27 0.22 0.02 0.51 0.26 – 0.77
Oceania 0.01 0.03 0.01 0.05 0.03 – 0.08
Former Soviet Union 0.17 0.18 0.03 0.30 0.19 – 0.57
Total 1.53 1.49 0.50 3.50 1.80 – 5.30

Ammonium-based fertilizers lead to higher N2O emissions than nitrate-based fertilizers [569], [575]. Farm manures generally produce higher N2O emissions,
mainly due to the simultaneous application of quickly decomposable organic matter [576].

N2O emissions due to N fertilization are mitigated by all measures to improve the efficiency of N use. The mitigation potential is estimated at up to 20 % [577].

NOx (NO + NO2 ) Emissions. NOx, which has an average atmospheric residence time of 1.5 d, contributes to ozone synthesis in the troposphere:

The reverse reaction does not take place in the presence of carbon monoxide or reactive hydrocarbons, including methane, which is produced mainly by
ruminants. Ozone can combine with unsaturated hydrocarbons from automobile exhausts to form ozonides, which react with NO2 to yield peroxyalkyl nitrates

Ozone and the peroxy compounds are strong oxidizing agents with high phytotoxicity. They have been blamed for damage to vegetation in both forestry and
agriculture.

The volume of NOx emissions due to fertilization (from N reactions in the soil, nitrification more than denitrification [578] ) and of plant NOx emissions [579-581]
is hard to assess. The contribution of agriculture to global NOx emissions was estimated at 22 % (ca. 11 Tg NOx N per annum), which consists of biomass
burning (14 %) and the influence of mineral fertilization and manuring (each ca. 4 %) [582]. When the photooxidation of emitted NH3 in the troposphere is
taken into account, the figure rises to 27 %. However, NOx is reabsorbed and metabolized by the plant, so that gross and net processes must be differentiated
[583-587].

NH3 Emissions. Ammonia emitted into the atmosphere reacts fairly rapidly (residence time < 9 d) to and, after reaction with, say, , is precipitated as
ammonium sulfate, (NH4 )2SO4. Atmospheric NH3 or promotes the long distance transport of SO2 or . Ammonia and ammonium nitrogen forms do
have fertilizing action, but in Western Europe the negative effects outweigh the beneficial ones in close-to-natural (forests, heath) and natural ecosystems
(nature preserves, surface waters). Aside from the phytotoxic action of NH3 in the area close to the emission source, deposition of causes long-range
damage:

1. Leaching of nutrients (e.g., K+, Ca2+, Mg2+ ) out of the phyllosphere (leaves, needles) and the pedosphere (soil) followed by acidulation of the soil and
waters [588-592]
2. Buildup of nitrogen in the pedosphere and nutrient imbalances in vegetation [589]
3. Injuries to mycorrhizae, the roots in symbiotic association with fungi [593]
4. Changes in the flora and fauna of terrestrial and aquatic ecosystems due to the promotion of nitrophilic species and the inhibition of nitrophobic species
[589], [594]
5. Increased loss of N with leach water, especially in damaged coniferous forests [595-597]
6. Increased N inputs to surface waters [598], corresponding N buildups in marine sediments, especially in the North Sea and Baltic Sea coastal regions
[558], [559]

Around the turn of the century (in remote regions even today) the mean annual depositions of atmospheric NO3 N and N were each ca. 1.3 kg/ha. Today,
10 – 15 kg/ha are deposited for each nitrogen form. On the basis of the filter capacity of the forest, the atmospheric N inputs may be increased by a factor of
1.2 – 2.0 (deciduous forest) or 3.0 (coniferous forest). In addition, a coniferous forest has a specific filtration capacity for N but not for N [596], [599].

Recent measurements of the atmospheric nitrogen deposition into the soil – plant system with a new integral measurement system for wet, dry, and gaseous
depositions even show annual net depositions of between 65 and 73 kg N per hectare at two locations in central Germany [600]. Clearly the earlier standard
measurements underestimated the true magnitude of nitrogen deposition. Such nitrogen depositions exert a high pressure on natural or close-to-natural
ecosystems because they greatly exceed the critical loads of these ecosystems.

The estimate of NH3 emissions by agriculture is based on statistical figures of animal husbandry and fertilizer production and application, which all are
multiplied by source-specific emission coefficients. Because of the different values of these specific coefficients given in the literature, all estimates of NH3
emissions have a high range of uncertainty. An estimate for Germany (1992) resulted in the range from about 350 to 840 with a mean value of 577 Gg NH3 N
[601]. There are very large differences in the emission densities between and even within the federal states.

The estimates for Western Europe from different authors are in the range of 3.1 – 4.0 Tg/a NH3 N [602]. As an example, Table 37 contains estimates of the
anthropogenic NH3 emissions from agriculture, industry, and other sources for 16 European countries. 90 % of the total emissions are due to agricultural
activities, 74 % alone originates from animal husbandry (stabling, grazing, application of manure), and 12 % is attributed to the use of mineral fertilizers. The

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total emission is 4.0 Tg/a NH3 N ± 30 %, that is, 2.2 – 5.2 Tg/a NH3 N.

Worldwide, including natural emissions, mineral fertilizers account for 2 – 5 % and stockbreeding 12.5 % of the total emissions of about 120 Tg/a NH3 N [560].
The high proportion due to stockbreeding in Western Europe is accounted for by the high population density of animals and by the changeover from solid
manure to slurry manure, which is less laborious but higher in NH3 emissions. In comparison with stockbreeding, NH3 emissions are lower even when solid
mineral fertilizers high in NH4 or amide N (ammonium sulfate, diammonium phosphate, urea) are used. This is especially true for soils where the pH and the
free lime content are high or where directly incorporating the fertilizer into the soil is not possible. Liquid fertilizers with , because they infiltrate the soil,
emit less NH3 than solid fertilizers.

Based on the specific NH3 emission coefficients of the various N fertilizers and their application, NH3 emission rates from mineral fertilizers in Germany are
calculated by different authors to be from 2.1 to 8.1 kg per hectare per annum NH3 N [603].

Table 37. Anthropogenic ammonia emissions from 16 European countries [602]

Country Animal husbandry Mineral fertilizers Cultivated plants Industry Other sources Total

Belgium/Luxembourg 99 4.2 2.3 1.1 9.2 115

Germany 504 78.4 27.1 1.5 53.1 664
Denmark 97 7.5 4.2 0.4 9.5 119
Finland 36 2.7 3.9 0.7 3.8 47
France 564 127.6 46.1 2.0 64.3 804
Greece 57 18.6 13.8 0.5 7.8 98
Great Britain 366 55.9 26.9 1.4 39.1 489
Ireland 124 12.5 8.5 0.8 12.6 158
Italy 390 64.0 21.0 3.3 41.6 520
Netherlands 200 8.5 3.0 3.6 18.7 234
Norway 32 1.1 10.5 0.9 3.1 39
Austria 62 1.6 5.3 0.4 6.1 76
Portugal 59 6.2 6.8 0.3 6.3 78
Sweden 54 2.2 5.1 0.3 5.4 67
Switzerland 48 3.4 3.0 0.0 4.7 59
Spain 270 96.1 45.8 1.8 36.0 449
Total (abs.) 2961 490 224 19 321 4016
Total (rel.) 74 12 6 0.5 8 100

Apart from the impact of nitrogen fertilization on greenhouse gases, there is growing concern about its influence on the sink capacity of soils for methane, the
most important greenhouse gas after CO2. Oxidation by methanotropic bacteria in the soil is the only biological sink for methane. An adverse effect of N
fertilization on methane oxidation was first reported in 1989 [604]. Later it was found that ammonium strongly inhibits methane oxidation, whereas nitrate has
only a minor effect if at all [605-607]. This is due to the competition between and CH4 for the enzyme methane monooxygenase [608].

9.1.4. Biosphere
Nitrogen fertilizer may produce undesirable N forms in the crop and changes in the composition of flora and fauna in nearby close-to-natural or natural
ecosystems.

Undesirable N Forms in Crop. Because of the potential formation of nitrosamines, crops should not contain too much nitrate. However, the nitrosation of
substances such as vitamin C [50-81-7] and -tocopherol [59-02-9] suppresses nitrosamine formation.

Fertilization with nitrogen alone increases the content of stored N forms (such as N, basic amino acids, amines, and amides, and lowers the content of
vitamin C in vegetative plant parts. This is more true for fertilization than for fertilization. The content of -tocopherol is virtually unaffected [609]. A
balanced NPK application, on the other hand, can raise the vitamin C content [610], [611]. This is important above all to vegetable farming, especially with
regard to the content arising from fertilizer, since the nitrate intake of human beings is derived about 70 % from vegetables consumed if the content
in drinking water is low (<10 mg/L). As a result, countries in Western Europe have adopted guidelines or maximum levels for nitrate in vegetables. Limits are
imposed, for example, in the Netherlands, Austria, and Switzerland. The Federal Republic of Germany has established guidelines, e.g., for fresh lettuce and
spinach, 3000 and 2000 mg/kg, respectively.

Biodiversity. The diversity of both faunal and floral communities is influenced by agriculture and fertilizer use. On a site-specific local scale, fertilizer use in
general and nitrogen fertilization in particular promote the growth of crops more than that of accompanying flora. In grassland, heavy use of nitrogen inhibits
the growth of many herbs and legumes.

High amounts of fertilizer salts or anhydrous ammonia may have adverse effects on earthworm population by direct contact. However, the detrimental effect on
the total population is very low. The greater supply of fresh organic material that becomes available when soils are raised low to high fertility by fertilization has
positive effects on both earthworms and soil microorganisms.

On a global scale the use of fertilizers has positive effects on biodiversity in reducing population pressure for cultivating unsuitable fragile soils, felling of
rainforests, and overgrazing, that is, by reducing or preventing soil erosion and degradation.

9.1.5. Pedosphere (Soil)

Nitrogen in cultivated soil (root zone, 0 – 120 cm) is an asset for agriculture, because nitrogen reserves and availability in this region are an important criterion
for soil fertility. However, in close-to-natural or largely natural ecosystems, atmospheric N inputs in the forest, heath, nature preserves, lakes, and rivers can
lead, over a long period, to a buildup of nitrogen in the soils; the harmless removal of this N (possible only through denitrification) is of concern to ecologists.

9.1.6. Countermeasures
Measures aimed at preventing or overcoming nitrogen problems due to N fertilization in all environmental zones can be divided into direct measures and
indirect measures. The aim of both is to minimize the residual nitrogen in the root zone at the end of the vegetation period and hence the leaching potential.

Direct Measures in Fertilization. For arable crops such as sugar beet [550], significant progress has been made in reducing the fertilizer-related nitrogen
leaching potential. To provide an economically and an ecologically accurate nitrogen recommendation, the nitrogen supply from soil reserves is assessed by
methods such as electroultrafiltration (EUF) or, if not measurable, by empirical estimation. Nitrogen fertilizer is added only to account for the difference
between the demand of the crop and the supply from the soil. The guideline for the plant N demand over time is the nitrogen depletion with the harvest.
Because of inevitable N losses (denitrification, leaching, etc.), roughly 20 – 30 % extra nitrogen must be supplied over and above the depletion. Optimal
distributing systems apply the fertilizer uniformly. Most farmers follow these principles.

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The only way to accurately find the actual nitrogen demand is a nitrogen balance for a single farm or field. The ecologically acceptable N level may be higher
than, equal to, or lower than the optimal fertilization level: this fact represents a potential incompatibility between economics and ecology. It is very important in
this concern, that the new German “Fertilizer Utilization Decree” contains a commitment of farmers to bookkeeping, thus calculating the balances of mineral
nutrients at form level.

Farm-Produced Fertilizers. The most urgent nitrogen problem in Western Europe is that the livestock population in large regions has long been above
acceptable levels. To comply with clean-air and clean-water requirements, the former liquid manure regulations of some states in Germany, that still permitted
using liquid manure of three live-animal units per hectare of agricultural land, an amount still far beyond what is economically beneficial and compatible with
the environment, were replaced in 1996 by a federal Fertilizer Utilization Decree with some special requirements for the application of farm-produced manures,
including the following:

– Limiting gaseous NH3 losses by appropriate technical measures, consideration of weather conditions, and the incorporation of liquid manure into
unplanted soils immediately after application.
– Using liquid manure in autumn after the harvest of main crops only for subsequent catch or in combination with straw incorporation and only in limited
amounts (equivalent to 40 kg of NH4 N or 80 kg of total N per hectare).
– No liquid manure application in winter from November 15 to January 15.
– Limitation of farm manure application to 170 and 210 kg N per hectare per annum on arable land and grassland, respectively, including nitrogen in animal
droppings on pastures. Up to 20 % of total N in manure may be subtracted to compensate unavoidable NH3 losses during spreading.

Mineral Fertilizers. The matching of N fertilizer application to economic and ecological requirements is much easier with mineral fertilizers than with farm
fertilizers, since the mineral products — in contrast to the farm-produced ones — are defined within narrow limits as to N content, N form, and availability.

The nitrogen form is of secondary importance, since and amide N are usually converted in a few days, perhaps 1 – 2 weeks, to nitrate nitrogen in
agricultural soils. Nitrification inhibitors, added to fertilizers to retard the conversion of to , may afford an extra measure of safety where there is
no acute ground water nitrate problem; however, they are only a partial solution to the problem [612]. (Nitrification inhibitors may promote the liberation of NH3
from fertilizers, especially when the fertilizers are not incorporated in the soil [613].)

Controlled-release forms of N may represent an improvement from the ecological point of view when they make it possible to satisfy the crop N demand over
time better than can be done with conventional nitrogen fertilizers, and when no substantial amount of nitrogen remains in the soil after the vegetation period.

Indirect Measures. All practices that lead to gains in yield without additional N alleviate environmental nitrogen problems due to fertilization.

Plant Cultivation. The selection of species and varieties and the planning of the entire rotation are crucial factors in reducing economically and ecologically
undesired nitrogen losses. The evergreen system, that is, keeping fields covered with crop plants year-round, is a desirable goal; whenever possible, the
intercrops should moderate N fertilization (nitrogen harvesting). This practice also protects against erosion. Fallow land should be avoided; semifallow area,
such as under corn, sunflowers, or summer grains, should be minimized.

An extraordinary reduction of nitrate loss by leaching is achieved by overhead crop irrigation, and, the extreme case, by moderate spraying to avoid frost
damage and possibly the loss of a crop in an early stage.

Plant Protection. Plant protection measures, whether mechanical (especially to combat weeds and grass), biological, or chemical, generally increase yield and
thus better utilize the nitrogen supply. In this way they indirectly reduce ecologically undesirable nitrogen losses.

Plant Breeding. Nitrogen-efficient plant species and varieties produce more dry matter per unit of nitrogen delivered than do inefficient species.

Soil Tillage. Tillage also has a decisive effect on ecologically undesirable N losses. Tilling as deep as possible, while still preserving soil structure, aids the
availability of the nitrogen and reduces the leaching loss by creating the optimal pore volume in combination with an ordered humus regime, thus optimizing
the water regime and the supply of water to the crop.

9.2. Phosphorus
Environmental problems connected with phosphate fertilizers are eutrophication and the buildup of heavy metals.

9.2.1. Eutrophication
The pollution of nonflowing or low-circulation surface waters (lakes, estuaries, and coastal zones, especially tidal mud flats) with plant nutrients is to be
avoided on account of eutrophication. This term refers to the excessive growth of algae and aquatic plants due to too great a supply of nutrients. Because the
putrefaction of these organisms requires a great deal of oxygen, the water becomes depleted in oxygen. Fish die, and the biological purification of the water
ceases to function. The lake has turned over.

The primary limiting factor for eutrophication is phosphate. Surface waters should contain ≤ 50 µg P per liter. Nitrogen can also become a factor for
eutrophication when increased biomass growth takes place.

Figure 46 compares the amounts and main sources of phosphates in surface waters of Germany from 1975 to 1995 [554]. The P input by point sources was
markedly decreased by improved sewage treatment practices and by the transition to phosphate-free detergents. Consequently, the share of diffuse sources in
the total P input increased from nearly 20 % to about 50 %, although the absolute diffuse input also began to fall from ca. 1990 onwards. Soil erosion and
surface runoff from agricultural fields are the most important diffuse sources (Fig. 47).

Figure 46. Changes in phosphorus input into surface waters in Germany from 1975 to 1995 [525], [526], [552], [554], [614], [615]

Figure 47. Nitrogen and phosphorus inputs into running waters by diffuse and point sources in Germany: prognosis for 1995 [553]

In contrast to nitrogen, phosphorus pollution via groundwater and drain water is not yet important, although vertical transport of this nutrient may create a
pollution problem where the P sorption capacity of deeper soil layers is already highly saturated. This has been reported for areas with high livestock densities
in the Netherlands [616] and in north-western Germany [617].

The agricultural contribution to phosphorus in surface waters on a regional scale makes the implementation of efficient countermeasures in agriculture
necessary [618], [619]:

– Prevention of erosion by field arrangement (e.g., reducing the slope length), crop management (mulched seeding, underseeding, changes in crop

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rotation), and soil management (tilling across the slope, improvement of soil structure and infiltration rate).
– Prevention of surface runoff from slopes by omitting the application of mineral or organic fertilizers in autumn and winter.
– Prevention of direct inputs of eroded soil and runoff water by planted margins along the banks of surface waters.
– Consequent adjustment of phosphorus fertilization to plant requirements: supply and removal must be kept in balance on soils with optimum P supply
status. On P-accumulated soils, fertilization can temporarily be reduced or even omitted.

In Germany, the implementation of countermeasures is accelerated by the German “Fertilizer Utilization Decree” of 1995.

Besides economic reasons, environmental concerns were also responsible for changes in mineral fertilizer consumption since 1985. As far as phosphorus is
concerned, the balance surplus showed a mean annual decrease of 7 % for the period of 1990 – 1995 [551], in particular due to reduced application of mineral
P fertilizer (mean application 11.0 kg P/ha in 1995 compared to 25.5 kg P/ha in 1985).

9.2.2. Heavy Metals Buildup

With regard to the impact of fertilizer use on heavy metals buildup in soils, the element cadmium is of primary concern. Fertilizer phosphates produced from
phosphate rock contain cadmium [7440-43-9]. The amount depends on the origin of the rock and the digestion process employed. The cadmium content of
phosphate rock varies from almost zero to about 700 mg/kg P. The acidification of phosphate rock partitions the Cd between the fertilizer and byproducts of
phosphoric acid production such as phosphogypsum.

The Cd input into agricultural land by phosphate fertilizers in Germany was significantly decreased during the last two decades, due to both the preference of
low-cadmium phosphate rock for fertilizer production and the dramatic decrease in mean phosphorus application rates. The mean Cd content is phosphorus
fertilizers is now reported with about 100 mg/kg P [620]. The mean application rate in 1995/1996 was 11 kg P/ha. Based on these figures, the average annual
Cd input is 1.1 g/ha, which compares to about 3.0 g/ha in 1980.

The quantities removed by the crops and by leaching are calculated at about 2.0 g Cd/ha. The background Cd contents in agricultural fields therefore, could
not be augmented by mineral fertilizers alone, even if current application rates were doubled [621-623]. However, additional cadmium sources must be taken
into account. Atmospheric input from industrial air pollution is the most important source in all industrial countries (3 – 6 g Cd/ha). Manures, sewage sludges,
and biowaste composts may be locally or regionally important heavy metal sources [624]. Legal regulations in Germany allow annual maximum heavy metal
inputs into soils that are much higher than the realistic inputs via mineral fertilizers. For cadmium these threshold values are 18 g/ha by atmospheric
depositions, 10 g/ha by biowaste composts or 16.7 g/ha by sewage sludges.

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10. Legal Aspects

Günter Kluge

Since the beginning of the mineral fertilizer industry, many countries have issued regulations to protect fertilizer users. These rules deal, in particular, with
nutrient contents and with safety for plants, human beings, animals, and the environment.

Fertilizer regulations are based on special fertilizer legislation or else form part of a more comprehensive regulatory scheme that governs areas such as animal
feeds or pesticides. As a rule, the government department of agriculture has jurisdiction over fertilizers.

The rules on fertilizers extend only to commerce in fertilizers (offering, selling, trading); in only a few cases do they cover other areas (Table 38).

Table 38. National and international regulations concerning fertilizers

Federal Republic of Düngemittelgesetz vom 15. November 1977

Germany
(Bundesgesetzblatt I, p. 2134)
Düngemittelverordnung vom 19. November 1977
(Bundesgesetzblatt I, p. 2845)
France Journal officiel du 29 juin 1980 (Loi No. 79 – 595 du 13 juillet 1979 relative à l'organisation du contrôle
des matières fertilisantes et des supports de culture ; Journal officiel du 14 juillet 1979)
Great Britain Statuory Instruments 1977 No. 1489
The Fertilisers Regulations
Italy Legge 19 ottobre 1984, n. 748. Nouve norme per la disciplina dei fertilizzanti
Gazetta Ufficiale 6. Novembre 1984
European Economic Council Directive of 18 December 1975 on the approximation of the laws of the member states
Community relating to fertilizers (76/116 EEC)
Council Directive of 22 June 1977 on the approximation of the laws of the member states relating to
sampling and methods of analysis of fertilizers (77/535 EEC)
Austria Bundesgesetz vom 7. November 1985 über den Verkehr mit Düngemitteln, Bodenhilfsstoffen,
Kultursubstraten und Pflanzenhilfsmitteln (Düngemittelgesetz – DMG)
Japan Fertilizer Control Law of Japan. MAFF Ordinance No. 87, Juli 5, 1978
United States Association of Official Analytical Chemists (AOAC), Washington, DC
International International Organization for Standardization (ISO), Genève, Switzerland

Definition. Laws on fertilizers either contain a definition or simply refer to a list of fertilizers. A definition may be scientifically or pragmatically oriented. While
mineral fertilizers present fewer difficulties, the diverse agents used for soil amendment are harder to define.

Examples:

Material, the main function of which is to provide plant food. (ISO)

The term “fertilizers” as used within this Law shall be defined as being any substance applied to the soil for the purpose of supplying nutrients to plants; for
producing a chemical change in the soil which will contribute to the cultivation of plants; or which, when applied to the plant, will supply plant nutrients. (Japan)

Fertilizers are substances that are intended to be supplied directly or indirectly to crop plants in order to promote their growth, increase their yield, or improve
their quality; excepted are . . . (Federal Republic of Germany)

In the regulations and annexes, fertilizers are systematically classified, for example, into straight and multinutrient fertilizers. The physical form, for example, in
liquid fertilizers, may also figure in the classification.

Approval, Registration, Type Lists, Standards. In principle there are two ways of regulating the trade in fertilizers: type approval and individual approval of
fertilizers. The European Economic Community (EEC) has chosen the following approach in the interest of harmonization of laws: A type list describes the
fertilizers covered (type designation, minimum nutrient contents, expression of nutrients, method of production, essential ingredients, nutrient forms, and

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nutrient solubilities). Fertilizers that meet these requirements may be marketed provided the labeling rules in all member states are complied with.

Such a system exists in similar form in many of the developed countries. Allowance is made for the fact that many fertilizers are products well known in
international trade, such as urea, triple superphosphate, and NPK fertilizers. The administrative cost is low. The type list must be supplemented from time to
time to take account of technical development. As a rule, effectiveness must first be proved (plant tests), as must safety for human beings, animals, the soil,
and the environment.

Another approach is individual licensing for each fertilizer offered by a manufacturer or importer. An administrative action must precede the sale of any
product. The government thus has a complete picture of the registered fertilizers and of the suppliers. Often, approval is granted only for a certain time.
Provisional approvals are usually possible.

Because both systems have advantages and drawbacks, many countries prefer a mixed approach: type approval and registration. Standards are defined for
fertilizers. Manufacturers and importers must seek registration, which requires stated tests. The certificates granted often have only a limited term.

The choice of approach is dictated, above all, by the system of laws and government in each country, in particular by the degree of supervision desired by the
state.

Labeling, Terminology, Packaging. Next to approval, labeling of the product on the package or accompanying documents is the most important rule. The
prescribed manner of labeling varies greatly from country to country. Before doing business, it is therefore vital to have an exact knowledge of these
regulations. In general, the following information is required as a minimum:

1. type designation or name of the fertilizer

2. guaranteed content of each nutrient
3. name and address of the person responsible for sale
4. weight of product

Special rules apply to trademarks and trade names. There are special rules for packaging and sealing; most of these are restricted to certain fertilizers.

Official Inspections, Sampling, Analysis. As part of the supervision of fertilizer marketing, the sampling and analysis methods to be employed in official
inspections are set forth. The variety of methods and their continual development make a selection for official tests necessary. The official checking of the
guaranteed nutrient contents must be governed by rules that state whether and to what extent, unavoidable deviations are tolerated. For example, the EEC
has adopted definite unified tolerances for each type of fertilizer.

Fertilizer legislation also includes the action to be taken when violations occur (fines, seizure).

Finally, besides the special laws pertaining to fertilizers there are also provisions in other areas of legislation that must be observed in the fertilizer market. The
regulations on transportation and storage and the rules aimed at preventing epidemics, important for organic fertilizers, should be kept in mind.

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11. Economic Aspects

Friedrich Kuhlmann, Hugo Steinhauser, Walter Brändlein, Karl-Friedrich Kummer

Consumption, production, and international trade of fertilizers are determined by technical, economic and legal factors, i.e., by output – input efficiencies, factor
and product prices, and legal constraints. This applies to the single plot of an individual farm up to the agricultural area of entire nations and continents. While
in developing countries consumption of fertilizers is still growing, in developed countries environmental concerns are making themselves felt, leading to legal
and economic disincentives against unduly high fertilization rates. However, because of sustained world population growth, world consumption of mineral
fertilizers will further increase within the next decades.

11.1. Economics of Fertilization

11.1.1. Input – Output Relationships: The Yield Function
Assessing economic benefits of fertilization is a relatively complex task, since the outputs of crop production processes are determined by numerous input
factors, affecting the output level and being interdependent among each other. The precondition for economic considerations, therefore, is quantitative
knowledge about (crop) yield functions. Although at present this knowledge is still not complete, it can safely be stated that plant growth obeys basic laws of
nature, especially chemical laws. The relevant yield function for a crop — as JUSTUS LIEBIG first showed with his “law of minimum” — can thus be written as:

(1)

y = amount of crop output

xj = supply of necessary inputs
bj = partial output – input coefficients

The xj comprise inputs which are controllable by the farmer (seed, fertilizers, pesticides, etc.), as well as those which are not controllable (solar energy, genetic
yield potential, water in rainfed agriculture, etc.). The output level y is determined by the input whose supply is minimal compared to all other inputs. Given
certain supplies of all but one particular input, the output increases proportionally with increasing supply of this input, until some other input becomes the
minimum factor. Further augmentation of the variable input does not lead to any further output; it would be wasted. When a fertilizer is the variable input, the
relationship is called a linear response and plateau function (LRP function; Fig. 48) [627].

Figure 48. Types of yield function

The LRP function, however, is not compatible with results of fertilizer field experiments, investigated by means of regression analysis [628-630], [640]. Usually,
these empirical investigations lead to curves shaped according to the “law of diminishing returns” (LDR function; Fig. 48). The difference between the two
types of response function can be explained by the fact that available supplies of one or more of the other inputs vary from plant to plant in a plot (e.g., genetic
potential, water) [641-643].

To simplify further discussion, it shall be assumed that the output (e.g., wheat) is only restricted by two inputs: the variable input xv (e.g., nitrogen) and a given
input xg, whose amount varies randomly from plant to plant (e.g., genetic potential). Equation (1) then simplifies to:

(2)

Assuming a discrete distribution for the amounts of xg, Equation (2) can be expanded to:

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(3)

y = wheat output in dt/ha

i = number of classes in the discrete distribution of the genetic potential
pi = probabilities of the different classes of the discrete distribution
xgi = genetic potentials of the plants in the different classes of the discrete distribution, measured in dt/ha
xv = variable supply of nitrogen, measured in kg/ha
bg, bv = partial input – output coefficients

If, e.g., i = 5, pi = [0.1; 0.2; 0.4; 0.,2; 0.1], xgi = [20; 40; 60; 80; 100], bg = 1 and bv = 0.33, increased amounts of nitrogen (in steps of 40 kg/ha) result in the plot
yields shown as dots in Figure 48. Applying regression analysis leads to the LDR function also depicted. Although each plant grows according to a LRP
function, the analysis of this small “experiment” suggests a law of diminishing returns.

The shape of the LDR function depends upon the variance of the spatial distribution of the input xg within a plot. A smaller variance produces LDR curves that
more closely resemble the LRP function. When the variance approaches 0, the LDR function transforms into a LRP function. This relation is especially
important because modern plant breeding has reduced genetic variance of varieties (sometimes to zero), and modern land cultivation has homogenized soil
conditions.

11.1.2. Factors Controlling the Optimal Nitrogen Fertilization Level

The above relation is of essential importance in determining the economically optimal supply of the variable input nitrogen. Assuming the LDR function of
Figure 48, a wheat price of 11 €/dt, a nitrogen price of 0,6 €/kg, and a nitrogen delivery from the soil of 80 kg/ha, the optimal nitrogen fertilization rate can be
derived as shown in Figure 49. The farmer tries to maximize the difference between the monetary return (LDR1) and the nitrogen costs (NC1). This maximum
is obtained at the nitrogen input level (Nop1) for which the slope of the monetary return curve equals the (constant) slope of the nitrogen cost line, that is, when
marginal monetary returns equal marginal nitrogen costs [631].

Figure 49. Economically optimal nitrogen supply in crop production, assuming the law of diminishing returns (LDR function)

Changes of output and/or input prices lead to different optimal nitrogen input levels and profitabilities. For example, doubling the wheat price to 22 €/dt results
in the monetary return curve LDR2. Tripling the nitrogen price to 1,8 €/kg results in the cost line NC2. The first variation leads to the increased optimal nitrogen
supply level Nop2, the second variation to the decreased optimal nitrogen supply Nop3. Generally speaking, increasing crop prices and/or decreasing factor
prices result in higher fertilizer consumption, and vice versa.

If, however, the crop yield responds to variable nitrogen input levels according to an LRP function, then the farmer who tries to maximize the profitability would
always provide the same nitrogen input level, regardless of price situations. Figure 50 shows monetary return functions for wheat prices of 11 €/dt (LRP1), and
22 €/dt (LRP2). In addition, the nitrogen cost lines, repeated from Figure 49, are depicted. Clearly, for all price situations the farmer would try to ensure the
same optimal nitrogen input level Nop1.

Figure 50. Economically optimal nitrogen supply in crop production, assuming linear response and plateau functions (LRP functions)

In modern agriculture, the yield functions are approaching LRP functions, so that price variations have less and less impact on levels of fertilization.

11.1.3. Factors Influencing the Optimal Nitrogen Fertilization Level

As can easily be derived from Equation (1), other factors, especially the levels of noncontrollable inputs for plant growth, exert a substantial influence on the
optimal nitrogen input level. Firstly, the soil and climate conditions of a particular piece of land play a major role. Increased availabilities of solar energy and/or
plant-available water allow for more productive fertilizer consumption, returning higher yields. As an example, Figure 51 shows the nitrogen response functions
LRP1 and LRP2 for two parcels of land with different water conditions. The higher optimal yield y2 of the “better” parcel can be obtained only if the nitrogen
supply is increased from Nop1 to Nop2. Water and nitrogen are complementary inputs with respect to crop yield.

Figure 51. Effects of increased yield potentials on nitrogen requirement

Secondly, modern plant breeding successively produces varieties with higher yield potentials, enabling the plants to consume water and/or solar energy more
effectively. This, of course, leads to higher yields, provided the fertilizer input level is increased appropriately. Figure 51 may be also interpreted in terms two
varieties of different productivity.

Thirdly, modern crop-protection agents keep the plants healthy during the vegetation period, enabling them to consume more solar energy and water. This
again leads to higher yields, provided the fertilizer input level is adjusted accordingly. The situation with and without the application of modern pestizides can
also be represented by the LRP functions of Figure 51.

Under a wide range of price situations, the farmer would make full use of favorable soil and climatic conditions, as well as of the advantages of improved seeds

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and crop-protection agents. As a rule, the additional monetary returns of the increased yields are much higher than the additional costs for fertilizers, seeds,
and pesticides.

11.1.4. Environmental Aspects of Fertilization

Ecological concerns with respect to fertilization are becoming more and more important. They arise from the fact that farmers apply more fertilizers than may
be consumed productively by the crops. Depending on soil conditions, some part of the surplus will not be stored in the soil to be used by the following crop,
but will be leached into the underground, eventually contaminating the ground water.

However, even state-of-the-art fertilization causes some nitrogen surplus. This is due mainly to two facts: First, as discussed above, the levels of certain
noncontrollable plant growth inputs are distributed randomly over a plot of land. Since the farmer does not know the exact locations, he will fertilize the whole
field evenly or, in case of precision agriculture methods, at least larger parts of it. He will try to provide a nitrogen level such that the average marginal costs for
the plot are equal to the average marginal monetary returns. Unavoidably, there will always be some low-yielding spots which receive too much fertilizer.

Second, under most climatic conditions for rainfed agriculture, plant-usable water supply varies from year to year. Since the farmer does not know the water
supply of a particular year in advance, he will always “shoot” for a “good” year. If, for example, in a good year the higher yield y2 in Figure 51 is achievable,
and in a “dry” year only the lower yield y1, the farmer will nevertheless always provide for the higher nitrogen level Nop2 instead of the lower level Nop1. The
reason is simple: the expected profitability value of strategy Nop2 is under realistic price and weather conditions much higher than that of the strategy Nop1.

If the farmer provided only for the low fertilization level Nop1, in a good year he would lose the monetary return of 20 dt/ha (see Fig. 51), because the
insufficient nitrogen supply would limit the yield. At a wheat price of 11 €/dt, this corresponds to a loss of 220 €/ha. At the higher nitrogen level Nop2, in a dry
year 60 kg/ha nitrogen would be wasted (Fig. 51). This corresponds to a loss of 36 €/ha.

These economically induced fertilizer surpluses can be reduced by further improvements of inputs, production techniques, and prognostic information. Seed
varieties with less genetic variance and homogenization of soil conditions lead to less variance of the noncontrollable growth factors within a field. Splitting
nitrogen fertilization into several applications as the vegetation period develops and new information about the water supply becomes available also reduces
waste of nutrients. Finally, improved long-term weather forecasts would be most valuable in reducing the uncertainty involved in fertilizing decisions.

Strict legal constraints for nitrogen application rates, however, would not be the strategy of choice. It would lead to a waste of valuable yield potential and in
addition to economic losses for farmers.

11.2. World Consumption, Production, and Trade

Consumption. World consumption of the three primary nutrients — nitrogen, phosphate and potash — reached a total of 135.0 × 106 t in 1996/97. The
previous record level of 145.6 × 106 t in 1988/89 was once again not reached. The consumption figures broke down as follows [625] in 106 t:

Nitrogen 82.9 N
Phosphate 31.1 P2O5
Potash 21.0 K2O

Over the past 10 years, agricultural consumption of fertilizers experienced a deep recession, mainly due to developments in Central and Eastern Europe, as
well as in the former Soviet Union. World consumption fell by 17 % from 1988/89 to 1993/94 and then recovered by 12 % up to 1996/97. Over the ten year
period, nitrogen increased by 16 %, phosphate fell by 10 %, and potash fell by 19 %.

The consumption ratio N : P2O5 : K2O was 1 : 0.6 : 0.5 in 1976/77; it changed in favor of nitrogen to 1 : 0.5 : 0.4 in 1986/87, and in 1996/97 it reached
1 : 0.4 : 0.25. While in North America and Western Europe the ratio is 1 : 0.4 : 0.4, it is less well balanced in other regions of the world (Table 39). Fertilizer
consumption and production are given for fertilizer years, running from 1 July to 30 June. For example, 1996/97 is the period from 1 July 1996 to 30 June
1997.

Table 39. World nitrogen, phosphate and potassium consumption in millions of tonnes over the period 1976/77 – 1996/97 broken down by
region/country [625] *

Region/country Fertilizer season

1976/77 1986/87 1996/97

106 t % 106 t % 106 t %

Nitrogen (N) fertilizer consumption

Western Europe 8.8 19.0 11.4 15.9 10.1 12.2

Central/Eastern Europe 3.7 8.0 4.4 6.2 2.4 2.9

Former Soviet Union 7.3 15.7 11.5 16.1 2.8 3.4

North America 10.3 22.2 10.4 14.5 12.9 15.6

Latin America 2.2 4.7 3.8 5.3 4.1 4.9

Asia ** 12.4 26.7 27.7 38.7 47.4 57.2

Africa 1.5 3.2 1.9 2.7 2.3 2.8

Other 0.2 0.4 0.4 0.6 0.9 1.1

World 46.4 100.0 71.5 100.0 82.9 100.0

Phosphorus (P2O5) fertilizer consumption
Western Europe 5.8 21.6 5.3 15.3 3.7 11.9

Central/Eastern Europe 2.7 10.1 2.0 5.8 0.7 2.3

Former Soviet Union 4.9 18.3 9.1 26.2 0.9 2.9

North America 5.6 20.9 4.3 12.4 4.8 15.4

Latin America 2.0 7.5 2.8 8.1 2.9 9.3

Asia ** 3.8 14.2 9.2 26.5 15.7 50.5

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Africa 0.9 3.4 1.0 2.9 1.0 3.2

Other 1.1 4.1 1.0 2.9 1.4 4.5

World 26.8 100.0 34.7 100.0 31.1 100.0

Potassium (K2O) fertilizer consumption
Western Europe 5.5 5.7 5.9 22.6 4.3 20.5

Central/Eastern Europe 2.9 3.0 2.8 10.7 0.7 3.3

Former Soviet Union 5.6 5.8 6.7 25.7 1.2 5.7

North America 5.5 5.7 4.8 18.4 5.2 24.8

Latin America 1.2 1.2 1.9 7.3 2.6 12.4

Asia ** 1.8 1.9 3.4 13.0 6.2 29.5

Africa 0.3 0.3 0.4 1.5 0.4 1.9

Other 0.2 0.2 0.2 0.8 0.4 1.9

World 23.0 23.9 26.1 100.0 21.0 100.0

Total fertilizer consumption (N + P2O5 + K2O)
World 96.2 132.3 135.0

* FAO Fertilizer Yearbook 1980, 1990 and 1997.

** Excluding Asian republics of former Soviet Union.

In case only calendar year figures are available, e.g., 1996 is summarized under 1996/97. A regional analysis of fertilizer consumption shows that over 60 % is
used in developing countries (in Asia, Latin America, Africa). The Asian markets are particularly important. About 50 % of all fertilizers consumed are applied in
Asia. North America takes second place with 17 %, followed by Western Europe. Three decades ago, Western Europe was the world's largest fertilizer
consumer; after 10 years, the Eastern Bloc had overtaken Western Europe; and another 10 years later, the developing countries have taken the lead —
having increased their consumption tenfold in 30 years. This change corresponds to a mean annual growth rate of 8 %.

The intensity of fertilizer use, however, is still greatest in Western Europe. In terms of nutrient per hectare of agricultural area, Western Europe averaged
121 kg applied in 1996/97 (Table 40). The corresponding figure for the developing countries is 24 kg. In these countries, however, virtually no fertilizer is
applied to pastureland. If the figures are referred to agricultural area minus pastureland, the rate in the developing countries was 88 kg of nutrients per hectare,
56 kg of this being N. Fertilizer application is extremely low in the former Soviet Union (8 kg/ha).

Table 40. Nutrient use per hectare of agricultural area, [625], [632]

Region Nutrient application, kg/ha

N P2O5 K2O Total

Western Europe 67.6 24.7 28.8 121.2

Central/Eastern Europe 36.1 10.6 9.9 56.6
Former Soviet Union 4.8 1.5 2.1 8.4
North America 26.0 9.8 10.5 46.4
Other 15.2 5.8 2.7 23.6
World average 16.9 6.3 4.3 27.5

aConsumption: FAO Fertilizer Yearbook, Agricultural Area: FAOSTAT Database results

Three countries account for over half of world fertilizer consumption: China with 36.6 × 106 t, the United States with 21.2 × 106 t, and India with 14.3 × 106 t.
Next on the list are India with 14.3 × 106 t, France with 5.1 × 106 and Brazil with 4.8 × 106.

In years to come, a further worldwide increase is expected. This growth will take place chiefly in Asia, Latin America and Africa. The recovery of fertilizer use in
Central/Eastern Europe and the former Soviet Union is anticipated but will take time.

Production. A survey of production in 1996/97 showed that Asia ranks first as world fertilizer producer, mainly for nitrogen, but also for phosphate fertilizers,
followed by North America, the leading potash producer (Table 41).

Table 41. World fertilizer production by nutrient and region 1996/97 [625]

Region Nutrient production, 106 t

N P2O5 K 2O Total

1986/87 1996/97 1986/87 1996/97 1986/87 1996/97 1986/87 1996/97

Western Europe 11.8 9.5 4.4 2.9 8.3 5.4 24.5 17.8
Central/Eastern Europe 6.1 4.8 2.8 0.9 0.0 0.0 8.9 5.6
Former Soviet Union 15.0 8.7 8.5 2.5 10.2 5.5 33.7 16.7
North America 13.6 19.3 9.4 11.3 8.2 8.9 31.2 39.5
Latin America 3.0 3.2 1.9 1.8 0.1 0.4 5.0 5.4
Asia * 26.0 42.6 7.7 11.5 2.0 3.2 35.7 57.4
Africa 1.7 2.7 1.9 2.5 0.0 0.0 3.6 5.2
Oceania 0.2 0.3 0.8 0.7 0.0 0.0 1.0 1.0
World 77.4 91.1 37.4 34.1 28.8 23.4 143.6 148.6
World supply ** 72.6 85.8 34.9 32.2 26.1 21.8 133.6 139.7

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* Excluding Asian republics of former Soviet Union.

** Available world supply was arrived at by deducting from production estimated amounts for technical uses, further processing, transport, storage, and
handling losses.

Over the past ten years the production pattern by region shows a considerable decrease in Western and Central/Eastern Europe (– 27 % and – 37 %,
respectively) but above all in the former Soviet Union (– 50 %). In North America (+ 27 %) and especially Asia (+ 61 %) production increased markedly. While
overall world production remained nearly stagnant (+ 3.5 %), nitrogen production increased by 18 %, but phosphate and potash dropped by 8 % and 16 %,
respectively.

The leaders in production of fertilizers are China, the United States, and India. They are followed by Canada, the world's largest potash producer, and Russia
(Table 42).

Table 42. Fertilizer production by country, 1996/97 [625]

Country Fertilizer production, 106 t

N P2O5 K2O Total

China 20.1 5.8 0.2 26.1

United States 12.5 * 10.9 0.8 24.2
India 8.6 2.6 0.0 11.2
Canada 2.7 * 0.4 8.1 11.2
Russia 4.9 1.6 2.6 9.1

* Author's estimate (available supply)

The rise in fertilizer production and consumption in recent decades could not have taken place without an enormous technical advance. Significant cost
savings in ammonia production, the intermediate for nitrogen fertilizer production, resulted from the changeover from multi-train to single-train plants and the
conversion to more economical feedstocks, mainly natural gas.

Due to improved product quality and well-balanced particle size spectrum, rational bulk transportation and easier application become possible. Higher analysis
fertilizer grades brought savings in shipping and storage per unit of nutrient.

The fertilizer processes were optimized to decrease energy consumption. Emission reduction with modern techniques improved the environmental
performance of the processes and at the same time increased the nutrient yield from the raw materials. These improvements are of great importance: the
149 × 106 t of nutrients produced worldwide in 1996/97 meant 430 × 106 t of fertilizers that had to be stored, transported, and applied (authors estimate).

World Trade. Recent decades have seen a sharper rise in world trade than in consumption. Because of the limited number of potash deposits, the ratio of
trade to consumption is highest for potash, with 91 %. Some 40 % of phosphate and 29 % of nitrogen are sold internationally (Table 43).

Table 43. World fertilizer trade in millions of tonnes (exports) (106 t) [625] *.

Nutrient Fertilizer season

1976/77 1986/87 1996/97

N 8.5 17.4 24.2

P2O5 4.4 9.5 12.4
K2O 13.7 17.6 19.1
Total 26.6 44.5 55.7

* FAO Fertilizer Yearbooks

In nitrogen, Russia and the USA have the largest exports, but Canada, Ukraine, and the Netherlands are also important in the world market. The most
important importing regions are China and the USA.

American exporters dominate the phosphate market, with sales in all regions, but primarily in the developing countries in Asia, Latin America and Africa. The
largest exporters of potash are Canada and Germany, followed by Belarus and Russia.

The largest exporters and importers in 1996/97 are listed in Table 44.

Table 44. Major exporting and importing countries for nitrogen, phosphate, and potash fertilizers, 1996/97 [625]

Country Exports, 106 t Country Imports, 106 t

Nitrogen (N)
Russia 3.6 China 4.7

United States 3.0 United States * 2.0

Ukraine 1.2 France 1.3

Netherlands 1.2 India 1.2

Canada * 1.3 Germany 1.2

Phosphate (P2O5)
United States 5.7 China 2.8

Russia 1.2 India 0.7

Morocco 0.8 Australia 0.7

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Tunisia 0.7 France 0.6

Netherlands 0.4 Thailand 0.5

Potassium (K2O)
Canada 7.9 United States 5.2

Germany 2.6 Brazil 1.8

Belarus 2.0 France 1.1

Russia 1.9 India 0.7

Israel 1.2 Malaysia 0.6

* Author's estimates.

Types of Fertilizers. As the quantities produced and applied have increased, the importance of fertilizer grades has changed. Low-analysis grades have
decreased, while highly concentrated grades such as urea, triple superphosphate, and NPK fertilizers have gained (Fig. 52). Sulfur-containing fertilizers have
gained importance to cope with sulfur deficiencies.

Figure 52. World fertilizer consumption by type, 1996/97 preliminary [632]

A) Nitrogen fertilizer; B) Phosphate fertilizer; C) Potassium fertilizer

Urea has become the preferred nitrogen fertilizer, especially in the developing countries. In Western Europe, for example, ca. 80 % of nitrogen consumption is
in the form of ammonium nitrate, calcium ammonium nitrate, and ammonium nitrate-based multinutrient fertilizers. Phosphate consumption is dominated by
multinutrient fertilizers. In the case of potash, straight potassium chloride is the most important grade, but potassium sulfate is of growing importance due to its
sulfur contents.

11.3. Future Outlook

The decisive factors for the development of fertilizer demand are population growth and changes in the available income per capita. A growing world
population needs more food and fiber. In addition, a wealthier population has a higher daily energy intake per capita and it generally consumes a higher share
of animal products (Table 45). Compared to direct human consumption, three to four times more plant products such as cereals are necessary to produce the
same amount of energy in the form of animal products like milk, eggs, and meat.

Table 45. Dietary energy supply per capita by economic group 1969 – 1971 and 1990 – 1992 [633]

Country Group Total kcal/d % animal

1969 – 71 1990 – 92 1969 – 71 1990 – 92

Industrialized 3120 3410 30.4 29.8

Transition 3330 3230 24.4 27.6
Low-income 2060 2430 6.1 9.3
Least developed 2060 2040 6.6 6.0
World 2440 2720 15.6 15.7

11.3.1. Food Situation

Since the 1950s world food production per capita has continuously increased, although world population has more than doubled (from 2.5 to almost 6.0
billion). New crop varieties and improved production techniques enabled a substantial growth of average yields. A significant advance was the broader use of
effective cereal fungicides in industrialized countries and the introduction of high-yielding varieties of rice, wheat, and maize in several developing countries,
known in the 1970s as the “green revolution”. These varieties, bred for tropical and subtropical regions, already offer a higher yield potential under traditional
growing conditions. But their full potential can only be exploited when crop husbandry and plant nutrition are adapted to their needs, and agrochemicals
provide protection against insects, diseases, and competition from weeds. In many cases they rendered the use of fertilizers and agrochemicals economic for
the first time. The average yields of cereals, the most important staple food of humans, increased substantially (Table 46).

Table 46. World production and average yields of cereals 1972 – 1974 and 1996/97

Production, 106 t Yield, t/ha

1972 – 74 1996 – 97 1972 – 74 1996 – 97

Wheat 359 581 1.66 2.53

Maize 300 562 2.75 4.02
Barley 164 155 1.88 2.33
Rye, Oats 81 54 1.68 1.85
Rice 325 558 3.23 3.76
Total 1229 1910 2.19 3.11

According to the FAO, on average each kilogram of fertilizer nitrogen applied to the soil produces about 12 kg of cereal units (1 kg of cereal unit is equal to the
nutritional value of 1 kg of barley); therefore, it can be calculated that the food for half of the world's population can only be provided due to the use of (75 –
80) × 106 t nitrogen in mineral fertilizers annually. Nevertheless, 840 million individuals still suffer from undernutrition and an estimated 20 million die annually
of hunger and undernutrition-related diseases. Civil wars, natural disasters, and poverty, often related to unemployment, are the main reasons for starvation.

Growth in Food Demand. The 1996 update of the UN World Population Prospect shows that the rate of world population growth has declined to 1.48 % per

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annum, but this still means an additional 80 million humans to be fed every year. By the year 2020 world population is predicted to reach 7.67 billions. Since
economic growth is expected to continue, a larger part of the population will be able to spend more money on food. Thus an increased demand per capita for
plant products to be used as animal feed must be taken into account. The demand for cereals is expected to increase by 41 % from 1993 to 2020, that for
meat by 63 %, and the consumption of tubers and root is estimated to rise by 40 % [634].

Agricultural Land Use. More than 70 % of the world's surface is covered by water. Of the 13.4 billion hectares of dry land, 4.7 billion hectares are used by
agriculture. The major portion is covered by extensively used grasslands, often in low-rainfall areas. Most of the food is supplied by the 1.4 billion hectares of
arable land — a mere 10 % of the dry land. Much of the remaining area is not suitable for intensive agricultural production since it is either too dry, too steep,
too cold, or infertile. The majority of soils usable for arable crops are covered by biotopes such as rain forests. There is no agreement to which extent they
should be used for agriculture and how much must be preserved. FAO [635] calculated that Sub-Saharan Africa and Latin America have the most land
reserves with crop-production potential.

At the same time 7 million hectares agricultural land are lost annually due to erosion and salination. The agricultural area available per capita declined from
0.44 ha (1960) to 0.27 ha (1990) and is expected to shrink further to 0.17 ha by 2020. Therefore FAO estimates that although newly cleared land may supply
21 % of the necessary increase in food production, and more frequent use of existing arable land 13 %, the most important contribution (66 %) must come
from higher yields on soils already under cultivation. Although neither the quality of soils nor the agroclimatic conditions will allow the same high yield to be
achieved everywhere, the wide variation in actual yields offers a vast potential for further improvement (Figure 53).

Figure 53. Average nutrient application rates (kg N + P2O5 + K2O per hectare) and average yields (t/ha) of countries with high, medium, and low fertilizer application
rates in 1995 [636]

Intensity of Agricultural Production. The intensity of agricultural production is highest in industrialized and transition economies, where the purchasing
power for food is high. Attractive markets create an efficient production system, whereas the subsistence farmer cannot invest in yield-raising inputs. Annual
nutrient application rates therefore vary widely (Figure 53). Western European countries, Egypt, Saudi Arabia, and Mexico for example apply on average more
than 200 kg N + P2O5 + K2O per hectare wheat and harvest 4 – 7 t of grain, whilst countries using less than 50 kg plant nutrients obtain barely more than 2 t
per hectare [636]. This of course can also be the result of unfavorable growing conditions, primarily insufficient supply of water, but for most countries it reflects
the socio-economic situation.

Wheat is the crop which receives most (22 %) of the fertilizer nutrients, followed by rice and maize (17 % each). Cereals in total count for 65 % of the nutrient
consumption, while 9 % are used on oil crops, 5 % each on vegetables and sugar beet/cane). Thus, fertilizers are predominately used for food production.
Fiber crops, tobacco, and stimulants receive 4 and 2 %, respectively [636].

In the past countries with economic and population growth have increased their fertilizer consumption (Table 47), whereas those with traditionally high
consumption only show moderate growth (e.g., United States, Canada, Spain) or a decrease in consumption. This is the case for most EU countries, where
nutrient levels in the soil have mostly been built up to the desirable level, environmental concern has led to strict regulations, and changes in agricultural
policy, such as leaving arable land fallow, have been introduced. Changes of the economic system in the former centrally planned economies resulted in a
dramatic decline in agricultural production and consequently in fertilizer consumption.

Table 47. Development of fertilizer use in the 20 countries with the highest actual nutrient consumption 1985/86 – 1995/96 in 106 t N + P2O5 + K2O
[637]

1985/86 1995/96

China 16 852 35 527

USA 17 831 20 113
India 8504 13 876
France 5695 4915
Brazil 3197 4309
Germany 4823 2818
Indonesia 1972 2512
Pakistan 1511 2443
Canada 2325 2436
UK 2524 2264
Italy 2162 1883
Spain 1734 1817
Australia 1155 1735
Russian Fed. 1700
Turkey 1427 1700
Japan 2034 1642
Poland 3413 1511
Vietnam 386 1448
Thailand 434 1443
Malaysia 611 1247
World 128 613 130 865

11.3.2. Development of Fertilizer Consumption

World fertilizer consumption will continue to rise by more than 2 % per annum from 1996/97 to 2002/03 [638], [639]. The rate of growth will be highest in the
densely populated countries of South Asia (+ 5.2 %), in Latin America (+ 5.0 %), Africa (+ 4.9 %) and Central Europe (+ 4.4 %) (Figure 54). The estimated
increase in Central Europe signals a recovery from economic depression, while the growth rate in Africa simply reflects the low base. For Western Europe, a
further decline in fertilizer consumption is forecast since the agricultural area in this densely populated, industrialized region will continue to decline, and more
efficient use of organic manures (farmyard manure, sewage sludge, etc.) will be necessary to achieve the goals set for the protection of the environment.

Figure 54. Fertilizer consumption forecast by region 1995 – 2002 [638]

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veredlungsstarken Gebieten Nordrhein-Westfalens als Prognosekriterien des potentiellen Phosphataustrags in Drain- und Grundwasser,”
Forschungsber. 64, Lehr- und Forschungsschwerpunkt “Umweltverträgliche und standortgerechte Landwirtschaft”, Landwirtschaftliche Fakultät,
Universität Bonn, Bonn 1998.
618. Th. Diez, K. Bucksteeg: “P-fluxes in a Watershead Area with Intensive Agriculture and Eutrophication of a Lake,” paper presented at the Int. Symposium
of CIEC Agricultural Waste Management and Environmental Protection, 4th, Braunschweig-Voelkenrode 1987.
619. W. Werner: “Implementation and efficiency of countermeasures against diffuse nitrogen and phosphorus inputs into surface waters from agriculture”, in
E. Romstad, J. Simonsen, A. Vatn (eds.): Controlling mineral emissions in European agriculture, CAB International, Oxon – New York 1997 , pp. 73 –
88.
620. Industrieverband Agrar e.V., personal communication, 1997.
621. K. Isermann: “Einfluß der Phosphatdüngung auf den Cadmiumgehalt des Bodens, ermittelt anhand zahlreicher Dauerversuche in Westeuropa,”
Landwirtsch. Forsch. Sonderh. 39 (1982) 283 – 301.
622. B. Machelett, W. Podlesak, J. Garz: “Zur Wirkung des Cadmiumgehalts im Düngerphosphat auf die Cadmiumkonzentration in Boden und Pflanze in
einem langjährigen Phosphatdüngungsversuch,” Arch. Acker-Pflanzenbau Bodenkd. 28 (1984) no. 4, 247 – 251.
623. J. J. Mortvedt: “Cadmium Levels in Soils and Plant Tissues from Long Term Soil Fertility Experiments in the United States,” Congr. Int. Soc. Soil
Science, 13th, vol. 3, Hamburg 1986.
624. W. Werner, C. Brenk: “Entwicklung eines integrierten Nährstoffkonzeptes als Basis eines umweltverträglichen, flächendeckenden Recyclings
kommunaler Abfälle in Nordrhein-Westfalen und regionalisierte Bilanzierung der Schwermetallflüsse”, Forschungsber. 48, Landwirtschaftliche Fakultät
Universität Bonn, Bonn 1997.
General References
625. FAO Fertilizer Yearbook , Food and Agricultural Organization of the United Nations, Rome.
626. FAO Production Yearbook , Food and Agricultural Organization of the United Nations, Rome.
Specific References
627. Q. Paris: “The von Liebig-Hypothesis,” Am. J. Agric. Econ, 74 (1992) 4, 1019 – 1028.
628. E. von Boguslawski: Ackerbau, Grundlagen der Pflanzenproduktion, Frankfurt/M. 1981.
629. K. Baeumer: “Düngung”, in R. Diercks, R. Heitefuss (eds.): Integrierter Landbau, 2nd ed., München 1994 pp. 88 – 110.
630. E. O. Heady, J. L. Dillon: Agricultural Production Functions, Ames, Iowa 1961.
631. F. Kuhlmann: Betriebslehre der Agrar- und Ernährungswirtschaft, 2nd ed., Frankfurt/M. 2003.
632. World Fertilizer Consumption Statistics April 1998 IFA International Fertilizer Industry Association, 1998. FAOSTAT Database results Internet
http://www.FAO.org
633. FAO: The Sixth World Food Survey, Food and Agricultural Organisation of the United Nations, Rome 1996.
634. P. Prinstrup-Anderson et al.: The World Food Situation: Recent Developments, Emerging Issues and Long Term Prospects, IFPRI, Washington 1997.
635. FAO: Dimension of Need, An Atlas of Food and Agriculture, Food and Agricultural Organisation of the United Nations, Rome 1995.
636. G. Harris: “An Analysis of Global Fertilizer Application Rates for Major Crops,” International Fertilizer Development Centre (IFDC), Muscle Shoals 1998.
637. FAO: Fertilizer Yearbook, vol. 46, Food and Agricultural Organisation of the United Nations, Rome 1996.
638. IFA: “Fertilizer Demand Forecast,” International Fertilizer Industry Association, Paris 1998.
639. FAO: Fertilizer Outlook, Food and Agricultural Organisation of the United Nations, Rome 1996
640. J. Debruck, G. Fischbeck, W. Kampe: Getreidebau aktuell, 7th ed., Frankfurt/M. 1983.
641. F. Kuhlmann: “Zum 50. Todestag von Friedrich Aereboe: Einige Gedanken zu seiner Intensitätslehre,” Agrarwirtschaft 41 (1992) 222 – 230.
642. F. Kuhlmann, K. F. Frick: “Produktionstheoretische Betrachtungen über das “Gesetz des Minimums”, und das “Gesetz vom abnehmenden
Ertragszuwachs”,” Berichte über Landwirtschaft 73 (1995) 591 – 623.
643. K. F. Frick: “Analyse und Entwicklung von Standardproduktionsfunktionstypen in der pflanzlichen Produktion,” Sonderheft der Agrarwirtschaft, vol. 153,
Holm 1997.
[Top of Page]

Related Articles
Individual fertilizers are also described under the separate keywords Ammonia, Ammonium Compounds, Nitrates and Nitrites, Phosphate
Fertilizers, Potassium Compounds, and Urea

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Tsuneo Nakahara1, Shigeru Tanaka2, Masayuki Nishimura2 Print this page
1Sumitomo Electric Industries, Ltd., Osaka, Japan
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2Sumitomo Electric Industries, Ltd., Yokohama, Japan

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DOI: 10.1002/14356007.a10_433.pub2 Search All Content
Article Online Posting Date: December 15, 2006 Acronym Finder

Abstract | Full Text: HTML

Abstract
The article contains sections titled:

1. Introduction
2. Structure of Optical Fibers
2.1 Basic Structure
2.2 Multimode Fibers
2.3 Single-mode Fibers
2.4 Dispersion-modified Fibers
2.4.1 Dispersion-shifted Fibers
2.4.2 Nonzero Dispersion-shifted Fiber
2.4.3 Dispersion-flattened Fibers
2.5 Functional Fibers
2.5.1 Dispersion-compensating Fibers
2.5.2 Rare-earth-doped Fibers
2.5.3 Polarization-maintaining Fibers
3. Raw Materials and Production
3.1 Silica Fibers
3.1.1 Preform Production
3.1.1.1 Modified Chemical Vapor Deposition (MCVD) Method
3.1.1.2 Outside Vapor Deposition (OVD) Method
3.1.1.3 Vapor-Phase Axial Deposition (VAD) Method
3.1.1.4 Plasma Chemical Vapor Deposition (PCVD) Method
3.1.2 Fiber Drawing
3.2. Non-silica Fibers
3.2.1 Multicomponent Glass Fibers
3.2.2 Plastic Cladding Fibers
3.2.3 All-plastic Fibers
3.2.4 Infrared Fibers
4. Characterisitics of Optical Fibers
4.1 Transmission Loss
4.2 Dispersion
4.3 Multimode Dispersion
4.3.1 Chromatic Dispersion
4.3.2 Polarization Mode Dispersion
4.4 Nonlinearity
5. Reliability of Optical Fibers
5.1 Mechanical Strength
5.2 Hydrogen-induced Loss Increase
5.3 Radiation-induced Loss Increase
6. Applications of Optical Fibers

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6.1 Optical Fiber Cables
6.2 Fiber Connection Technologies
6.3 Optical Fiber Sensors
7. Future Prospects
7.1 New Fibers
7.1.1 Photonic Crystal Fiber (PCF)
7.1.2 Holey Fiber (HF)
7.1.3 Photonic Band-gap Fiber (PBGF)
7.2 New Systems
7.2.1 Soliton System
7.2.2 Code Division Multiplex (CDM)

The optical fiber is one of the most important key technologies that support the current information technology (IT) era.
Optical fibers are now widely used not only as an excellent transmission medium for optical communication but also as
optical functional devices, such as optical amplifiers. Both optical fibers and their manufacturing technologies have evolved
dramatically toward higher performance and improved productivity. Their applications have also been expanded from optical
communication to a variety of fields, such as optical sensors. This article reviews various aspects of optical fibers: structures
& materials, fabrication techniques, optical characteristics & reliability, and applications.

[Top of Page]

1. Introduction
The oldest scientific record concerning light transmission in a confined path is attributed to the British physicist J. TYNDALL
who, in 1870, studied the transmission of light in a curved stream of water. In 1930, the German physicist H. LAMM conducted
experiments on image transmission through a crude assembly of quartz fibers. In 1936, G. C. SOUTHWORTH, in the United
States, carried out theoretical and experimental studies on the behavior of electromagnetic waves in cylindrical
nonconductive materials; in the late 1950s, T. NAKAHARA made a theoretical and experimental study on a loosely bounded
electromagnetic wave along variously shaped dielectric lines using quasi-millimeter waves [1]. The phenomena they
observed are exactly the same as those encountered in the transmission of laser light through optical fibers.

In the 1930s, many physicists studied the transmissivity of materials (e.g., F. URBACH, K. A. STACEY, and B. SZIGETY). They
observed peaks in light absorption in the infrared region, which suggested the existence of a band with low absorption and
thus a low transmission loss between the ultraviolet and infrared regions.

An optical communication method using glass as a transmission medium had been proposed in Japan in 1936 [2]. In the
early 1960s, optical waveguides using lenses or lenslike media for optical signal transmission were studied by Bell
Laboratories in the United States. KAO and HOCKHAM [3] of Standard Telephone Laboratories (STL) in the United Kingdom
demonstrated in 1966 that removal of impurities from glass fibers reduced the loss (attenuation) of optical transmission to a
level acceptable for use in long-distance communications; they recommended quartz as a suitable transmission material. In
1968, KAWAKAMI and NISHIZAWA [4] proposed that an optical fiber with a refractive index distribution similar to that of a lens
could be used effectively as a high-capacity transmission medium.

Methods for fabricating transparent, pure fused silica glass have been in use since 1910. In 1935, a method of producing
synthetic silica glass was developed, based on the decomposition of volatile silicon compounds such as silicon tetrachloride [
10026-04-7]. Furthermore, by the early 1960s, the discovery had been made that the refractive index of pure fused silica
glass could be increased easily with various additives; the structure, materials, and characteristics of a suitable optical fiber
for signal transmission had also been described on a theoretical basis.

In 1969, Nippon Sheet Glass and the Nippon Electric Corporation (NEC) jointly produced a graded-index multicomponent
glass fiber, which they called Selfoc, using an ion-exchange process [5]. In the first trial production, the light attenuation of
the fiber was 80 to 200 dB km–1. In 1970, Corning Glass Works in the United States announced a silica fiber with an
attenuation of 20 dB km–1 [6], which was manufactured by depositing a particulate TiO2–SiO2 glass layer inside a silica tube
by flame hydrolysis. In 1974, Bell Laboratories reported the production of a low-loss fiber with an attenuation of 1.1 to 2 dB
km–1 by modified chemical vapor deposition (MCVD) [7]. The method of outside vapor deposition (OVD) was announced by
Corning Glass Works in 1973 [8]. Sumitomo Electric filed a continuous vapor-phase axial deposition process patent that
covered an arbitrary refractive index profile in 1974. Philips reported the plasma chemical vapor deposition (PCVD) method
in 1975 [9]. The Nippon Telegraph & Telephone Corporation (NTT) announced the development of the vapor-phase axial
deposition (VAD) process for step-index profile in 1977 [10]. The VAD process was rapidly improved, leading in 1981 to the
successful manufacture of long, uniform optical fibers whose light attenuation was 0.2 dB km–1.

The theoretical transmission loss of a silica fiber at a wavelength of 1.55 µm is about 0.13 dB km–1 and is limited by Rayleigh
scattering and the vibrational absorption of the Si O bonds. After the development of fluorine-stuffed pure silica fiber
announced in 1972, the transmission loss was decreased. Champion data of transmission loss 0.154 dB km–1 at 1.55-µm
wavelength and 0.1484 dB km–1 have been recorded in 1986 and in 2002, respectively [11].

As for mechanical strength, ordinary manufacturing equipment could not be used owing to the extreme brittleness of silica
fiber. Sufficient mechanical strength for practical use could not be attained by applying polyamide (nylon) extrusion to drawn

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fiber. However, the development in 1974 of the method of tandem resin coating immediately after drawing dramatically
improved the mechanical strength [12].

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2. Structure of Optical Fibers

2.1. Basic Structure
Optical fibers consist of a central core and a cladding layer that surrounds the core. The core has a slightly higher refractive
index than that of the cladding. The transmission of light in the optical fiber is illustrated in Figure 1.

Figure 1. Fundamental structure of an optical fiber

n1 = refractive index of core; n2 = refractive index of cladding; = angle of reflection at core–cladding interface;
= launching angle

When light is launched into the core at the endface of the optical fiber, the portion of the light whose angle is within a certain
range will be trapped inside the core by total internal reflection at the core–cladding interface. The critical angle for the total
internal reflection depends on the refractive index difference between the core and the cladding. It can be derived from
Snell's law. As a parameter determining the light-capturing efficiency, the numerical aperture, NA, is defined by the following
equation:

(1)

where n1 and n2 are the refractive indexes of the core and the cladding, respectively, max is the maximum launching angle
of the light, and c is the critical angle for total internal reflection.

Optical fibers are generally classified into two types: multimode fibers and single-mode fibers (SMFs).

2.2. Multimode Fibers

Multimode fibers have a relatively large refractive index difference (typically 1 to 2 %) between the core and the cladding and
a large core diameter, which is significantly larger than the wavelength of light and is typically several tens of micrometers or
larger. Because of these structural parameters, the multimode fibers have many light paths (or modes) traveling through the
core with slightly different angles.

The multimode fibers are further classified into two types depending on the refractive index profiles of the core: step-index
fibers and graded-index fibers. Figure 2 illustrates those two types of multimode fibers. The core of the step-index fiber has a
constant refractive index higher than that of the cladding, while the graded-index fiber has the refractive index gradually
changing as a function of the radial position.

Figure 2. Classification of optical fibers according to propagation modes

(a) step-index fiber; (b) graded-index fiber; and (c) single-mode fiber. a) Core; b) Cladding; c) Refractive index, n

2.3. Single-mode Fibers

When both the core–cladding refractive index difference and the core diameter are reduced, the number of the transmitting
modes (light paths) is decreased. Only one mode can be transmitted through the core, when these two parameters are
sufficiently small. This is the case of the SMF as illustrated in Figure 2.

The basic type of silica-based SMF has a typical refractive index difference of 0.3 to 0.4 % and a core diameter of several
µm. This standard type SMF is currently being used very widely in telecommunications. In optical communication systems
using the standard SMFs, the optical signal wavelengths mostly used are 1.3 µm, at which the fibers have small or zero
chromatic dispersion, and 1.55 µm, at which the fibers exhibit the lowest transmission loss, as described in detail in Section
Characterisitics of Optical Fibers.

2.4. Dispersion-modified Fibers

Although the standard SMFs are superior transmission media for optical communication, even higher performance optical
fibers of various types have been developed within the SMF category. The key parameter here is the chromatic dispersion.
Since all silica-based fibers exhibit the lowest transmission loss around the 1.55-µm wavelength, this wavelength band is
naturally suited for long-distance transmission. The chromatic dispersion of the standard SMF is, however, relatively large in
the 1.55-µm band. This may limit the transmission capacity or the transmission distance. Various types of SMFs whose
chromatic dispersion, especially in the 1.55-µm band, is modified or tailored to improve the transmission performance have
been developed. These dispersion-modified fibers usually have somewhat complicated refractive index profiles as illustrated
in Figure 3.

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Figure 3. Refractive index profiles of dispersion-modified fibers and chromatic dispersion characteristics of various fibers

2.4.1. Dispersion-shifted Fibers

The dispersion-modified fibers of the first generation are dispersion-shifted fibers (DSFs) [13, 14]. The DSFs have their zero
dispersion wavelengths (the wavelengths at which the chromatic dispersion is zero) shifted from the 1.3-µm band to the 1.55-
µm band, where the transmission loss is minimized. The DSFs are well suited to long-distance transmission of high bit-rate
optical signals.

2.4.2. Nonzero Dispersion-shifted Fiber

As the optical transmission technologies have recently been evolved with the advent of the optical fiber amplifier and
wavelength-division-multiplexed (WDM) transmission, further modification of the chromatic dispersion characteristics has
been applied to the DSFs. In long-distance WDM transmission with narrow wavelength spacing using optical amplifiers, the
signal quality tends to deteriorate because of nonlinear effects in the optical fiber. Such detrimental effects become
significant especially when the chromatic dispersion of the optical fiber is close to zero in the signal wavelength band.

The modified versions of DSFs whose chromatic dispersion is small but not zero in the 1.55-µm band are called nonzero
dispersion-shifted fibers (NZ-DSFs) [15, 16]. The NZ-DSFs are being widely used in long-distance and large-capacity WDM
transmission systems.

2.4.3. Dispersion-flattened Fibers

In general, the chromatic dispersion of the optical fiber has some dependence upon the wavelength. The wavelength
dependence of the dispersion (the differential of the dispersion with respect to the wavelength) is called dispersion slope.
Since both the DSFs and the NZ-DSFs have some dispersion slopes, the chromatic dispersion varies to some extent within
the signal wavelength range. This dispersion variation is increased and may become undesirable when the signal wavelength
band to be used is extended.

The SMFs whose dispersion slope is nearly zero in the wavelength range of concern are called dispersion-flattened fibers
(DFFs) [17, 18]. Because precise control of such dispersion characteristics is generally difficult in view of the fiber design and
fabrication, DFFs are still in the developmental stage and not yet fully commercialized.

2.5. Functional Fibers

Although optical fibers were originally developed as transmission media for optical signals, they have also found a number of
applications in which their optical functionality, other than optical transmission, is utilized. Among these functional fibers are
dispersion-compensating fibers (DCF), rare-earth-doped fibers, and polarization-maintaining fibers (PMFs).

2.5.1. Dispersion-compensating Fibers

When high bit-rate optical signals in the 1.55-µm band are transmitted through long standard SMFs, the signal waveforms
are deformed because of the relatively large positive chromatic dispersion. This signal deterioration can be suppressed by
inserting some SMFs that have large negative chromatic dispersions, which compensate for the positive dispersions of the
transmission fibers [19]. These DCFs are typically coiled and packaged in small boxes. Such DCF modules are placed in the
transmission equipment and used as optical functional devices.

2.5.2. Rare-earth-doped Fibers

Some of rare earth elements are known to be luminescent. Optical fibers whose cores are doped with specific rare earth
elements function as optical amplifiers. One of the most important rare earth elements is erbium, which is capable of
amplifying optical signals around the wavelength of 1.55 µm [20, 21]. The 1.55-µm band is one of the major wavelength
bands used in optical fiber communication, because silica fibers exhibit the lowest transmission loss. Praseodymium and
thulium are also known as additives for optical amplification in the 1.3-µm and 1.45-µm bands, respectively [21, 22].

Figure 4 illustrates the basic configuration of the erbium-doped fiber amplifier (EDFA). The pumping light at 0.98 µm or
1.48 µm launched into the fiber excites the erbium ions in the core, and the 1.55-µm optical signals traveling through the fiber
are amplified through stimulated emission from the erbium ions. The EDFAs are not only highly efficient in terms of the signal
gain or the output power but are also capable of simultaneously amplifying multiple optical signals that are WDM in the 1.55-
µm band. This feature has strongly supported the recent dramatic progress of WDM transmission.

Figure 4. Basic configuration of an erbium-doped fiber amplifier

2.5.3. Polarization-maintaining Fibers

Single-mode optical fibers that maintain the linear polarization state of the light transmitted through the fibers are called
polarization-maintaining fibers (PMFs). A typical cross section of the PMF is illustrated in Figure 5 [23]. The polarization of
light is maintained by the birefringence that is induced by two stress-applying parts composed of SiO2–B2O3 placed beside

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the core. The PMFs are often used in optical fiber sensors, such as fiber-optic gyroscopes, or for interconnection between
optical devices that have polarization dependence, such as laser diodes, optical modulators, and so on.

Figure 5. An example of a polarization-maintaining fiber

a) Core; b) Cladding; c) Stress-applying part

[Top of Page]

3. Raw Materials and Production

Optical fibers are basically made of optically transparent materials. Most of the optical fibers currently used in optical
communication are silica-based fibers because of their low transmission loss. There are also several materials other than
silica that are used for optical fibers, such as multicomponent glass, plastic, fluoride glass and so on.

3.1. Silica Fibers

Silica fibers are composed of SiO2 and some additives that modify the refractive index of silica. The additives are essential
for forming the basic fiber structure consisting of the core and the cladding, which have slightly different refractive indexes.
The refractive index of silica can be decreased by adding fluorine or B2O3 and increased by adding other metal oxides or
anions. The most popular additive or dopant for increasing the refractive index is GeO2. P2O3 and Al2O3 are also known to
increase the refractive index. Figure 6 shows the effects of various materials on the refractive index of silica.

Figure 6. Relationship between dopant concentration and refractive index of silica

3.1.1. Preform Production

In the production of silica fibers, silica-based glass rods, called preforms, are prepared first, and then the preforms are drawn
into thin fibers. A vapor-phase method is generally used to form silica fiber preforms. There are four major preform fabrication
techniques: modified chemical vapor deposition (MCVD), outside vapor deposition (OVD), vapor-phase axial deposition
(VAD), and plasma chemical vapor deposition (PCVD).

In preform production by the MCVD and the PCVD methods, the following oxidation reaction is utilized to synthesize SiO2:

The following hydrolysis reaction is employed in the OVD and the VAD methods:

The typical raw materials are volatile liquids (e.g., SiCl4, GeCl4, BBr3, POCl3) and gases (e.g., BCl3, CCl2F2, SiF4). Since the
vapor pressures of transition-metal halides are much lower than those of the raw materials, the fibers fabricated using these
techniques are very pure in terms of transition-metal impurities.

3.1.1.1. Modified Chemical Vapor Deposition (MCVD) Method

The MCVD technique, which was developed by Bell Laboratories [24], achieves glass deposition by letting the raw material
vapors and oxygen flow through a rotating silica tube, as illustrated in Figure 7. The tube is heated by using a traversing O2–
H2 burner. To obtain the desired refractive index profile, a number of glass layers of different compositions are deposited on
the inner wall of the tube. In some cases, P2O5 is added to decrease the deposition temperature. After the deposition, the
temperature is raised to 1800 to 2000 °C to collapse the tube into a solid preform.

Figure 7. Modified chemical vapor deposition (MCVD) method

(a) Deposition and (b) collapsing. a) Mass flow controller; b) Rotating silica tube; c) Synthetic glass layer; d) Traversing
burner

3.1.1.2. Outside Vapor Deposition (OVD) Method

The OVD technique was developed by Corning Glass Works [8]. Figure 8 illustrates the principle of the OVD technique. Fine

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glass particles (soot) are produced by flame hydrolysis of the raw materials with an O2–H2 burner and deposited on a
rotating rod. A number of soot layers are deposited by moving the burner many times along the rotating rod. The vapor
composition is changed layer by layer to produce a desired refractive index profile. After the deposition, the original rod is
removed from the soot rod, which is then dehydrated by heating in chlorine gas and sintered to form a solid preform.

Figure 8. Outside vapor deposition (OVD) method

(a) Soot deposition and (b) consolidation. a) deposited soot; b) rotating rod; c) traversing burner; d) soot rod; e) heater

3.1.1.3. Vapor-Phase Axial Deposition (VAD) Method

The VAD technique was developed by several Japanese companies [25]. Soot generated by flame hydrolysis is deposited on
the end of a rotating seed rod. A soot preform then grows in the axial direction, as illustrated in Figure 9. In the case of
graded-index fiber preform production, the refractive index profile is determined by controlling the temperature distribution on
the growing soot surface. Multiple O2–H2 burners may also be used to simultaneously deposit both the core and the cladding
for step-index fiber preforms. The soot preform is then dehydrated by heating in chlorine gas, and finally sintered to form a
solid preform.

Figure 9. Vapor-phase axial deposition (VAD) method

a) rotating seed rod; b) soot preform; c) O2–H2 burner; d) mass flow controller

Since the soot grows continuously in the axial direction in the VAD method, there is no fundamental limit to the soot length
that can be fabricated. The VAD technique enables fabrication of very large preforms with high productivity.

3.1.1.4. Plasma Chemical Vapor Deposition (PCVD) Method

The PCVD technique was developed by Philips [26]. Its concept is illustrated in Figure 10. A silica tube is evacuated to
reduce its internal pressure and raw materials and oxygen are fed in. Oxidation occurs in nonisothermal plasma produced by
a microwave cavity. The tube is typically placed in a furnace whose temperature is raised to 1200 °C, for example. After the
deposition, the tube is collapsed at a high temperature.

Figure 10. Plasma chemical vapor deposition (PCVD) method

a) Furnace; b) Traversing microwave cavity; c) Silica tube

3.1.2. Fiber Drawing

Silica fibers are fabricated by heating the end of a preform in a furnace and drawing it, as shown in Figure 11. The drawing
temperature is typically 2100 °C. There are two types of drawing furnaces: a carbon resistance furnace and a radio-
frequency induction furnace. The fiber diameter (typically 125 µm) is precisely controlled during the drawing process by
monitoring the diameter and adjusting the drawing speed.

Figure 11. Fiber drawing process

a) Preform; b) Furnace; c) Fiber diameter monitor; d) Coating applicator; e) Curing furnace; f) Capstan; g) Take-up bobbin

In order to maintain the mechanical strength of silica fibers, it is essential to immediately coat the fiber with some sort of resin
before it comes in contact with rollers or take-up bobbins in the drawing process. This prevents the generation of microscopic
cracks on the fiber surface. Figure 12 shows a comparison of the tensile strength between uncoated fibers and coated fibers.
Typical coating materials are urethane acrylate and silicone. The former is cured by ultraviolet light, and the latter is usually
cured by heat. A standard coating diameter is 250 µm.

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Figure 12. Tensile strength of coated and noncoated fibers

3.2. Non-silica Fibers

3.2.1. Multicomponent Glass Fibers
Multicomponent glass fibers are fabricated from ultrapure powders such as SiO2, Na2CO3, CaCO3, and KNO3. These
powders are mixed and melted in a crucible to form homogeneous, bubble-free glass. The core and cladding glasses are
melted separately, and then processed by the so-called double-crucible method, which employs two crucibles that have
concentric orifices at the bottom. The core glass is placed in the center crucible and the cladding glass in the outer crucible.
The crucibles are heated and the core and cladding glasses are drawn into a fiber having the core–cladding structure.

Although the multicomponent glass fibers are relatively easy to fabricate because of their low melting temperatures, their
transmission losses are higher than silica fibers. The transmission loss is typically 5 dB km–1 at 0.85 µm [27].

3.2.2. Plastic Cladding Fibers

While the standard silica fibers have the core and the cladding both of which are composed of silica, the cladding can be
replaced by some kind of polymer whose refractive index is lower than that of the silica core. This type of optical fiber is
called plastic cladding fiber.

The plastic cladding fibers can be fabricated by using techniques very similar to those developed for silica fibers. The fiber is
drawn from a silica rod and coated immediately with a low refractive index resin, such as silicone, as the cladding. The core
can be either pure silica with a constant refractive index (the step-index fiber) or germanium-doped silica with a graded-index
profile (the graded-index fiber).

3.2.3. All-plastic Fibers

All-plastic fibers consist of a plastic core and a plastic cladding. Polystyrene or polymethyl methacrylate is used as the core
material and fluoropolymer as the cladding material, for example. The all-plastic fibers feature excellent flexibility and large
dimensions (large core and cladding diameters), which enable easy connection and handling. Their transmission losses are,
however, relatively high at wavelengths exceeding 0.6 µm because of C–H vibration absorption. Lower transmission losses
at 1.3 µm have recently been achieved by using fluoropolymer as the core material [28]. Recent advances in fabrication
techniques have also enabled the formation of graded-index profiles [29]. Graded-index all-plastic fibers featuring large
bandwidths are believed to be useful for short-distance large-capacity transmission in buildings.

3.2.4. Infrared Fibers

As described in detail in Chapter Characterisitics of Optical Fibers, silica fibers have the lowest transmission loss around
1.55 µm, because of Rayleigh scattering, which is proportional to –4 and therefore decreases as the wavelength is
increased, and the infrared vibration absorption by the Si O bond in silica. It is anticipated that alternative materials having
vibration absorption in much longer wavelength bands may exhibit a transmission loss lower than that of silica at
wavelengths longer than 1.55 µm. Such non-silica materials that have been investigated are germanium dioxide, fluoride
glasses, chalcogenide glasses, and crystalline halides [30, 31].

Figure 13 shows examples of the transmission loss spectra of those infrared fibers. It is clear that the infrared fibers realize
transmission losses lower than those of silica fibers in wavelengths longer than 2 µm. Attempts to achieve ultralow loss
(lower than the silica fiber's minimum loss around 1.55 µm) in the infrared region, however, have never been successful. The
infrared fibers are used in short-distance applications with signal wavelengths longer than 2 µm, such as optical sensors.

Figure 13. Typical loss spectra of infrared fibers compared with those of silica and plastic fibers

a) Silica fiber; b) Plastic fiber; c) Chalcogenide glass fiber; d) Fluoride glass fiber; e) GeO2 fiber; f) Polycrystalline (AgBr)
fiber

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4. Characterisitics of Optical Fibers

4.1. Transmission Loss
The transmission loss of the optical fiber represents a decrease in optical power per unit length. It is directly related to the
maximum distance over which optical signals can be transmitted in optical communication systems, and is one of the most
important parameters of the optical fiber. The transmission loss of the optical fiber is generally given by the following
equation:

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(2)

where
= wavelength of light (µm)
A = Rayleigh scattering coefficient (dB km–1 µm–4)
B = loss induced by structural imperfection (dB km–1)
C( ) = wavelength-dependent loss induced by impurities and intrinsic absorption (dB km–1)

A typical transmission loss spectrum of silica fiber is shown in Figure 14. The first term in Eq. (2) is Rayleigh scattering, which
is caused by microscopic fluctuation of the density and/or the composition in glass, and it is one of the fundamental losses of
glass. The Rayleigh scattering loss is proportional to –4. The Rayleigh scattering coefficient, A, is approximately 0.7 dB
km–1 µm–4 for pure silica, and it increases as the concentration of index-changing additives, such as GeO2, is increased.

Figure 14. Typical transmission loss spectrum of silica fiber

The second term, the structural-imperfection-induced loss, is related to longitudinal fluctuation of the core – cladding
interface, for example, and it is generally independent of the wavelength. Improvement of the fabrication techniques has
reduced the structural-imperfection-induced loss to negligibly small levels.

One of the major contributions included in the third term of Eq. (2) is the intrinsic absorption induced by vibration of the Si
O bond in silica. A large absorption having a peak at 9.1 µm affects the transmission loss at wavelengths longer than
1.55 µm. Other important causes of absorption are hydroxyl bonds and transition-metal impurities, such as iron, copper,
cobalt, or nickel. In general, the concentration of the transition metal is so small that it does not affect the transmission loss of
silica fibers manufactured properly. On the other hand, the hydroxyl bonds exhibit a peaky absorption loss spectrum around
1.39 µm. However, it is also possible to reduce the hydroxyl content to sufficiently small levels by using improved dehydration
techniques in preform production [32]. Optical fibers with no hydroxyl loss around 1.39 µm are now commercially available.

In the end, the fundamental loss causes in silica fibers are only Rayleigh scattering and the Si O bond absorption. Since
the Rayleigh scattering coefficient depends on the dopant concentration in the core, the lowest transmission loss can be
achieved by a pure-silica-core fiber, which consists of a pure silica core with no additives and a cladding containing fluorine
that lowers the refractive index. Sumitomo Electric has reported the lowest transmission loss record of 0.1484 dB km–1 [11],
which is significantly lower than the standard germanium-doped-core fibers' loss of 0.2 dB km–1.

4.2. Dispersion
The dispersion represents the variation in the group velocity of light transmitted through the optical fiber. In general, the
dispersion determines the deformation of the optical signal waveforms, thus the transmission bandwidth of the optical fiber.
The dispersion is classified into three categories: multimode dispersion, chromatic dispersion, and polarization mode
dispersion.

4.2.1. Multimode Dispersion

The multimode dispersion is the variation in the group velocity among many different transmission modes, or many light rays
traveling with slightly different angles through multimode fibers. The multimode dispersion is applicable only to multimode
fibers. The concept of the multimode dispersion is shown in Figure 2.

The refractive index profiles of the graded-index fibers are designed so that almost all light paths have the same group
velocity. Note that the apparently shortest light path traveling straight along the core axis does not necessarily have the
highest velocity, since the velocity of light depends on the refractive index of the material (the higher the refractive index, the
lower the velocity). The optimum refractive index profiles of the graded-index fibers, which minimize the group velocity
variation among all transmission modes (light paths), are known to be nearly parabolic. The bandwidths of the step-index
fibers are significantly smaller than those of the graded-index fibers because of the multimode dispersion.

4.2.2. Chromatic Dispersion

There is no multimode dispersion in SMFs, since they have only one transmission mode. Therefore, SMFs, in general, exhibit
much larger transmission bandwidths than multimode fibers. The dispersion characteristics of SMFs are determined by the
chromatic dispersion and the polarization mode dispersion.

Figure 15 schematically shows the chromatic dispersion. The chromatic dispersion is the differential of the group delay of
light transmitted through the optical fiber with respect to the wavelength. The chromatic dispersion can be divided into two
effects: material dispersion and waveguide dispersion. The material dispersion is the characteristic intrinsic to the material,
silica in this case, and it varies depending upon the additives, such as germanium, but not very much. On the other hand, the
waveguide dispersion is the dispersion induced by the fiber structure, and it strongly depends on the refractive index profile.
By properly designing the refractive index profile, it is possible to some degree to tailor the waveguide dispersion, and thus
the chromatic dispersion. This is the base of the various dispersion-modified fibers described in Chapter Structure of Optical

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Fibers.

Figure 15. Group delay and chromatic dispersion characteristics of optical fibers

4.2.3. Polarization Mode Dispersion

Actually, SMF has two transmission modes, both of which are basically the same but whose polarization axes are
perpendicular to each other. The polarization mode dispersion (PMD) is the group delay difference between those two
orthogonal polarization modes. If the optical fiber is perfectly circular, the polarization modes have the same group velocity,
but slight noncircularity of the fiber structure and/or asymmetric stress distribution applied to the fiber induce some
birefringence, thus the PMD. Because optical power transfer between the two modes randomly occurs during transmission
through the fiber, behavior of the PMD has a somewhat statistical nature. The PMD is generally proportional to the square
root of the fiber length.

4.3. Nonlinearity
In general, phenomena whereby the material properties of a given medium change when high-intensity light is transmitted
through it are called nonlinear effects (see Nonlinear Optics and [33]). The nonlinearity of silica is significantly small
compared with various other glasses. It has, however, become important recently because optical fiber amplifiers increase
the optical signal power and the number of multiplexed optical signals in the optical fiber, resulting in noticeable levels of
nonlinear effects even in silica fibers.

The nonlinear effects that are of most concern for optical fibers are nonlinear refractive index (optical Kerr effect) and
stimulated scattering. The nonlinear refractive index is a small variation of the refractive index dependent upon the light
intensity. This may cause various detrimental effects in the optical fiber communication, such as self-phase modulation,
cross-phase modulation, and four-wave mixing. Among the stimulated scattering phenomena are stimulated Raman
scattering and stimulated Brillouin scattering. While nonlinear effects are generally harmful in optical fiber communication,
they are also useful in a variety of applications, such as fiber Raman amplifiers.

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5. Reliability of Optical Fibers

5.1. Mechanical Strength
The mechanical lifetime of the optical fiber depends on the stress applied to the fiber and the environmental conditions [34].
Figure 16 shows the relationship between the average time to fiber breakage and the applied stress in air and water. The
time to fiber breakage or the time to failure, tf, is given by

(3)

where a is the applied stress, and n and ks are constants that depend on the glass material and the environmental
conditions. For silica fibers in air, n is approximately 25 and ks about 2.2 × 1012. In production of the optical fiber, a certain
level of stress is applied to the fiber after drawing in order to eliminate any weak portion; this is called proof testing. The
expected lifetime of the fiber, tmin, is given by

(4)

where p is the stress applied during the proof testing and a is the stress applied to the fiber in use, for example, the fiber in
a cable. The constant B depends on the glass material and the environmental conditions. In general, high humidity and high
temperature shorten the fiber lifetime. However, proper proof testing in the fiber production and appropriate cable designs
ensure long-term reliability in standard applications.

Figure 16. Relationship between time to failure and applied stress for silica fibers in air and water

5.2. Hydrogen-induced Loss Increase

Hydrogen may be produced in optical fiber cables as a result of thermal dissociation of plastic, corrosion of metal by water, or

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electrolysis of water when two different metals are used in a cable. Two types of loss increase due to hydrogen are known:
absorption by hydrogen gas permeated into the glass and absorption by hydroxyl bonds formed as a result of reactions
between the glass and the hydrogen gas [35, 36]. The former loss increase is reversible, while the latter is not. Figure 17
shows the loss spectra of an optical fiber before and after 36-week exposure to hydrogen gas at room temperature. The
permeated hydrogen causes absorption of 8 dB km–1 at 1.24 µm.

Figure 17. Transmission loss spectra of a silica fiber before and after 36-week exposure to hydrogen at room temperature

Figure 18 shows the loss spectra of two SMFs before and after exposure to hydrogen at 200 °C. At high temperatures, the
hydroxyl absorption having a peak at 1.39 µm increases in the standard germanium-doped-core fiber, while the pure-silica-
core fiber exhibits no loss increase. This is because GeO2 reacts with hydrogen to form hydroxyl bonds but pure silica does
not. The pure-silica-core fiber is superior in terms of the transmission loss stability against hydrogen.

Figure 18. Stability of optical fibers after heating in hydrogen at 200 °C

(a) Single-mode fiber with a pure silica core; and (b) single-mode fiber with a GeO2-doped silica core

5.3. Radiation-induced Loss Increase

The transmission loss is also increased by irradiation [37]. The loss increase depends upon the type of radiation, its intensity
(dose rate), the composition of the fiber, the fiber fabrication process, and the fiber temperature during irradiation. The effects
of -ray, X ray, ultraviolet light, or neutron irradiation have been examined.

Among various silica-based fibers, the pure-silica-core fiber exhibits the smallest loss increase after irradiation. Addition of
GeO2 or P2O5 to silica results in a high sensitivity to all forms of irradiation, while B2O3 specifically increases the sensitivity to
neutron irradiation. The sensitivity is reduced by adding hydroxide ions or hydrogen and is increased by adding chlorine.

For a given total radiation dosage, the transmission loss increase is much larger for higher dose rates. In addition, irradiation
at a higher temperature results in a smaller loss increase and faster recovery of the radiation-induced loss. Visible or infrared
light irradiation also helps to suppress the loss increase and accelerate the loss recovery; this phenomenon is called
photobleaching [38].

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6. Applications of Optical Fibers

6.1. Optical Fiber Cables
Optical fibers are used most typically in the form of optical fiber cables. Optical fiber cables are generally thinner and lighter
than conventional communication cables, such as copper wire cables or coaxial cables. Optical fiber cables are free from any
influence from electromagnetic induction; this is another advantage over conventional copper cables. Optical fiber cables
have a wide variety of applications, such as long haul or metropolitan telecommunication networks, submarine cable
networks, local area networks, broadband access (fiber to the home) networks, and so on. There are also various composite
type cables, which contain optical fibers for addition of the communication function. Examples of such composite cables are
electric power/optical fiber composite cables and optical ground wires (OPGW).

Figure 19 illustrates the cross sections of three major optical fiber cable types used in telecommunications: the loose tube
type cable, the slotted-core type cable, and the single tube type cable. Optical fiber cables are designed so that the optical
fibers inside are free from excessive strain or bending during and after installation. In loose tube type cables, optical fibers
are loosely encased in plastic tubes, and the tubes are stranded around a central strength member. In the case of slotted-
core type cables, a number of individual fibers or fiber ribbons (fiber arrays formed with some resin) are placed in each slot or
groove, which is helically formed on the surface of a central rod having a strength member. Single tube type cables contain
individual fibers or fiber ribbons in the central tube. In any case, proper design of the cable structure ensures stable
performance of optical fibers.

Figure 19. Examples of optical fiber cables

(a) Loose tube type cable; (b) Slotted-core type cable; and (c) Single tube type cable

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6.2. Fiber Connection Technologies

It is highly important to connect optical fibers in various situations. The loss of the optical signal at the connection should be
as small as possible. Since the core of the optical fiber is very small, precise alignment of the ends of two optical fibers to be
connected is key. There are three types of fiber connecting technologies: fusion splicing, optical connectors, and mechanical
splicing.

Figure 20 illustrates the principle of fusion splicing. Fiber ends are melted by means of a high-frequency electric discharge
and permanently joined. Prior to fusion splicing, perfectly flat fiber ends are prepared by utilizing fiber-cleaving tools. In the
case of the optical connector, the ends of the optical fibers are inserted and fixed in high-precision ferrules, which are then
mated by using an alignment sleeve, as illustrated in Figure 21. In fabrication of the optical connectors, the end faces must
be polished flat. The optical connectors can be connected and disconnected repeatedly. Multifiber connectors, which
simultaneously connect multiple fibers or fiber ribbons with the fiber count of 4, 8, or more, have also been developed and put
to practical use.

Figure 20. Principle of fusion splicing

a) Optical fiber; b) Electrode; c) V-groove; d) Fiber coating

Figure 21. Principle of an optical fiber connector

a) Optical fiber; b) Ferrule; c) Alignment sleeve

Mechanical splicing is a technique for semipermanent fiber connection that utilizes relatively simple tools, unlike fusion-
splicing machines. The optical fiber ends are prepared by using the fiber-cleaving tool and then connected by utilizing high-
precision fiber aligning parts. In general, the connection loss is lowest for fusion splicing, and relatively high with optical
connectors and mechanical splicing.

6.3. Optical Fiber Sensors

A variety of sensors that utilize optical fibers have been developed, and some of them have already been brought into
practical use. Examples of such optical sensors are fiber-optic gyroscopes and fiber-optic temperature distribution sensors.

The fiber-optic gyroscopes utilize a phenomenon called the Sagnac effect, in which light traveling clockwise and light
traveling counterclockwise in the same optical fiber coil experience slightly different phase shifts when the optical fiber coil is
rotating. Since the phase difference depends on the angular velocity of the coil, the rotation can be detected by observing the
phase difference. Ultrahigh sensitivity can be realized by properly designed fiber-optic gyroscopes.

Fiber-optic temperature distribution sensors utilize the Raman scattering effect, which is one of the nonlinear effects in optical
fibers. Since the amount of light generated by the Raman scattering effects in the optical fiber depends upon the temperature
of the fiber, it is possible to determine the fiber temperature by observing the Raman scattering–induced light signals. By
further examining the signals as a function of the location along the fiber, the temperature distribution along the fiber can be
observed. Fiber-optic temperature distribution sensors are actually being used, for example, for monitoring the temperature
distribution along electric power cables (which contain optical fibers as sensors).

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7. Future Prospects
In the ubiquitous communications era, the transmission and exchange of huge amounts of data will be indispensable. As
described in the previous chapters, various technologies have been developed to increase data transmission rates, such as
Time Division Multiplexing (TDM) and Wavelength Division Multiplexing (WDM).

7.1. New Fibers

At present, dispersion-controlled silica fibers are developed for long-distance communication with TDM and/or WDM systems
to achieve maximum transmission speed. Also, several types of transmission along new types of optical fiber have been
proposed. These fibers are briefly described below.

7.1.1. Photonic Crystal Fiber (PCF)

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In 1995, BIRKS et al. reported on Photonic Crystal Fiber (PCF) and Holey Fiber (HF), a type of PCF, and thereafter these
types of fibers have been actively investigated [39]. PCF is manufactured by stacking an array of silica capillary rods to form
a macroscopic preform and then by drawing it into fiber. Typically, PCF is made from hexagonal lattice of circular air columns
in which the periodicity is relatively uniform.

Photonic Band Gap (PBG) is defined as the range of frequency and propagation constant of light in which light is prohibited
to propagate. It appears by arranging air holes in silica glass adequately.

7.1.2. Holey Fiber (HF)

HF has a periodic lattice of air holes distributed in the oblique section so as to form a core-clad microstructure that enables
total reflection.

Owing to the large refractive index contrast that exists between glass and air, HF has unique properties, such as very high
nonlinearity, a small effective core area, an enormous amount of waveguide dispersion that can be used for compensating
the large material dispersion of silica, and so on [40].

7.1.3. Photonic Band-gap Fiber (PBGF)

CREGAN et al. demonstrated in 1999 that light can be strictly guided without leakage along a hollow core [41]. Light in certain
well-defined wavelength bands is trapped in air by a full two-dimensional photonic band gap. PBGF is expected to greatly
reduce Rayleigh scattering and nonlinearity. It also may hold the promise of yet undiscovered properties that are not
attainable in standard fibers.

Recently, ultrashort pulse lasers such as femtosecond and picosecond pulse lasers have been developed. With ultrashort
pulses, the wavelength spectrum can be very broadly spread. However, there are no fibers that can cover such a wide
spectrum. Therefore, new types of fiber that use new materials or an air containing structure with a wider wavelength region
will be required.

7.2. New Systems

As far as using ordinary optical fiber bit rate and distance of repeater spacing are inevitably limited owing to dispersion of
optical fiber, that is, wavelength dependency of group velocity. In order to cope with these limitations, optical soliton
transmission utilizing the nonlinear optics effect and Code Division Multiplex (CDM) have been proposed as new
breakthrough technologies.

7.2.1. Soliton System

In 1973, HASEGAWA and TAPPERT proposed that soliton waves could be applied to optical fiber communications [42]. The
pulse, a soliton wave, is generated when the group velocity dispersion of glass fiber and the tertiary nonlinear optical effect
called self-phase modulation effect are balanced.

The self-phase modulation effect appears when the power level of optical pulse is increased and the nonlinear optical effect
accordingly becomes larger. An equilibrium condition occurs and very long-distance repeater spacing is possible thanks to
the absence of distortion.

This proposition has been verified through laboratory testing. However, no practical soliton system has yet been deployed,
because power level control has not yet reached a sufficient level of sophistication.

7.2.2. Code Division Multiplex (CDM)

With very high-speed digital transmission, all-photonic switching will be required because electronic switching cannot function
at such high speed. Therefore, new components including fiber for all-photonic switching, such as two-dimensional space
modulation, will be required.

The extension of today's TDM and WDM technologies will have limitations because of nonlinearity, polarization, and the
temperature dependency of fiber. Therefore, new modulation systems, such as CDM using a concept like spread spectrum
[43], will be required in the future.

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References
1. M. Sugi, T. Nakahara, I.R.E. Trans. M.T.T. 7 (1958) no. 3), 366.
2. JP 125 946, 1936 (M. Seki, H. Negishi).
3. K. C. Kao, G. A. Hockham, Proc. IEE 133 (1966) no. 7, 1151 – 1158.
4. S. Kawakami, H. Nishizawa, IEEE Trans. MTT-16 (1968) no. 10, 814 – 818.
5. T. Uchida, M. Furukawa, I. Kitano, K. Koizumi, H. Matsumura, IEEE J. Quantum Electron. QE-6 (1970) no. 10, 606 –
612.
6. F. P. Kapron, D. B. Keck, R. D. Maurer Proceedings of Conference on Trunk Telecommunications by Guided Waves
(1970), London, Sept.–Oct., pp. 148–153.
7. J. B. MacChesney, P. B. O'Conner, F. V. DiMarcello, J. R. Simpson, P. D. Lazay, Proceedings of 10th International
Congress on Glass (1974), pp. 6/40–6/45.
8. Corning Glass Works, US 3 737 292, 1973 (D. B. Keck, B. Flats, P. C. Schultz).
9. D. Küppers, J. Koenings, Proceedings of ECOC '76 (1976) pp. 49–54.

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10. T. Izawa, S. Kobayashi, S. Sudo, F. Hanawa, Proceedings of IOOC '77, Tokyo/Osaka (1977), pp. 375–378.
11. K. Nagayama, M. Kakui, M. Matsui, T. Saitoh, Y. Chigusa, Electron. Lett. 38 (2002) 1168.
12. T. Nakahara, A. Tsukamoto, H. Kumamaru, M. Hoshikawa, Proc. IEEE 123 (1976) no. 6, 603–608.
13. N. Kuwaki, M. Ohashi, C. Tanaka, N. Uesugi, Electron. Lett. 21 (1985) 1186.
14. D. T. Croft, J. E. Ritter, Technical Digest of OFC'85(1985) Paper WD2.
15. D. W. Peckham, A. F. Judy, R. B. Kummer, Proceedings of ECOC '98 (1998) Vol. 1, pp. 139, 140.
16. T. Ooishi, Y. Kubo, Y. Yokoyama, T. Kato, M. Yoshida, M. Onishi, Y. Makio, Proceedings of OECC 2000 (2000), Paper
12B3-4, pp. 136, 137.
17. Y. Liu, W. B. Mattingly, D. K. Smith, C. E. Lacy, J. A. Cline, E. M. DeLiso, Proceedings of ECOC '98 (1998) Vol. 1, pp.
37, 38.
18. Y.Yokoyama, T. Kato, M. Hirano, M. Onishi, E. Sasaoka, Y. Makio, M. Nishimura, Proceedings of ECOC '98 (1998) Vol.
1, pp. 131, 132.
19. J. M. Dugan, A. J. Price, M. Ramadan, D. L. Wofl, E. F. Murphy, A. J. Antos, D. K. Smith, D. W. Hall, Technical Digest of
OFC '92 (1992) Paper PD14, pp. 367–370.
20. E. Desurvire: Erbium-Doped Fiber Amplifiers, John Wiley & Sons, New York 1994.
21. S. Sudo: Optical Fiber Amplifiers: Materials, Devices, and Applications, Artech House, Norwood 1997.
22. Y. Ohishi, T. Kanamori, T. Kitagawa, S. Takahashi, E. Snitzer, G. H. Sigel, Technical Digest of OFC '91 (1991) Paper
PD2.
23. T. Hosaka, K. Okamoto, T. Miya, Y. Sasaki, T. Edahiro, Electron. Lett. 17 (1981) 530, 531.
24. J. B. MacChesney, P. B. O'Conner, F. V. DiMarcello, J. R. Simpson, P. D. Lazay, Proceedings of 10th International
Congress on Glass (1974) pp. 6/40–6/45.
25. T. Izawa, S. Kobayashi, S. Sudo, F. Hanawa, Proceedings of IOOC '77 (1977) pp. 375–378.
26. D. Küppers, J. Koenings Proceedings of ECOC '76 (1976) pp. 49–54.
27. K. J. Beeles, P. W. France, S. F. Carter, S. Partington, Proceedings of ECOC '82 (1982) pp. 601–605.
28. Y. Koike, Proceedings of ECOC '96 (1996) pp. 41–48.
29. T. Ishigure, Y. Koike, Technical Digest of OFC 2001 (2001) Paper ThC7.
30. T. Kanamori, S. Takahashi, Jpn. J. Appl. Phys. 24 (1985) L785–L760.
31. S. Takahashi, I. Sugimoto, J. Lightwave Technol. LT-2 (1984) 272–275.
32. F. Hanawa, S. Sudo, M. Kawachi, M. Nakahara, Electron. Lett. 16 (1981) 669, 700.
33. G.P. Agrawal: Nonlinear Fiber Optics, Academic Press, New York 1989.
34. Y. Mitsunaga, Y. Katsuyama, H. Kobayashi, Y. Ishida, J. Appl. Phys. 53 (1982) 4847–4853. Links
35. K. Mochizuki, Y. Namihira, H. Yamamoto, Electron. Lett. 19 (1983) 743–745. Links
36. N. Uchida, N. Uesugi, Y. Murakami, M. Nakahara, Proceedings of ECOC '83 (1983) PD Paper.
37. G. H. Sigel, B. D. Evans, Appl. Phys. Lett. 24 (1974) 410–412. Links
38. E.J. Friebele, M.E. Gingerich, J. Non-Cryst. Solids 38 (1980) 245–250.
39. T. A. Birks, P. St. J. Russell, D. M. Atkin, T. J. Shepherd, Electron. Lett. 31 (1995) no. 22, 1941. Links
40. J. C. Knight, T. A. Birks, P. St. J. Russell, D. M. Atkin, Opt. Lett. 21 (1996) no. 19, 1547. Links
41. R. F. Cregan, B.J . Mangan, J. C. Knight, T. A. Birks, P. St. J. Russell, P. J. Roberts, D. C. Allan, Science 285 (1999)
1537–1539. Links
42. A. Hasegawa, F. Tappert, Appl. Phys. Lett. 23 (1973) 142–144. Links
43. T.Nakahara, Proc. International Symposium on Microwave and Optical Technology (ISMOT 2001) (2001).
Further Reading
Cancellieri, G. (1993), "Single-Mode Optical Fiber Measurement: Characterization and Sensing". Boston: Artech House.
Izawa, T., Sudo, S. (1987), Optical Fibers: Materials and Fabrication. Tokyo: KTK Scientific Publishers.
Li, T. (1985), Optical Fiber Communications. New York: Academic Press.
Miller, S.E., Chynoweth, A.G. (1979), Optical Fiber Telecommunications. San Diego: Academic Press.
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Glossary

MCVD
Modified chemical vapor deposition, one of the silica optical fiber fabrication methods developed by Bell Laboratories.
The deposition of the core and the cladding layer is achieved by passing the oxygen and the raw material vapors, that
is, SiCl4 and GeCl4, through a rotating heated silica tube. After deposition, the temperature is increased to collapse
the tube into a solid preform. The preform is drawn into fiber by heating it in a drawing furnace.
Optical Communication System
The combination of a light source that converts electrical signals to light signals, an optical fiber that is a transmission
medium for the optical signals, and a detector that reconverts the optical signals to electrical signals. It is a low-cost
system because of the long repeater spacing and high transmission capacity compared to a conventional
telecommunication system.
Optical Fiber
A transmission medium for optical communications systems made with transparent materials, i.e, glass or plastic. It
consists of a core surrounded by a cladding layer that has a lower refractive index than the core material. An optical

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signal is transmitted in the core by total internal reflection.
OVD
Outside vapor deposition, one of the silica optical fiber fabrication methods developed by Corning Glass Works. Fine
glass particles produced by flame hydrolysis of the raw materials, i.e, SiCl4 and GeCl4, with a C2H6O2 burner are
deposited on the lateral surface of a rotating rod. After deposition, the rod is removed from the soot boule, which is
then dehydrated by heating in chlorine gas and sintered to a transparent preform. The preform is drawn into fiber by
heating it in a drawing furnace.
PCVD
Plasma chemical vapor deposition, one of the optical fiber fabrication methods developed by Philips. The oxygen and
the raw material vapors, that is, SiCl4 and GeCl4, pass through a rotating heated silica tube, which is evacuated. In the
silica tube, oxidation of the raw materials occurs in a plasma, and core and cladding glass layers are deposited on the
inner surface of the tube. After deposition, the temperature is increased to collapse the tube into a solid preform. The
preform is drawn into fiber by heating it in a drawing furnace.
VAD
Vapor-phase axial deposition, one of the silica optical fiber fabrication methods developed by Japanese companies.
Fine glass particles produced by flame hydrolysis of the raw materials, that is, SiCl4 and GeCl4, with an O2–H2 burner
are deposited on one end of a rotating seed rod. A soot preform then grows along the axis of the rod. The core and the
cladding soots are deposited simultaneously. After that, it is dehydrated by heating in chlorine gas and sintered to
transparent preform. The preform is drawn into fiber by heating it in a drawing furnace.

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 Fibers, 1. Survey 1

Fibers, 1. Survey
Fritz Schultze-Gebhardt, Düsseldorf, Federal Republic of Germany (Chaps. 2 – 7)
Karl-Heinz Herlinger, Institut für Chemiefasern der Deutschen Institute für Textil- und Faserforschung
Stuttgart, Denkendorf, Federal Republic of Germany (Chaps. 2 – 8)

1. Introduction . . . . . . . . . . . . . . . . . 1 5.4. Crystallization . . . . . . . . . . . . . . . 7

2. History . . . . . . . . . . . . . . . . . . . . 2 5.5. Organization of Structural Elements 8
3. Characteristics of Fibers . . . . . . . . . 3 5.6. Structural Models . . . . . . . . . . . . . 8
3.1. Fineness . . . . . . . . . . . . . . . . . . . . 3 5.7. Molecular Symmetry and Physical
3.2. Tenacity and Modulus of Elasticity . . 3 Properties . . . . . . . . . . . . . . . . . . 9
3.3. Elongation . . . . . . . . . . . . . . . . . . 3 5.8. Changes in Properties Caused by Sym-
4. Spinning . . . . . . . . . . . . . . . . . . . 3 metry Defects . . . . . . . . . . . . . . . . 9
4.1. Wet Spinning . . . . . . . . . . . . . . . . 4 6. Fiber Properties Required by Textiles 10
4.2. Dry Spinning . . . . . . . . . . . . . . . . 4 6.1. Requirements to Be Met by Textiles . 11
4.3. Melt Spinning . . . . . . . . . . . . . . . . 4 6.2. Modification of Fiber Properties . . . 11
5. Prerequisites for Fiber Formation . . 5 6.3. Comfort Properties of Textiles . . . . . 12
5.1. Molecular Mass and Fiber Formation 5 7. Economic Aspects . . . . . . . . . . . . . 13
5.2. Molecular Structure and Fiber Prop- 8. Tabular Survey of Fibers . . . . . . . . 14
erties . . . . . . . . . . . . . . . . . . . . . . 5 9. References . . . . . . . . . . . . . . . . . . 35
5.3. Property Requirements for the Forma-
tion of Fiber Structures . . . . . . . . . 6

1. Introduction into natural materials brought into fiber form by

a chemical reaction (regenerate fibers) and fibers
The term fibers refers collectively to a wide va- made from synthetic polymers (synthetic fibers).
riety of forms of fibrous materials. Standards The following classification includes standard-
have been established to introduce order into ized abbreviations that are used occasionally
the field. The most frequently employed terms throughout this article:
are defined here. Natural fibers that can be spun 1. Natural fibers
into yarn are called staple fibers. The primary 1.1. Plant fibers, e.g.,
spinning of man-made fibers results in the pro- cotton
duction of continuous filaments (endless fibers). flax
Indeed, both monofilaments (threads; spinneret hemp
has one hole) and multifilaments (spinneret has jute
many holes) can be produced. A filament yarn 1.2. Animal fibers, e.g.,
consists of a large number of filaments that can wool
be given texture by twisting, crimping and/or camel hair
heat setting. angora
The word tow refers to a fiber tape made from silk
thousands of filaments. If a tow is cut or torn, it 2. Man-made fibers
gives rise to staple fibers. Fiber tapes obtained 2.1. Fibers based on natural polymers, e.g.,
by cutting or tearing parallel to the fibers are viscose rayon (CV)
known as fiber bands. Lyocell (CLY)
Conventional standards divide fibers into (1) cellulose acetate (CA)
natural fibers and (2) man-made fibers (also elastodiene (LA)
called chemical fibers). 2.2. Fibers based on synthetic polymers
Natural fibers are subdivided into plant and (synthetic fibers), e.g.,
animal fibers. Man-made fibers are subdivided polypropylene (PP)

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 451
2 Fibers, 1. Survey

polyacrylonitrile (PAN) The production of synthetic fibers was the

poly(vinyl chloride) (PVC), result of pioneering work on the formation of
polyamide 6 (PA 6, nylon 6) synthetic polymers and the development of ex-
polyamide 66 ( PA 6,6; nylon 66) trusion techniques known as wet, dry, and melt
poly(ethylene terephthalate) (PET) spinning.
poly(ether ether ketone) (PEEK) Nylon 66 was first synthesized by W. H.
polyurethane (PUR; spandex) Carothers in 1935. This was closely followed
by the discovery of nylon 6 by P. Schlack in
1938. The work of J. R. Whinfield and I. T.
Dickson led to the development of polyester
2. History fibers in 1941. Today, polyamides and poly-
esters are the largest-volume polymers capable
Natural Fibers. Natural fibers have been of being melt-spun. The production of synthetic
used by humans for thousands of years. Animal fibers based on familiar polymers such as poly-
hair and plant fibers were spun into yarn and acrylonitrile, which cannot be melt-spun, was
woven into textiles. Indeed, the textile industry made possible by the introduction of new sol-
today is still based on this ancient technology. vents, e.g., dimethylformamide (H. Rein, 1942).
Discovery of the stereospecific polymerization
Man-Made Fibers. The idea of making “ar- of propylene (G. Natta, 1954) led to the in-
tificial” fibers and threads is over 300 years troduction of polyolefins into the fiber industry.
old. In fact, the start of the chemical fiber The development of technology and the simul-
industry dates from about 1884. The process taneous elucidation of structure and properties
of regenerating fiber-forming cellulose was resulted in “tailor-made” polymers and fibers.
based on the discovery of solvents such as Specific properties such as rubber elasticity (O.
copper oxide – ammonia by E. Schweizer in Bayer, 1947) or extreme tenacity and stiffness
1857. Later, Count Chardonnet succeeded in were realized (high-modulus fibers, P. W. Mor-
forming derivatives of cellulose which could be gan and S. L. Kwolek, 1968). In addition, high-
solubilized and spun into threads; “Chardonnet temperature fibers were made from polyhetero-
silk” was first made in 1884. A detailed account cyclic compounds.
of the history of man-made fibers is not given in Apart from organic polymers, inorganic sub-
this article. The subject was dealt with compe- stances such as glass, carbon, BN, and SiC were
tently by H. Klare in 1985 [19]. also spun into fibers.
The most important developments in the pro- Future developments are likely to be directed
duction of man-made fibers based on cellulose toward classical mass production, particularly
were: towards the attaining of optimal processing char-
1) the cuprammonium process for solubiliza- acteristics and clothing comfort. New types of
tion and spinning of cellulose; application – above all in the field of industrial
2) the formation of spinning solutions of cellu- fibers and in medical technology – will stimu-
lose derivatives, such as cellulose nitrate and late the development of special fibers with very
cellulose acetate; specific properties.
3) the intermediate derivatization of cellulose
to cellulose xanthate which in turn is spun
into cellulose fibers; 3. Characteristics of Fibers
4) the development of new solvent sys-
tems for cellulose, such as N-methylmor- 3.1. Fineness
pholine oxide (NMMO) or dimethylacet-
amide – lithium chloride. The thickness of fibers and filaments ranges
from 1 to 100 µm. Measuring thickness by
In 1927, H. Staudinger used means of conventional instruments is very diffi-
polyoxymethylene as a model of cellulose to cult. Indeed, even small variations in fiber uni-
demonstrate that fiber-forming polymers were formity, thickness, and cross-sectional area hin-
linear polymeric molecules. der microscopic measurement. To make a sta-
 Fibers, 1. Survey 3

tistically valid statement about the fineness of a never attained because otherwise fibers undergo
fiber (fiber density), length and mass are com- partially irreversible stretching.
puted instead of thickness. The unit tex is used Temperature and moisture (weather) affect
to express fiber fineness. According to the ISO, both the tenacity and the elongation of fibers to
varying extents, depending on the type of poly-
1tex = 1g per1000m mer. The same applies to dimensional stability
If 1000 m of fiber weigh 1 g, the fineness is 1 tex. and wrinkling tendency, properties that are also
Another unit commonly used to express fineness influenced by the type of fiber and by the textile
is dtex. If the mass per length is given in dtex, the structure.
numerical values will be comparable to those in
the formerly used unit denier [46]:
4. Spinning
1denier = 1g per9000m
Both natural and synthetic fibers are consist-
ing of linear polymers. These polymers are con-
verted into fibrous form by growth (animal hair,
plant fibers) or extrusion (spider, silkworm, spin-
3.2. Tenacity and Modulus of Elasticity ning technology) and are specifically oriented to
the fiber axis. The many mechanisms found in
The cross-sectional area of fibers is generally nature for the formation of filamentous struc-
nonuniform and cannot be determined easily. tures are, by no means completely understood
Hence, measurements based on area have lim- (see e.g. [87]). Only a few processes are avail-
ited applicability. For this reason, tenacity is not able for large-scale production of man-made
measured in gigapascal (GPa) units (ISO) but fibers. Specific production techniques are based
is expressed relative to the fineness. Usually, the on the deformability of fiber polymers. In prin-
maximal tensile force (at break) is employed, ex- ciple, a distinction is made between spinning
pressed in centinewtons per tex (cN/tex); other methods involving solutions and those involv-
units used are cN/dtex (1 cN/dtex = 10 cN/tex) or ing molten polymer. For a detailed description
N/tex (1 N/tex = 100 cN/tex). Textile and indus- of spinning, see → Fibers, 3. General Produc-
trial fibers have tenacities ranging from 10 to tion Technology.
more than 300 cN/tex (see Table 4). The mod-
ulus of elasticity corresponds to the tangent to
the stress – strain curve at the origin (→ Fibers,
6. Testing and Analysis, Chap. 3.). It is also ex-
4.1. Wet Spinning
pressed relative to the fineness, in cN/tex. Typ-
Polymer solutions are converted into fibers by
ical moduli range from 50 to 1000 cN/tex for
diluting a highly concentrated polymer solu-
textile fibers and from 1000 to 40 000 cN/tex for
tion in a coagulating bath. The extremely vis-
industrial fibers. (See Table 5.)
cous polymer solution, e.g., 3.5 – 10 Pa · s (still
higher values are obtained with viscose rayon)
can be extruded, i.e., spun, by forcing it through
3.3. Elongation a spinneret to form threadlike structures. In gen-
The highest possible degree of elongation eral, polymers are soluble only in specific sol-
at break (→ Fibers, 6. Testing and Analysis, vents. The viscous polymer solution is extruded
Chap. 3.) varies greatly with the type of fiber. into a coagulating bath where the solvent is di-
Industrial fibers, e.g., carbon fibers and high- luted, which results in precipitation of polymer
modulus aramids, have values of 0.1 – 2 %; tex- threads. For instance, polyacrylonitrile is solu-
tile fibers and yarns have values of 5 – 70 %; and ble in dimethylformamide (DMF). In the coag-
values of 300 – 700 % are obtained for spandex ulating bath, DMF is washed out of the viscous
fibers (see Table 4). polymer threads with water, and polyacryloni-
In practical applications, fibers are elongated trile fibers precipitate (Fig. 1).
only to a small extent. Maximal elongation is
4 Fibers, 1. Survey

4.3. Melt Spinning

In melt spinning, the polymer is melted by heat-

ing and then passed through a spinneret via a
spinning pump. Only polymers that are ther-
mally stable under melt conditions can be sub-
jected to this extrusion (i.e., spinning) process.
The fluid threads emerging from the spinneret
Figure 1. Fiber formation by solvent extraction in the spin- solidify on cooling (usually air cooling) to form
ning bath
PAN = polyacrylonitrile: DMF = dimethylformamide filaments. This technique is applied in spinning,
e.g., nylon 6, nylon 66, or poly(ethylene tere-
The solvent concentration in the fiber de- phthalate) (→ Fibers, 4. Synthetic Organic).
creases along the length of the coagulating bath. The difference between melting and spinning
In wet spinning, several physicochemical pro- temperatures depends on the viscosity of the
cesses occur simultaneously, e.g., solvent dif- melt. Usually, the spinning temperature is about
fusion, polymer precipitation, and formation of 30 K higher than the melting temperature T m .
membrane-like interfaces and system-specific However, if the viscosity is still too high, the
morphological structures. One of the main pur- spinning temperature must be increased even
poses of developing wet-spun polymers is to pro- further. For example, T m of polypropylene is
duce specific fiber structures in the coagulating 170 ◦ C but the polymer is spun at 260 ◦ C. The
bath. This is achieved, in principle, by modifica- melt index, not the viscosity, is generally used
tion in the coagulating bath, which is described to characterize the melting properties of poly-
in more detail under → Fibers, 4. Synthetic Or- mers. In fact, the tedious measurement of melt
ganic, Chap. 5.3.3., wet spinning of polyacry- viscosity has now been replaced by simple mass
lonitrile. In a spinning process of this type, the determination (→ Fibers, 6. Testing and Analy-
polymer can also undergo a chemical reaction; sis).
e.g., the viscose process involves acid hydroly- Hence, melt spinning requires polymers that
sis of cellulose xanthate in the coagulating bath are thermally stable and, as far as possible, re-
(→ Cellulose, Chap. 3.1.3.). sistant to thermal oxidation at temperatures ap-
To make the process economical, the polymer proximately 30 K higher than their melting tem-
concentration should be kept as high as possi- peratures (PA-6, PA-66, and PET).
ble during spinning. In the case of soluble poly- Production conditions must be optimally co-
mers, the viscosity of the spinning solution, and ordinated with the properties of the product to
thus its basic spinnability, are directly related achieve the desired melt viscosity, on the one
to the concentration and solvation of the poly- hand, and the required fiber tenacity, on the
mers. However, complicated processes, such as other. Rapid advances in process technology,
exchange, diffusion, and drying, that occur dur- however, have made possible not only the pro-
ing wet and dry spinning result in polymer- and cessing of very highly viscous melts, but also the
solvent-dependent limitations on the polymer extrusion of solids.
concentration.

5. Prerequisites for Fiber Formation

4.2. Dry Spinning
5.1. Molecular Mass and Fiber
In dry spinning, the polymer solution is also Formation
forced through a spinneret. Solvent is then evap-
orated in a warm current of air to produce al- The spinnability of polymer melts or solutions
most solvent-free filaments. Cellulose acetate, depends on their viscosity at technically feasi-
polyacrylonitrile, and polyurethane are spun by ble spinning conditions. The viscosity η of lin-
this technique (→ Cellulose Esters, → Fibers, ear polymers depends, in turn, on the molecular
4. Synthetic Organic). mass M r :
 Fibers, 1. Survey 5
Table 1. Polymer type and molecular mass suitable for fiber formation

The interaction energy (cohesion energy) con-

η=K ·Mrα trols the solubility and compatibility of struc-
where K is a constant that is known for most tural units with each other. These factors finally
common polymers. lead to specific morphological domains, which
The fiber-forming tendency of a polymer in- frequently occur in block structures of varying
creases with increasing molecular mass. The chemical composition along the polymer chain,
varying forces of interaction between individ- e.g., in polyurethane (spandex) fibers. The gen-
ual structural groups of polymers are directly eral relationship between the structure and prop-
related to the chemical nature of these linear erties of polymers suitable for fiber production
molecules. For this reason, optimal conditions is discussed in the literature [47]. In this section
for fiber formation are very polymer-specific. the structural elements of technically important
In principle, the weaker the interaction between fibers are compared.
structural segments, the higher is the molecular Table 2. Structural characteristics of polymers and their importance
mass required (Table 1) [47]. for fiber properties

Structural characteristics Importance for fiber properties

Chemical structure thermochemical and

5.2. Molecular Structure and Fiber photochemical stability,
Properties (primary structure) textile chemical processes
(dyeing, textile finishing)
Molecular organization and general properties,
The thermochemical and photochemical stabil- symmetry melting point, shrinkage behavior
ity of a fiber polymer is controlled by its chemi- Type of binding and thermophysical and
cal structure. The possibility of chemically mod- stereochemistry (secondary thermomechanical properties
structure) (moduli, elasticity)
ifying textile properties is determined by the Conformation and
chemical reactivity and polarity of the individ- conformational mobility
ual structural units (Table 2). The type of chem- Morphological structures, diffusion (dyeing), breaking
superstructures mechanism
ical bonds and the stereochemistry are impor-
tant for molecular geometry, interaction of struc-
tural units, and thermal conformational stabil- Crystallization. The interaction between
ity. Low conformational mobility is generally structural units is of considerable importance for
related to high mechanical tenacity, modulus, crystallization. The chemical structure, stereo-
and torsion modulus. Finally, the molecular or- chemistry, and symmetry of polymers deter-
ganization is influenced by the symmetry of the mine, to a large extent, the structural conforma-
structural units and of the entire molecular chain.
6 Fibers, 1. Survey

tion of the polymer under prevailing conditions These requirements were fulfilled by
such as temperature (melt or solid), condition Staudinger’s model of cellulose as polymeric
of solution (solvation of molecules), coil struc- formaldehyde [48]. Even this simple compound
ture, and aggregation. Higher orientation or met all the conditions for fiber formation. It is a
parallelism of the chain molecules increases meltable linear polymer, capable of crystalliza-
orientation of the structure elements. Their in- tion with formation of fiber fibrils.
teraction also depends on the possible molecular The simplest model for intermolecular dis-
conformations. persion forces (van der Waals forces) is shown
During spinning, a preliminary orientation of in a polyolefin molecule such as polyethylene or
the molecules occurs, which is enhanced dur- polypropylene:
ing drawing, and stabilized by partial crystal-
lization. The individual segments usually crys-
tallize independently of each other; hence amor-
phous intercrystalline areas exist unavoidably.
The course of polymer crystallization, especially
of fibers, is quite different from the crystalliza-
tion characteristics of low molecular mass com- In poly(ethylene terephthalate), interaction bet-
pounds. ween the aromatic π-electron systems of the
benzene rings and of the carbonyl groups makes
dipole – dipole interaction possible:
5.3. Property Requirements for the
Formation of Fiber Structures

Fiber-forming polymers require certain proper-

ties that make possible the formation of typical
fiber structures; these are linearity, intermolec-
ular forces, and the possibility of crystallization Hydrogen bonds act on amide or urea groups in
whereby, in general, supermolecular structures polyamides, such as nylon 66 or nylon 6, or in
result. polyurethane, respectively:
1) Linearity. Only linear polymers can be ex-
pected to have optimal fiber-forming prop-
erties. Linearity is specifically a prerequisite
for the spinnability of polymer solutions and
melts.
2) Intermolecular Forces. After orientation of
linear polymers during spinning and draw-
ing, dispersion forces, e.g., dipole-dipole in-
teractions or hydrogen bonds between the The OH groups of poly(vinyl alcohol) and of
polymer segments contribute to the fixation cellulose (viscose rayon) are also able to form
of the polymer chains. hydrogen bonds. Very strong dipole – dipole in-
3) Crystallization. The well-developed organi- teraction occurs between the nitrile groups of
zation of the polymer chains usually results polyacrylonitrile:
in crystallization. Polymer-specific crystal-
lization results in crystalline domains and
amorphous intercrystalline areas.
4) Supermolecular Structure. The crystallites
are oriented so that they lie parallel to the
fiber axis, which results in supermolecu- However, this all-trans conformation of poly-
lar structures, e.g., fibrils and fibril bundles acrylonitrile can change into lower energy heli-
(→ Fibers, 2. Structure). cal structures [49]:
 Fibers, 1. Survey 7

In this step, spun fibers are stretched by more

than 200 %, resulting in partial crystallization
of polymer molecules (Fig. 2 D). In high-speed
spinning, the extremely high windup speeds
(3000 – 6000 m/min; 50 – 100 m/s) induce crys-
tallization during fiber formation. The resulting
preoriented yarns (POY) have to be stretched
by only 40 – 100 % in subsequent steps (tex-
turing). Additional polymer-specific increases
in windup speeds lead to fully oriented yarns,
which require almost no further stretching.
Wu et al. [77] succeeded to orientate spin-
ning PET in a threadline modification process.
The one-step orientation (without separate draw-
The strong dipole–dipole interaction of poly-
ing) could be realized by the installation of a liq-
acrylonitrile is one of the reasons for the specific
uid bath in the spinline. High-performance fila-
solubility behavior of that polymer.
ments, however, have to be drawn after spinning
Weak dispersion forces are effective only in a
to reach maximum fiber strength.
highly symmetrical conformation. This high de-
Liquid Crystals. Some linear polymers, in
gree of symmetry, in turn, is possible only with a
solution or molten form, tend to undergo
highly symmetrical arrangement of substituents,
self-organization by forming liquid – crystalline
e.g., along an aliphatic carbon chain. Such a
structures. Soluble linear polymers (lyotropic
high degree of symmetry in linear polymers can
systems) form liquid crystals as a result of their
be achieved only by coordination polymeriza-
rigid conformation and the formation of poly-
tion, in the presence of organometallic catalysts
electrolytes, e.g., the system poly(p-phenylene-
(Ziegler – Natta), to yield isotactic polymers. If
terephthalamide) – H2 SO4 . Liquid crystals can
this symmetry (e.g., in polypropylene) is dis-
also be formed in polymer melts (thermotropic
turbed by the presence of other structural units
systems). Examples of suitable systems are the
(e.g., carboxylic acid ester groups; acrylic acid
aromatic polyesters of the poly(4-hydroxyben-
comonomers), both polymer and fiber properties
zoic acid) type or aromatic blocks built up in
change drastically.
segments and separated by flexible spacers. Fig-
ure 2 E shows the resulting structures of some
5.4. Crystallization high-modulus aramids; pronounced amorphous
intercrystalline areas are not visible.
The flexible linear polymer takes on a vari-
ety of conformations during fiber formation,
seeking the conformation with the lowest free 5.5. Organization of Structural
energy (i.e., highest molecular organization). Elements
However, spinning conditions do not allow poly-
mers to attain this state completely, and fiber The arrangement of fibrils and fibril bundles in
polymers usually undergo only partial crystal- man-made fibers is controlled by the produc-
lization. The ratio of crystalline to amorphous tion procedure, i.e., by physical and physico-
regions varies from almost totally amorphous to chemical processes. Therefore, resulting struc-
highly crystalline, single-phase systems (Fibers, tures depend on production parameters, and de-
2. Structure). spite the different types of polymers employed,
Linear polymers exist in solution or as the tertiary structures of all man-made fibers are
molten polymer in a more or less coiled form very similar.
(Fig. 2 A). In the shearing field during spin- In contrast, natural fibers have organized,
ning, the molecules are partially uncoiled and evolved structures which differ considerably
oriented in the direction of flow (Fig. 2 B). A from each other, depending on the organism.
higher degree of orientation is achieved dur- Structural variations are reflected in different ge-
ing the subsequent drawing operation (Fig. 2 C). ometric positions of the fibrils with respect to the
8 Fibers, 1. Survey

Figure 2. Various conformations of fiber polymers

A: Unstirred solution (coil of polymer molecules)
B: Molecular orientation in the shearing field during spinning
C: Molecular orientation during drawing or liquid crystal formation from the melt or solution (polyelectrolyte molecules)
D: Formation of structure on crystallization of flexible polymer chains. Examples are polyethylene, polypropylene, polyamide,
and polyester.
a) Crystallite; b) Intercrystalline (amorphous) region; l) Long period (10 – 20 nm)
E: Formation of structure of lyotropic and thermotropic systems, such as crystallization of rigid polymer chains. Examples
are high-modulus fibers of the aramid type, polyesters, and carbon fibers.

fiber axis (e.g., in cotton fibers) or in different Even more planar molecules form graphite-
chemical structures along the fiber cross section like structures (Fig. 3 D). Structural defects lead
(e.g., in animal hair, such as wool). Fibers could to cavities and weakly bent planes of the aro-
thus be classified into two principal structural matic systems; for more details on carbon fibers,
categories, namely, organized and unorganized, see → Fibers, 5. Synthetic Inorganic.
if the structure of each fiber were known.

5.7. Molecular Symmetry and Physical

5.6. Structural Models Properties
The chemical structure of linear polymers de- The importance of molecular symmetry for ther-
termines the degree of conformational mobil- mophysical properties (melting point, glass tran-
ity of the chain segments of these molecules. sition temperature) can be demonstrated for
Both chain mobility and molecular structure, polyamides. Figure 4 shows the fluctuation of
in turn, greatly influence fiber structure. Flex- melting points in the series of polyamides PA-
ible chain molecules may crystallize partially to 3 to PA-13 (nylon 3 to nylon 13). Apparently,
form structures that conform with the classical polyamides with an even number of carbon
crystalline – amorphous model (Fig. 3 A). Span- atoms and those with an odd number of carbon
dex fibers, on the other hand, have a special do- atoms belong to different structural series [47].
main structure, because the chemical structure of This can be explained by the different overall
these polymers changes considerably in the vari- symmetry and, consequently, the different pos-
ous segments along the polymer chain (Fig. 3 B). sibilities for hydrogen-bond formation (Fig. 5).
The relatively planar structure of aramids and In PA-7, more hydrogen bonds can be formed –
polyheterocyclic compounds, their conforma- at least in the all-trans conformation – than in
tional rigidity, and their tendency to form ly- PA-6. Analogously, all nylon types with an even
otropic structures in the spinning solution are number of carbon atoms have lower melting
consistent with a structural model in which the points than those with an odd number of carbon
intercrystalline segments are bridged (Fig. 3 C). atoms (Fig. 5).
 Fibers, 1. Survey 9

insertion of comonomers, such as vinyl com-

pounds. The resulting copolymer has altered
properties and is no longer suitable for textile
production. In addition, polar comonomers in-
terfere with the isotactic course of the polymer-
ization process itself.

Figure 4. Melting points of nylons as a function of chain

length n.

Figure 3. Various structural models of different polymer

types
A: Classical structural model of amorphous – crystalline
fiber polymers. Examples are polyamide, polyester, and vis-
cose rayon. Long period (l) 10 – 30 nm.
B: Structural model of spandex fibers (polyurethane).
Length of hard segment 2.5 nm; length of soft segment
15.0 nm
C: Structural model of aramid fibers (p-structures). No
amorphous phases present; stretched molecules due to ly-
otropic structures during fiber formation Figure 5. Hydrogen bonding in nylon 6 (A; mp 225 ◦ C) and
D: Structural model of carbon fibers; graphite structure with nylon 7 (B; mp 232 ◦ C)
defects (cavities, bent layers; D = position of defect).
Polyacrylonitrile is rarely used for textile
fibers without comonomers being incorporated
into the polymer, because the desired fiber prop-
5.8. Changes in Properties Caused by erties (e.g., deformability, dyeability) cannot be
Symmetry Defects achieved with polyacrylonitrile alone. This, of
course, changes the solubility of the polymer.
The incorporation of comonomers affects not
Polyesters of similar chemical structure, but
only chemical structure, but also symmetry and,
quite different molecular symmetry, also have
therefore, other fiber properties. For instance,
very different melting points. For example, the
the tacticity of polypropylene is changed by the
10 Fibers, 1. Survey

highly symmetrical poly(ethylene terephthalate) spun and, at the same time, retain their di-
has a melting point of 265 ◦ C, whereas the melt- mensional stability during processing, use
ing point of poly(m-phenyleneisopthalamide) is and care.
only 102 ◦ C [47].
The same situation arises with aramids. The requirements to be met by fibers and their
Here, too, the highly symmetrical para-linked parent polymers are, therefore, determined by
polyamides have higher melting points (in this the demands on the final products.
case, decomposition temperatures) than the less
symmetrical meta-linked polymers (Fig. 6). The
different dipole orientation, oppositely directed 6.1. Requirements to Be Met by Textiles
or in the same direction (arrows in Fig. 6), and
the total symmetry cause higher fiber tenacity The need for a variety of textile fabrics having
and modulus. specific properties should be clear from the di-
versity of textile uses. The priorities and order
of importance of properties depend on the appli-
cation in question.
For clothing, textile properties like appear-
ance, aesthetics, optics, drape, formability (iron-
ing, pleating), comfort, heat and moisture trans-
port, handle, ease of care, and fastness of all
types are of considerable importance. In ad-
dition, certain chemical requirements, such as
dyeability, crease-resistant finishing, and dimen-
sional stability, must be met in the production
of textile materials. Finally, processibility to the
finished textile product in partially automated
production lines has become increasingly im-
portant.
Industrial textiles must also possess specific
properties, depending on their application. For
example, high tenacity is required for ropes; high
modulus, for fiber reinforcement; heat stability,
Figure 6. Effect of dipole orientation on the melting point for protective clothing and insulation; high water
(decomposition temperature) of aramids absorption, for articles of hygiene; resistance to
chemicals and flue gas, for filter materials; and
long-term stability, for geotextiles [45].
6. Fiber Properties Required by In the past, fiber production and the utiliza-
tion of specific properties were optimized pri-
Textiles marily. Today, fibers with desired properties are
made specifically to fulfill the requirements of
Despite the fact that a large number of polymers
the final product. The correlation between re-
possess the basic properties required for fiber
quirements and properties of the finished prod-
formation, they are not all suitable for large-
uct and corresponding fiber (polymer) properties
scale production of fibers. In textile production
is given in Table 3.
and in commercial applications, polymers must
fulfill a variety of requirements:
1) Chemical Stability. Polymers must be stable 6.2. Modification of Fiber Properties
under the influence of heat, light, air, water,
and the chemicals commonly used in textile The specific properties of the finished product
finishing and care. depend directly on its end use. Since the fiber
2) Thermomechanical Stability. Polymers must itself is not the final product, changes in fiber
possess the ability to be solution- or melt- structure result in changes in the property profile
 Fibers, 1. Survey 11
Table 3. Correlation of textile properties with fiber properties

Properties of the final product Corresponding fiber properties

Optical properties luster, fiber surface

Aesthetics profile, fiber cross section
Mechanical properties modulus of elasticity, tenacity, elongation
Comfort
Physiological properties of clothing moisture absorption, moisture transport
Antistatics electrical resistance
Thermal insulation heat capacity, porosity, heat conduction ∗
Hand textile structure, bending modulus
Feel roughness, modulus of elasticity, fineness
Ease of care and washability wetting, moisture absorption, glass transition temperature (wet and dry) [78]
Dry cleaning polymer (in)solubility, swelling
Soiling characteristics zeta potential, adsorption and dissolution of soil components
Fastness
Mechanical stability tenacity, elongation, moduli, abrasion resistance
Dimensional stability melting point, glass transition point (wet and dry)
Forming (e.g., pleating) thermoplasticity, glass transition temperature (T g )
Lightfastness chemical structure, sensitizers, stabilizers
Lightfastness of dyeing polymer – dye interaction, radical lifetime
Specific properties
Flame resistance chemical structure, combustion mechanism
Impermeability to water moisture absorption, wetting properties
Water vapor permeability surface properties, morphology, yarn structure
Dyeability glass transition point during dyeing
Mechanical properties
(ropes, material, tire cord) modulus of elasticity, tenacity, elongation, dynamic modulus
Rubber elasticity chemical structure, glass transition temperature, morphological structure,
domain structure

∗ The thermal insulation of a textile is largely due to the air inside the pores, which is of low thermal conductivity.

of the finished product. Matching the require- 1) introduction of a sulfonic acid group into
ment profile with the property profile is not al- poly(ethylene terephthalate) to bind cationic
ways possible. the purpose of numerous mod- dyes (sulfoisophthalic acid as comonomer);
ification procedures (e.g., of the fiber polymer, 2) introduction of a sulfonic acid group into
production method, processing, and finishing) is polyacrylonitrile with the help of vinylsul-
to confer special functional properties on the end fonic or styrenesulfonic acid or a similar
product. some of these procedures are described comonomer to make possible the use of
in more detail in the following sections. cationic dyes;
3) introduction of flexible chain segments into
copolymers. Fibers are used predominantly poly(ethylene terephthalate) to change its
as raw materials in textile manufacture. specific dyeing characteristics. Polymer modifica-
fabric properties, such as dimensional stability, tion [copolycondensation with poly(ethyl-
brightness, color, pattern, or luster, are imparted ene glycol)] in the production of carrier-free
to textiles during the physical and physicochem- dyeable polyester makes use of this princi-
ical processes of textile finishing. These charac- ple.
teristics should remain unchanged, particularly
during use and cleaning. Chemical modification Polymer Mixtures. Polymers are generally
of the fiber polymer is generally employed to incompatible. If two different polymers are spun
achieve this goal. Chemical treatment involves, together, fibril structures are formed (matrix fib-
above all, the introduction of special structural ril fibers) that are known as biconstituent fibers.
groups into the basic polymer, groups that are If two polymer streams are combined in the
capable of taking part in polar and homopolar spinneret without blending, bicomponent fibers
interactions with the chemicals used in textile are obtained (→ Fibers, 3. General Production
finishing. Some examples are Technology).
12 Fibers, 1. Survey

Additives. Many specific fiber characteris- fiber lead to fiber shrinkage or stretching, de-
tics can be achieved by use of additives in the pending on the degree of thermosetting. In other
spinning solution or the melt. For example, the words, the textiles lose their shape.
following effects can be obtained: Even in the dry state, dimensional stabil-
ity decreases with increasing temperature, fibers
1) Delustering: use of titanium dioxide as addi- can undergo permanent deformation at dry heat.
tive in spinning Suitable fixation and textile finishing, e.g., ther-
2) Spin dyeing: use of pigments as additives in mofixation (heat setting) of polyester, felting or
spinning shrink-resistant finishing of wool, and crease-
3) Antistatic properties: use of electrically con- resistant finishing of cotton, can enhance dimen-
ducting additives in spinning sional stability and ease of care. Textiles that
4) Flame resistance: use of flame retardants as are still not dimensionally stable enough to be
additives in spinning washed with water must be dry-cleaned. Here,
The use of additives in spinning produces a very soil release is achieved by using organic solvents
broad spectrum of properties. For economic rea- such as perchloroethylene or fluorochloro-hy-
sons, this type of fiber modification is the method drocarbons (→ Dry Cleaning); the temperature
of choice, if it produces the required effect. By must be maintained below the glass transition
comparison, the development of special poly- points of the fiber – solvent system throughout
mers is a much more expensive procedure. the process.

6.3. Comfort Properties of Textiles

Fibers used to produce clothing must possess a

variety of properties. The term comfort refers to
those properties responsible for the wash and
wear performance of garments. Physiological
studies have shown that apart from fiber sub-
stance, i.e., the chemical structure of the fiber
polymer, the most important factors that influ-
ence textile wearability are fiber, yarn, and tex-
tile construction [50]. Along with moisture ab-
sorption, moisture transport across the fiber sur-
face or through textile spaces is of particular sig-
nificance for the moisture balance of textiles.
Textiles must retain their appearance and form
during washing and dry cleaning. In this connec-
tion, certain inherent fiber properties are of vital
importance. The thermomechanical stability of
textiles is controlled by the glass transition tem-
perature (T g ) of the fiber polymers. However,
this temperature is not a structural property but,
Figure 7. Total production of man-made fibers [2]
rather, is directly related to the fiber system, e.g.,
the type of polymer and polymer – water interac-
tion. Deformability generally increases with in- 7. Economic Aspects
creasing moisture absorption because the chain-
segment mobility of polymers is increased. The The production of natural and man-made fibers
glass transition temperature of fiber polymers is influenced by a number of factors, such as de-
with a high moisture-absorbing capacity de- mand (state of the economy), availability (pro-
creases dramatically with increasing moisture duction and trade), prices, and availability of raw
content. The resulting structural changes in the materials. The per capita consumption varies
 Fibers, 1. Survey 13

considerably from country to country and de- 8. Tabular Survey of Fibers [6], [53],
pends on climate, supply, domestic production [54]
versus imports, standard of living, fashion, state
of the economy, and degree of industrialization. A quantitative survey of the most important
The balance between the consumption of nat- properties of fibers based on polycondensation
ural and of man-made fibers is also controlled and polymerization, as well as some inorganic
by these factors, although a certain “awareness fibers, is shown in Tables 4, 5, 6, 7, 8, 9, 10. Prop-
of nature” currently tips the scales in favor of erties of these fibers, are compared with those of
natural fibers. The production of natural fibers, natural and semisynthetic fibers. The properties
e.g., cotton or wool, is determined in terms of of all textile and industrial fibers are determined
the profit made per area cultivated. A dramatic by variables related to production and aftertreat-
increase in production cannot be expected at ment. Hence, in general, only a range of values
present. However, new developments in genetic characteristic of individual fiber classes is given
engineering could rapidly improve the yields ob- in this survey. In fact, only the order of magni-
tained per given area. tude is indicated for electric resistance of fibers
The economic importance of individual fiber because of considerable variations in measured
types can be deduced from their annual world- values. No entries have been made when reliable
wide consumption [51], and Figure 7 shows the information was unavailable.
worldwide production of man-made fibers. The numbers in brackets are plausible
Both the consumption and the production of estimated values. Figures for tenacity and
fibers also depend directly on the level of devel- modulus are based on both fiber fineness
opment and on per capita income [52]. The con- (1tex = 1g/km) and cross-sectional area of the
sumption per person in individual countries dif- sample. The following relationship is applica-
fers considerably for a variety of reasons. Some ble:
countries have already reached a high level of


consumption, and despite their high standard of Fineness (tex) = 105 ×Density gcm−3
living, the population spends only a fixed per-
2
×Crosssection cm
centage of their available income on textiles. The
growth of fiber production for industrial use, on In general, the characteristic stress – strain curve
the other hand, is likely to continue. In 1984, 7 kg σ (ε) of fibers does not show a constant gradi-
of fiber was consumed per capita; for the year ent, even at low elongation. Hence, the modulus
2000, a total fiber production of 43×106 t is ex- of elasticity is usually defined as the differential
pected if per capita consumption remains at 7 kg, quotient dσ (ε)/dε. Experimental determination
or 48.6×106 t if it increases to 8 kg. The growth at low fiber elongation ε is difficult but can be
rate of 2.8 % achieved in the period 1968 – 1984 conducted successfully by extrapolation of the
is not expected to continue. Up to 1995 the aver- function dσ (e) /de for e= 0 [55].
age growth rate was only 2.3 %/a. Nevertheless, The elastic recovery of a fiber (in percent)
a world fiber volume of about 50×106 t is ex- can be measured by standard methods [56] and
pected in the year 2000 [52], [79]. is shown in Table 5 as
The limited means of production in Eastern  er 
Europe also contributed to reduced consump- 1− 100
e
tion. In the developing countries, lack of spend-
ing power, capital, and means of production all where εr = residual elongation, ε = total elonga-
combine to reduce growth of consumption. Re- tion.
gional differences in population growth will lead
to an increase in fiber consumption in the devel-
oping countries.
Table 4. Mechanical properties of fibers (data at break)

14
Fiber name/polymer Trade names Fiber type a Density (
), Elongation εH (21 ◦ C) Tenacity (σ H ) at 21 ◦ C Relative Relative
3
g/cm at 65 % “wet/dry,” at 65 % R.H. Wet/dry loop knot
b
R.H. , % % σ H /
, σH (relative), tenacity tenacity
cN/tex GPa % [62], % [63], %

Natural fibers
Cotton st 1.50 – 1.54 6 – 15 100 – 110 25 – 50 0.35 – 0.7 100 – 110 65 – 75 60 – 100
Wool st 1.32 25 – 50 110 – 130 10 – 20 0.15 – 0.25 70 – 90 75 – 85 80 – 85
Silk fi 1.25 10 – 30 120 – 200 25 – 50 0.3 – 0.6 75 – 95 60 – 80 80 – 85
Hemp st 1.48 2–5 ≈ 100 36 – 75 0.5 – 1.1 100 – 106
Flax st 1.438 – 1.456 1–4 110 – 125 30 – 55 0.43 – 0.8 105 – 120 20 – 40

Fibers, 1. Survey
Jute st 1.436 1.3 100 20 – 40 0.3 – 0.57 99 – 104
Regenerate cellulose
Viscose rayon, Viscose Modal Evlan, Fibro, st/fi 1.52 – 1.54 10 – 30 100 – 130 16 – 45 0.25 – 0.7 40 – 80 25 – 65 25 – 60
Sarille,...
Cuprammonium rayon Asahi Bemberg, st/fi 1.52 10 – 40 170 – 200 14 – 21 0.2 – 0.32 60 – 70 60 – 75 60 – 85
Bemberg
Cellulose acetate Arnel, Celco, st/fi 1.29 – 1.32 20 – 45 120 – 150 10 – 15 0.13 – 0.2 50 – 80 70 – 95 80 – 90
Dicel
Cellulose triacetate Estron, Silene, st/fi 1.29 – 1.32 20 – 45 120 – 150 10 – 15 0.13 – 0.2 50 – 80 70 – 95 80 – 90
Tricel
NMMO fibers [88] Lyocell, st 1.5 10 – 16 110 – 115 32 – 48 0.5 – 0.7 55 – 70 45 – 50 ≈ 75
Tencel,...
Protein fibers st 1.315 25 – 60 60 – 110 11 – 12 0.14 – 0.16 40 – 65
Alginate fiber (Ca-Alginate) fi 1.78 5 11 – 18 0.2 – 0.3 27 – 30
Polycondensate fibers
Nylon 6 (PA 6) Perlon, Acelon, st 1.14 30 – 70 105 – 125 30 – 40 0.35 – 0.45 80 – 90 65 – 85;
Amilan, Anso,
Caprolan,
Grilon,...
fi 1.14 20 – 45 105 – 125 40 – 60 0.45 – 0.7 85 – 90 70 – 95 80 – 90;
hd 1.14 15 – 20 105 – 125 60 – 90 0.7 – 1 85 – 90 70 – 90 60 – 70
Nylon 66 (PA 66) Nylon, Antron, st 1.14 30 – 60 105 – 125 35 – 40 0.4 – 0.45 see PA 6 see PA 6 see PA 6
Cantrece,
Meryl,
Timbrelle,
Ultron...
fi 1.14 20 – 40 105 – 125 40 – 60 0.45 – 0.7
hd 1.14 15 – 20 105 – 125 60 – 90 0.7 – 1
Table 4. (Continued)

Fiber name/polymer Trade names Fiber type a Density (
), Elongation εH (21 ◦ C) Tenacity (σ H ) at 21 ◦ C Relative Relative
3
g/cm at 65 % “wet/dry,” at 65 % R.H. Wet/dry loop knot
b
R.H. , % % σ H /
, σH (relative), tenacity tenacity
cN/tex GPa % [62], % [63], %

Aramids Compressive
strength, axial
in GPa, [80],
[81], [82]
Poly(m-phenyleneisophthalamide) Nomex, Conex fi 1.38 15 – 30 60 – 80 ≈95 80 – 85
Kevlar 29, fi 1.44 3–4 185 – 195 2.7 – 2.8 0.35 ≈45 ≈50
Twaron
Poly(p-phenyleneterephthalamide) Kevlar 49 fi/an 1.45 2 – 2.5 185 – 195 2.7 – 2.8 0.365 50 – 78 35 – 50
(PPTA)
Kevlar 149 fi/an 1.47 1.2 – 1.9 150 – 160 2.2 – 2.4
Kevlar 981, fi/hd 2.8 – 3.5 230 – 260 3.5 – 3.8
Twaron
Kevlar Hp fi 1.44 3.6 140 – 150 2.05
Dacron, Diolen, st 1.36 – 1.41 25 – 50 100 – 105 30 – 55 0.4 – 0.75 95 – 100 75 – 95
Fortrel, Grilene, st/ap 1.36 – 1.41 30 – 55 100 – 105 25 – 40 0.35 – 0.55 95 – 100 75 – 85
Poly(ethylene terephthalate) (PET)
Serene, fi 1.36 – 1.41 20 – 30 100 – 105 40 – 60 0.55 – 0.85 95 – 100 70 – 98 70 – 80
Terylene,
Trevira,.... fi/hd 1.36 – 1.41 8 – 20 100 – 105 60 – 100 0.85 – 1.5 95 – 100 60 – 90 40 – 70
Poly(butylene terephthalate) (PBT) Trevira 810, st/fi 1.25 35 – 40 40 – 45 0.5 – 0.56
Trevira 813
Poly(1,4-dimethylenecyclohexane Kodel st 1.22 – 1.23 15 – 35 22 – 36 0.37 – 0.45 ≈ 100 30 – 95
terephthalate) (PDCT) [59]
Polyarylate Ekonol [60], fi 1.40 – 1.41 2–5 200 – 280 2.8 – 3.9 Compressive 23 – 34
Vectran strength, axial
[80], [81], [82]
GPa
0.04 – 0.075
Poly(etherether ketone) (PEEK) Zyex fi 1.27 – 1.298 15 – 60 20 – 100 0.25 – 1.3 55 – 80 65 – 68
Polyimide (PI) P 84 st/fi 1.41 for st 30 – 38 27 – 37 0.38 – 0.53 60 – 65 70 – 75
and for fi
19 – 21
Novolak Kynol, Philene, st 1.2 – 1.3 20 – 60 13 – 22 0.17 – 0.27 70 80
Novoloid
Poly(amide imide) (PAI) Kermel st 10 – 25 25 – 60
Fibers, 1. Survey

Poly(ether imide) (PEI) st/fi 16 – 38 15 – 27 0.2 – 0.35

Polyurethane elastomers (spandex) Dorlastan, fi 1.1 – 1.3 400 – 700 ≈ 100 5 – 12; 0.06 – 0.15 75 – 100
Lycra, . . . 30 – 70 = σ H (1 + εH )/
c
15
Table 4. (Continued)

16
Fiber name/polymer Trade names Fiber type a Density (
), Elongation εH (21 ◦ C) Tenacity (σ H ) at 21 ◦ C Relative Relative
3
g/cm at 65 % “wet/dry,” at 65 % R.H. Wet/dry loop knot
b
R.H. , % % σ H /
, σH (relative), tenacity tenacity
cN/tex GPa % [62], % [63], %

Polymerizate fibers
Polyethylene (HD – PE) (HM – HD – PE: Hiralon, fi 0.95 – 0.96 10 – 45 100 30 – 70 0.3 – 0.65 100 60 – 90 70 – 90
M̄ r > 106 ) Vegon,...
Spectra 1000... hd 0.97 3–6 100 270 – 370 2.6 – 3.6 100 ≈ 50
Polypropylene (PP) Herculon, st/fi 0.90 – 0.92 15 – 50 100 25 – 60 0.22 – 0.55 100 85 – 95 70 – 90
Meraklon...

Fibers, 1. Survey
Polyacrylonitrile (PAN) Dralon T,... st/fi 1.17 – 1.19 25 – 40 ≈ 100 35 – 58 0.42 – 0.69 80 – 100 ≈ 60 ≈ 70
Copolymerizates with PAN ≥ 85 % Dolan, Dralon, st 1.17 – 1.19 20 – 60 100 – 120 18 – 32 0.2 – 0.37 75 – 95 30 – 80 75 – 80
Euroacril, fi 1.17 – 1.19 15 – 40 100 – 120 35 – 45 0.42 – 0.53 80 – 100 30 – 80 ≈ 70
Leacril,...
Modacrylics (50 – 84 % PAN) Kanekalon, st 1.3 – 1.4 25 – 50 100 – 110 15 – 25 0.2 – 0.35 80 – 100 50 – 70 ≈ 80
SEF,...
Poly(vinyl chloride) (PVC)
atactic Clevil, st/fi 1.38 – 1.40 10 – 40 100 20 – 24 0.28 – 0.34 100 35 – 70
Rhovil,....
syndiotactic [61] st 1.40 35 – 60 100 25 – 30 0.35 – 0.42 100 60 – 90 65 – 85
Kuralon, st 1.26 – 1.31 13 – 26 120 – 140 20 – 55 0.25 – 0.7 65 – 85 35 – 40 55 – 65
Poly(vinyl alcohol) (PVA)
Mewlon,
Solvron, fi 1.26 – 1.31 9 – 22 120 – 140 55 – 77 0.7 – 1 65 – 85 35 – 40 55 – 65
Vilon,...
6
(HM: M̄ r > 10 ) hd 1.31 3–4 150 – 230 2–3
Polytetrafluoro-ethylene (PTFE) Gore-Tex st/fi 2.1 – 2.3 20 – 40 100 8 – 18 0.16 – 0.38 100 60 – 90 75 – 90
Fibers,...
Poly(phenylene sulfide) (PPS) Procon, Rylon st/fi 1.37 – 1.38 25 – 40 28 – 47 0.4 – 0.65 78 60 – 80
Melamine resin fiber Basofil 1.4 – 1.5 15 – 25 15 – 40 0.2 – 0.6
Table 4. (Continued)

Fiber name/polymer Trade names Fiber type a Density (
), Elongation εH (21 ◦ C) Tenacity (σ H ) at 21 ◦ C Relative Relative
3
g/cm at 65 % “wet/dry,” at 65 % R.H. Wet/dry loop knot
b
R.H. , % % σ H /
, σH (relative), tenacity tenacity
cN/tex GPa % [62], % [63], %

Inorganic fibers Fiber Compressive

diameter, µm strength, axial,
GPa
Textile glass Gevetex, 2.45 – 2.6 2–5 100 70 – 120 1.7 – 2.7 15 – 30
Fiberglas
E glass E-Fiber, 5 – 15 2.52 – 2.54 2 – 3.5 100 80 – 140 2 – 3.5 0.5
Enkafort
Aluminum silicate (e.g., 3 Al2 O3 Nextel 312 17 2.63 – 2.7 65 1.7
· 2 SiO2 · B2 O3 ) Nextel 440 3.1
Nextel 480 3.05 1.1 75 2.3
Nicalon 5 – 20 2.6 – 3.1 1 ≈ 100 3
β-Silicon carbide (Nippon
Carbon)
FP (DuPont) 20 0.4 1.4 – 1.5
Saffil, Saffimax 3 – 3.2 2.8 – 3.3 0.7 30 – 60 1–2
(ICI)
Silica (SiO2 ) Silica (Akzo) 9 – 10 1.8 – 2.0 1.4 – 2.0 15 – 40 0.25 – 0.8
Steel (20 % Cr, 7 % Ni) Bekinox fi 7.9 1–2 100 22 – 29 1.75 – 2.25 65 – 75 60 – 70
Carbon (pitch based)
Tornel, Grafil, 6–9 2.0 – 2.06 0.4 (-2) ≈ 100 2 (-4) 0.4 – 0.8 0
High-modulus types (HM)
Fiber G 9 – 12 2.02 0.5 – 2 ≈ 250 ≈5 0.5 – 1.1 0
High-strength types (HS)
Carbon (PAN based) Magnamite,
Pyrofil, 6–7 1.8 – 1.96 0.4 – 1.2 100 – 180 1.9 – 3.5 1.4 – 1.5 0
High-modulus types (HM)
Torayca,... 7–9 1.74 – 1.82 1.5 – 2.4 170 – 380 3–7 1.44 – 4 0
High-strength types (HS)
a
st = staple fiber, fi = filament, hd = highly drawn, an = annealed, ap = antipilling; b R.H. = relative humidity; c effective breaking strength
Fibers, 1. Survey
17
Table 5. Elastomechanical properties of fibers

18
Fiber name/polymer Trade Fiber Elastic recovery, %: Initial Modulus Torsion modulus [64] Torsion
a
names type (1 – εr /ε) 100 for (elongation ε → 0) G/
, G, brittleness
ε = 2 % (5 %) E/
, E, N/tex GPa [66], degrees
N/tex GPa

Natural fibers
Cotton st 75 45 3–6 4.5 – 9 1.6 2.4 53 – 56
Wool st 95 – 99 60 – 70 1.5 – 3 2–4 0.8 – 1 ≈1 48 – 52
Silk fi 95 70 7 – 10 9 – 12.5 1.5 – 2.3 1.9 – 2.9 51
Hemp st 60 90
Flax st ≈ 60 8 – 25 12 – 36 0.95 1.3 – 1.4 68

Fibers, 1. Survey
Jute st 21 – 22 30 – 31
Regenerate cellulose
Viscose rayon, Viscose Modal Evlan, Fibro, st/fi 70 – 100 40 – 60 2 – 3 (6.5 – 7.5) 3 – 4.5 (4.2 – 4.9) 0.5 – 1 ≈1 51 – 55
Sarille,..
Cuprammonium rayon Asahi Bemberg, st/fi 70 – 95 40 – 60 2–3 3 – 4.5 48 – 57
Bemberg
Cellulose acetate Arnel, Celco, st/fi 90 – 95 (40 – 60) 2 – 3.5 2.5 – 4.5 0.6 – 0.8 ≈1 44 – 50
Dicel,
Cellulose triacetate Estron, Silene, st/fi 90 – 95 55 – 70 2 – 3.5 2.5 – 4.5 0.6 – 0.8 ≈1 44 – 50
Tricel,...
NMMO Fiber Lyocell, Tencel,.. st/fi 4 6
Protein fiber st 26 2 2–3 0.9 ≈1 30 – 40
Alginate fiber (Ca-Alginat) fi 7 12 – 13 1.2 ≈2
Polycondensate fibers
Perlon, Acelon, st 27 – 41
Nylon 6 (PA 6) Amilan, Anso, fi 95 – 100 95 – 100 0.5 – 3 0.6 – 3.5 ≈ 0.3 ≈ 0.3 33 – 42
Caprolan, hd 95 – 100 90 – 95 4–5 4.5 – 5.5 0.7 0.8
Grilon,...
Nylon, Antron, st 27 – 41
Nylon 66 (PA 66) Cantrece, Meryl, fi 95 – 100 95 – 100 0.5 – 3 0.6 – 3.5 0.45 0.5 40 – 41
Timbrelle, hd 95 – 100 90 – 95 4–5 4.5 – 6
Ultron,...
Table 5. (Continued)

Fiber name/polymer Trade Fiber Elastic recovery, %: Initial Modulus Torsion modulus [64] Torsion
a
names type (1 – εr /ε) 100 for (elongation ε → 0) G/
, G, brittleness
ε = 2 % (5 %) E/
, E, N/tex GPa [66], degrees
N/tex GPa

Aramids
Poly(m-phenyleneisophthalamide) Nomex, Conex, fi 8 – 14 11 – 20 ≈ 50
Kevlar 29, fi 95 – 100 41 – 53 59 – 77
Twaron,
Poly(p-phenyleneterephthalamide) Kevlar 49, fi/an 95 – 100 85 124
(PPTA) Twaron,
Kevlar 149, fi/an 96 103 150
Kevlar 981, fi/hd 70 – 83 102 – 120
Twaron,
Kevlar Hp fi 50 72
Dacron, Diolen, st 2.5 – 4 3.4 – 5.5 30 – 49
Terylene, ap 2.5 – 4 3.4 – 5.5 ≈ 48
Poly(ethylene terephthalate) (PET)
Trevira,
Fortrel, Grilene, fi 90 – 98 70 – 90 7 – 18 10 – 25 0.65 0.9 41 – 48
Serene,... hd 7 – 18 10 – 25 1.1 1.5 47 – 48
Poly(butylene terephtalate) (PBT) Trevira 810...813 fi 100 99 – 100 4–5 5–6
Poly(1,4-dimethylene cyclohexane Kodel st 85 – 95 50 – 60 2.5 – 4 3–5 49
terephthalate) (PDCT) [59]
Polyarylate Vectran, Ekonol fi 60 – 128 80 – 180
[61]
Poly(ether ether ketone) (PEEK) Zyex fi 4 – 12 5 – 15
Polyimide (PI) P84 st/fi 3.5 – 5 5–7
Novolak Kynol, Philene, st 2.6 – 3.6 3.3 – 4.6
Novoloid
Poly(amide imide) (PAI) Kermel st 3.5 – 7.5
Poly(ether imide) (PEI) st 2.7 – 4.2 3.5 – 5.1
Dorlastan, fi 93 – 98 ≈ 0.005 – 0.01 0.006 – 0.012
Polyurethane elastomers (spandex)
Lycra,... for ε = 300 % 0.004 0.005
Fibers, 1. Survey
19
Table 5. (Continued)

20
Fiber name/polymer Trade Fiber Elastic recovery, %: Initial Modulus Torsion modulus [64] Torsion
a
names type (1 – εr /ε) 100 for (elongation ε → 0) G/
, G, brittleness
ε = 2 % (5 %) E/
, E, N/tex GPa [66], degrees
N/tex GPa

Polymerizate fibers
Polyethylene (HD – PE) Hiralon, Vegon, fi 95 – 100 90 – 95 0.2 – 5 0.2 – 5 0.05 0.05
(HM – HD – PE: M̄ r > 106 ) Spectra 1000,... hd 100 51 – 165 50 – 160 1.5 [65] 1.5 [65]
Polypropylene (PP) Herculon, st/fi 95 – 100 85 – 95 0.5 – 5 0.5 – 5
Meraklon,...
Polyacrylonitrile (PAN) Dralon T,... st/fi 90 – 95 50 – 90 9.5 – 14 11 – 17 1.5 – 1.7 1.8 – 2

Fibers, 1. Survey
Dolan,Dralon st 90 – 95 50 – 90 3–5 3.5 – 6 45 – 52
Copolymerizates with PAN ≥ 85 %
Euroacril, fi 90 – 95 50 – 90 9 – 10 10 – 12 1 1.2 55 – 60
Leacril,...
Modacrylics (50 – 84 % PAN) Kanekalon, st 95 – 99 85 – 98 1 – 2.5 1.3 – 3.5
SEF,..
Poly(vinyl chloride) (PVC)
atactic Clevyl, st/fi 70 – 90 55 – 65 2–4 3 – 5.5 0.6 – 0.7 0.8 – 1 27 – 50
Rhovyl,...
syndiotactic [61] st 90 – 95 75 – 80 2.5 – 3 3.5 – 4
Kuralon, st 60 – 80 40 – 60 3–4 4–5 0.9 1.2
Poly(vinyl alcohol) (PVA)
Mewlon
Solvron, Vilon,... fi 60 – 80 40 – 60 3 – 4.5 4–6 1.2 – 1.5 1.6 – 2
(HM: M̄ r > 106 ) hd 30 – 60 40 – 80
Polytetrafluoroethylene (PTFE) Gore-Tex Fibers st/fi 0.35 – 2 0.7 – 4 0.2 – 0.3 0.4 – 0.7
Poly(pheneylene sulfide) (PPS) Procon, Ryton,... st/fi 2.7 – 5 3.7 – 6.8
Table 5. (Continued)

Fiber name/polymer Trade Fiber Elastic recovery, %: Initial Modulus Torsion modulus [64] Torsion
a
names type (1 – εr /ε) 100 for (elongation ε → 0) G/
, G, brittleness
ε = 2 % (5 %) E/
, E, N/tex GPa [66], degrees
N/tex GPa

Inorganic fibers Fiber

diameter,
Textile glass Gevetex, µm 100 28 – 34 70 – 90
16
40 85 – 88
Fiberglas,...
E glass E-Fiber, 5 – 15 100 28 – 34 70 – 90
16
40 85 – 88
Enkafort,...
Nextel 312, 17 5.5 – 52 15 – 140
Aluminum silicate
Nextel 440, 65 200
(e.g. 3 Al2 O3 · 2 SiO2 · B2 O3 )
Nextel 480 [89] 73 224
Nicalon (Nippon 5 – 20 67 – 100 200 – 300
β-Silicon carbide Carbon)
FP (DuPont) 20 120 – 125 350 – 385
Saffil, Saffimax 3 – 3.2 33 – 83 100 – 250
(ICI)
Silica (SiO2 ) Silica (Akzo) 9 – 10 6 – 30 12 – 56
Steel (20 % Cr, 7 % Ni) Bekinox fi 100 for ε = 1 % 19 – 25 150 – 200 7.9 – 9.5 60 – 70
Carbon (pitch based)
High-modulus types (HM) Thornel, Grafil, 6–9 250 – 400 500 – 800
High-strength types (HS) Fiber G 9 – 12 124 – 200 250 – 400
Carbon (PAN based) Magnamite
High-modulus types (HM) Pyrofil, 6–7 160 – 260 300 – 500
High-strength types (HS) Torayca,... 7–9 110 – 165 200 – 300 2.2 4
a
st = stable fiber, fi = filament, hd = highly drawn, an = annealed, ap = antipilling.
Fibers, 1. Survey
21
Table 6. Thermal properties of fibers

22
Fiber name/polymer Trade names Fiber type a Fiber shrinkage Specific Thermal Glass transition Melting Heat resistance
in water of 95 ◦ C, % heat capa- conductivity, temperature, temperature in air up to t, ◦ C
◦
drawn thermoset city [67], W m−1 K−1 C (decomposition
J g−1 K−1 temperature),
◦
C

Natural fibers
Cotton st 1.3 0.3 – 0.5 (400) 120
Wool st 1.3 – 1.6 0.2 – 0.4 45 [90] 120
Silk fi 1.4 0.2 – 0.4 40 – 50 (170 – 180) 120

Fibers, 1. Survey
Flax st 1.4 0.3
Regenerate cellulose
Viscose rayon, Viscose, Modal Evlan, Fibro, st/fi 0.5 – 10 b 1.3 – 1.5 0.3 – 0.6 (175 – 190) 120
Sarille,...
b
Cuprammonium rayon Asahi Bemberg, st/fi 0.5 – 10 1.4 (175 – 205) 120
Bemberg
Cellulose acetate Arnell, Celco, st/fi 5 – 20 1.3 – 1.5 0.3 255 120
Dicel,
Cellulose triacetate Estron, Silene, st/fi 5 – 20 0.7 1.5 0.3 170 – 180 [68] 300 130
Tricel,...
Polycondensate fibers
Perlon, Acelon, st 8 – 15 0.5 – 1.5 1.5 – 1.8 80 – 85 (dry) 215 – 220 120
Nylon 6 (PA 6) Amilan, Anso, fi 8 – 15 1–5 1.5 – 1.8 0.2 – 0.3 ≈ 20 (3.7 % 215 – 220 120
water)
Caprolan, hd 8 – 15 1.5 – 1.8 0.4 90 – 95 (dry) 215 – 220 120 – 150
Grilon,...
Nylon, Antron, st 8 – 15 0.5 – 1.5 1.5 90 – 95 (dry) 255 – 260 120
Nylon 66 (PA 66) Cantrece, Meryl, fi 8 – 15 1–5 1.5 0.2 – 0.3 ≈ 30 (3.7 % 255 – 260 120
water)
Timbrelle, hd 8 – 15 1.5 0.4 255 – 260 120 – 150
Ultron,...
Table 6. (Continued)

Fiber name/polymer Trade names Fiber type a Fiber shrinkage Specific Thermal Glass transition Melting Heat resistance
in water of 95 ◦ C, % heat capa- conductivity, temperature, temperature in air up to t, ◦ C
◦
drawn thermoset city [67], W m−1 K−1 C (decomposition
J g−1 K−1 temperature),
◦
C

Aramids
Poly(m-phenyleneisophthalamide) Nomex, Conex fi 1.5 1.2 0.13 280 – 290 (≈ 370) 180 – 200
Kevlar 29, fi 1.4 0.05 340 – 360 (≈ 550) 180 – 200
Poly(p-phenyleneterephthalamide) Twaron,
(PPTA) Kevlar 49, fi/an 0.05 340 – 360 (≈ 550) 180 – 200
Kevlar
149,Twaron,
Kevlar 981, fi/hd 340 – 360
Twaron,
Kevlar Hp fi 340 – 360
Dacron, Diolen, st 0.5 – 1 80 – 110 250 – 260 120 – 150
Fortrel, Grilene, ap 0.5 – 1 80 – 110 250 – 260 120 – 150
Poly(ethylene terephthalate) (PET)
Serene, Terylene, fi 5 – 10 0.5 – 1.5 0.4 – 1.9 [70] 0.2 – 0.3 80 – 110 250 – 260 120 – 150
Trevira, . . . hd 7–8 80 – 110 250 – 260 150 – 160
Poly(butylene terephtalate) (PBT) Trevira 810, st/fi 68 – 75 224 120
Trevira 813
Poly(1,4-dimethylene cyclohexane Kodel st 0.1 – 0.5 ≈ 100 285 – 290 ≈ 200
terephthalate) (PDCT) [59]

Polyarylate Vectran, Ekonol fi 320 – 290 180 – 260

[60]
Poly(ether ether ketone) (PEEK) Zyex fi 0.4 – 0.5 139 – 153 334 – 345 200 – 250
Polyimide (PI) P84 st/fi 315 260
Novolak Kynol, Philene, st 0
Novoloid
Poly(amide imide) (PAI) Kermel st (> 380) 250
Poly(ether imide) (PEI) st/fi 4–8 0.7 215 – 225 160 – 170
Polyurethane elastomers (spandex) Dorlastan, fi ≈ 3 – 12 0.15 Polyether:≈ − 60 230 – 290 120
Lycra,... [70] ;
Polyester − 40
Fibers, 1. Survey

to − 20
23
Table 6. (Continued)

24
Fiber name/polymer Trade names Fiber type a Fiber shrinkage Specific Thermal Glass transition Melting Heat resistance
in water of 95 ◦ C, % heat capa- conductivity, temperature, temperature in air up to t, ◦ C
◦
drawn thermoset city [67], W m−1 K−1 C (decomposition
J g−1 K−1 temperature),
◦
C

Polymerizate fibers
Polyethylene (HD-PE) Hiralon, Vegon, fi 5 – 10 1.4 – 2.0 0.2 – 0.4 − 20 to − 30 124 – 138 70 – 90
(HM – HD – PE: M̄ r > 106 ) Spectra 1000 hd 10 – 38 [84], − 20 to − 30 124 – 138
[85]

Fibers, 1. Survey
Polypropylene (PP) Herculon, st/fi 0–5 1.6 0.2 – 0.3 160 – 175 ≈ 120
Meraklon
Polyacrylonitrile (PAN) Dralon T fi/st 14 – 16 ≈1 0.2 ≈ 95 (dry) ≈ 320 140
Dolan, Dralon st (20 – 40 c ) 0.5 – 5 1.2 – 2.5 0.2 85 – 95 (dry); (>250) 140
Copolymerizates with PAN ≥ 85 %
50 – 60 (wet)
Euroacril, fi 16 – 22 ≈1 1.2 – 1.5 0.2 85 – 95 (dry); (>250) 140
Leacril, 50 – 60 (wet)
Modacrylics (50 – 84 % PAN) Kanekalon, st 0.2 – 5 85 – 95 ( 170) ≈ 120
SEF,...
Poly(vinyl chloride) (PVC)
atactic Clevyl, Rhovyl, st/fi 20 – 30 0.8 – 0.9 0.16 – 0.17 70 – 90 (160 – 200) < 65
syndiotactic [61] st 0 90 – 100 (160 – 200)
Kuralon, st 2–3 75 – 90 140
Poly(vinyl alcohol) (PVA)
Mewlon,
Solvron, Vilon, fi 75 – 130 (240 – 260) (water vapor:
120)
Polytetrafluoroethylene (PTFE) Gore-Tex Fibers st/fi 2 1.0 – 1.1 0.23 127 – 130 327 – 342 [72] 180
Poly(phenylene sulfide) (PPS) Procon, Ryton,... st/fi  16 85 – 95 270 – 290 190 – 200
Melamine resin fiber Basofil st 200 – 220
a
st = stable fiber, fi = filament, hd = highly drawn, an = annealed, ap = antipilling;
b
Depending on fiber type;
c
High-shrinkage (HS) fiber.
Table 7. Thermal and electrical properties of inorganic fibers

Fiber name Trade name Fiber diameter, µm Specific heat capacity Thermal Heat resistance in air Fire Limiting Oxygen Melting temperature Specific electrical
[67], Jg−1 K−1 conductivity, up to , ◦ C Index (LOI), % (Glass transition Tg ), resistance, Ω cm
◦
Wm− K−1 C
Textile glass Gevetex, Fiberglas 5 – 15 ≈ 0.75 ≈ 0.8 300 – 400 (600
Tg
700) 1012 – 1015
E Glass E-Fiber, Enkafort 5 – 15 ≈ 0.75 ≈ 0.8 300-400 (600
Tg
700) 1012 – 1015
Aluminum silicate Nextel 312 17 1200 – 1300 1800
(e.g., 3 Al2 O3 Nextel 440 1200 – 1300 1800
· 2 SiO2 · B2 O3 ) Nextel 480 1200
Nicalon (Nippon 5 – 20 12 > 800 2700
β-Silicon carbide Carbon)
FP (DuPont) 20 900
Saffil, Saffimax (ICI) 3 – 3.2 1000
Silica (SiO2 ) Silica (Akzo) 9-10 1000 – 1100 1750
Steel (20 % Cr, 7 % Bekinox filaments 0.46 15 1400 – 1450
Ni)
Carbon (pitch based) 0.7 ×10−4
High-modulus Thornel, Grafil, 6–9 300 (-500)
types (HM)
High-strength Fiber G,... 9 – 12 300 (-500) >10−3
types (HS)
Carbon (PAN based)
High-modulus Magnamite, Pyrofil, 6–7 60 – 115 [73] 300 (-500) > 60 3600 ≈ 10−3
types (HM)
High-strength Torayca,... 7–9 0.7 15 – 20 [73] 300 (-500) > 60 ≈ 1.5× 10−3
types (HS)
Fibers, 1. Survey
25
Table 8. Electrical resistance, ironing temperature, water absorption and solubility of fibers

26
Fiber name/polymer Trade names Fiber type a Specific Ironing Water Water Solubility in selected solvents c
electrical tempera- absorption retention
resistance, b ture, ◦ C at 21 ◦ C, [74], %
Ω cm 65 % R.H.,d
%

Natural fibers
Cotton st 106 – 108 180 – 220 7 – 11 40 – 50 concentrated H2 SO4 , Cuoxam-solution
Wool st 108 – 1011 160 – 170 15 – 17 40 – 45 conc. inorg. acids, conc. KOH
Silk fi 109 – 1010 140 – 165 9 – 11 40 – 45 conc. inorg. acids, conc. KOH, conc. HCO2 H
Flax st 215 – 240 8 – 10 50 – 55 concentrated H2 SO4
Regenerate cellulose

Fibers, 1. Survey
Viscose rayon Evlan, Fibro, st/fi 106 – 107 150 – 180 12 – 14 85 – 120 conc. inorg. acids
Sarille,...
7 8
Cuprammonium rayon Asahi Bemberg, st/fi ≈ 10 – 10 150 – 180 11 – 12 100 – 125 conc. inorg. acids
Bemberg,...
Cellulose acetate Arnel, Celco, Dicel st/fi 109 – 1012 180 6–7 20 – 28 conc. inorg. acids, acetone, dioxane, phenols
Cellulose triacetate Estron, Silene, st/fi ≈ 1014 220 – 250 2–5 10 – 18 conc. inorg. acids, acetone, dioxane, phenols
Tricel,...
NMMO Fiber Lyocell, Tencel,... st/fi 150 65 – 70 N-methylmorpholine oxide (NMMO)
Polycondensate fibers
Perlon, Acelon, st 150 3.5 – 4.5 10 – 15 conc. inorg. acids, phenols
Nylon 6 (PA 6) Amilan, Anso, fi 109 – 1011 150 3.5 – 4.5 10 – 15 conc. inorg. acids, phenols
Caprolan, Grilon,... hd 150 3.5 – 4.5 9 – 11 conc. inorg. acids, phenols
Nylon, Antron, st 180 – 200 3.5 – 4.5 10 – 15 conc. inorg. acids, phenols
Nylon 66 (PA 66) Cantrece, Meryl, fi 109 – 1011 180 – 200 3.5 – 4.5 10 – 15 conc. inorg. acids, phenols
Timbrelle, Ultron,... hd 180 – 200 3–4 9 – 11 conc. inorg. acids, phenols
Aramids
Poly(m-phenyleneisophthalamide) Nomex, Conex fi 4.5 – 5 12 – 17 polar org. solvents and solutes (LiCl, CaCl2 ), conc.
H2 SO4
Kevlar 29, Twaron, fi 2–3 7 conc. H2 SO4
Poly(p-phenyleneterephthalamide) Kevlar 49, Kevlar fi/an 1015 2–3 7 conc. H2 SO4
(PPTA) 149, Twaron
Kevlar 981, Twaron fi/hd 2–3 7 conc. H2 SO4
Kevlar Hp fi 2–3 7 conc. H2 SO4
Dacron, Diolen, st 150 – 200 0.3 – 0.4 3–5 conc. H2 SO4 , conc. KOH, phenols, tetrachloroethane
Poly(ethylene terephthalate) (PET) Fortrel, Grilene, fi 1011 – 1014 150 – 200 0.2 – 0.5 3–5 conc. H2 SO4 , conc. KOH, phenols, tetrachloroethane
Terylene, Trevira,... hd 150 – 200 0.2 – 0.4 3–5 conc. H2 SO4 , conc. KOH, phenols, tetrachloroethane
Poly(1,4-dimethylene cyclohexane Kodel st ≈ 200 0.2 conc. H2 SO4 , conc. KOH, phenols, tetrachloroethane
terephthalate) (PDCT) [59]
Table 8. (Continued)

Fiber name/polymer Trade names Fiber type a Specific Ironing Water Water Solubility in selected solvents c
electrical tempera- absorption retention
resistance, b ture, ◦ C at 21 ◦ C, [74], %
Ω cm 65 % R.H.,d
%

Polyarylate Ekonol [60], Vectran fi 0 NMP + CaCl2

Poly(ether ether ketone) (PEEK) Zyex fi conc. H2 SO4
Novolak Kynol, Philene, 6–8
Novoloid,...
Poly(amide imide) (PAI) Kermel 3 polar org. solvents (DMA, NMP)
Poly(ether imide) (PEI) st/fi 0.25 – 1.25 dichloromethane
Polyurethane elastomers (spandex) Dorlastan, Lycra, ... fi 150 – 180 0.5 – 1.5 7 – 11 noncross-linked fibers: DMA, DMF, HMPA, conc.
inorg. acids (decomp.)
Polymerizate fibers
Polyethylene (HD-PE) Hiralon, Vegon, fi 1013 – 1017 0 0 conc. H2 SO4 , benzene, chlorinated hydrocarbons
Spectra,...
13
Polypropylene (PP) Herculon, st/fi > 10 130 0 0 conc. H2 SO4 , toluene, chlorinated hydrocarbons
Meraklon,...
Polyacrylonitrile (PAN) e.g., Dralon T fi/st ≈ 1014 150 – 180 ≈1 4–6 conc. inorg. acids, DMA, DMF, DMS, ethylene
carbonate, conc. ZnCl2 or NaSCN solutions
Copolymerizates with PAN ≥ 85 % Dolan, Dralon,... st/fi 108 – 1014 150 – 180 1 – 1.5 5 – 12 conc. inorg. acids, DMA, DMF, DMS, ethylene
carbonate, conc. ZnCl2 or NaSCN solutions
12 13
Modacrylics (50 – 84 % PAN) Kanekalon, SEF,... st 10 – 10 0.4 – 3 10 – 20 conc. H2 SO4 , DMF, acetone, phenol, cyclohexanone
Poly(vinyl chloride) (PVC)
12 14
atactic Clevyl, Rhovyl st/fi 10 – 10 0 – 0.2 4–6 conc. H2 SO4 , chlorinated hydrocarbons, dioxane,
cyclohexanone, DMF
syndiotactic [61] st 1012 – 1014 0 4–6 conc. H2 SO4 , chlorinated hydrocarbons, dioxane,
cyclohexanone, DMF
Fibers, 1. Survey
27
Table 8. (Continued)

28
Fiber name/polymer Trade names Fiber type a Specific Ironing Water Water Solubility in selected solvents c
electrical tempera- absorption retention
resistance, b ture, ◦ C at 21 ◦ C, [74], %
Ω cm 65 % R.H.,d
%

Poly(vinyl alcohol) (PVA) Kuralon, Mewlon,... st/fi 3.5 – 5 25 – 35 conc. inorg. acids, phenols, DMF
Poly(tetrafluoroethylene) (PTFE) Gore-Tex Fibers,... st/fi > 1014 0 perfluorinated solvents > 300 ◦ C
Poly(phenylene sulfide) (PPS) Procon, Ryton,... st/fi ≈ 0.03 – 0.25 < 200 ◦ C no solvent
(< 0.6)
Melamine resin fiber Basofil st 9
Inorganic fibers

Fibers, 1. Survey
Textile glass Gevetex, Fiberglas st/fi 1012 – 1015 0.1 0 hydrofluoric acid
E glass E-Fiber, Enkafort fi 1012 – 1015 0.1 0 hydrofluoric acid
Aluminum silicate Nextel 312 st ≈0 0 hydrofluoric acid
(e.g., 3 Al2 O3 · 2 SiO2 · B2 O3 ) Nextel 440 st ≈0 hydrofluoric acid
Steel (20 % Cr, 7 % Ni) Bekinox fi 0.7×10−4 0 (attacked by halogenated solvents)
a
st = staple fiber, fi = filament, hd = highly drawn, an = annealed, ap = antipilling;
b
of fibers without additives or special finishes;
c
DMA = dimethylacetamide, DMF = dimethylformamide, DMS = dimethyl sulfoxide, HMPA = hexamethylphosphoramide, NMP = N-methyl pyrrolidone;
d
R.H. = relative humidity.
Table 9. Resistance of fibers c

Fiber name/polymer Trade names Fiber type a Heat (air) Light/weather b Biological influence c Chemicalsc Fire
◦
up to t, C Residual Micro- Insects Residual tenacity, % limiting
◦ ◦
tenacity, % organisms After 1000 h at 20 C/10 h at 100 C oxygen
[57], [58], dilute acid dilute alkali index
[75], [76] (LOI), %

Natural fibers
Cotton st 120 20 – 30/0 – 20 − (+) 60 – 80/0 – 20 80 – 100/80 – 100 19 – 20
Wool st 120 0 – 20/0 – 20 − − 90 – 100/selective selective 25 – 28
Silk fi 120 0 – 20/0 – 20 (+) (+) lower than wool selective
Flax st 0 – 20/0 – 20 bleached (+) more resistant than lower than cotton
cotton
Regenerate cellulose
Viscose rayon, Viscose Evlan, Fibro, st/fi 120 0 – 30/0 − − similar to cotton 19 – 20
Modal Sarille,...
Cuprammonium rayon Asahi Bemberg, st/fi 120 0 – 30/0 − − similar to cotton 19 – 20
Bemberg
Cellulose acetate (CA) Arnell, Celco, Dicel, st/fi 120 20 – 45/0 – 25 (+) − 60 – 100/selective 0 – 20/20 – 60 18 – 19
NaOH
Cellulose triacetate Estron, Silene, st/fi 130 20 – 45/0 – 25 (+) − 60 – 100/selective better than CA 18 – 19
Tricel,...
NMMO Fiber Lyocell, Tencel st/fi 150 similar to similar to cotton similar to cotton
cotton
Polycondensate fibers
Perlon, Acelon, st 120 20 – 30/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 21.5
Nylon 6 (PA 6) Amilan, Anso, fi 120 20 – 30/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 21.5
Caprolan, Grilon,... hd 120 – 150 20 – 30/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 21.5
Nylon, Antron, st 120 20 – 30/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 21.5
Nylon 66 (PA 66) Cantrece, Meryl, fi 120 20 – 30/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 21.5
Timbrelle, Ultron,... hd 120 – 150 20 – 30/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 21.5
Fibers, 1. Survey
29
Table 9. (Continued)

30
Fiber name/polymer Trade names Fiber type a Heat (air) Light/weather b Biological influence c Chemicalsc Fire
◦
up to t, C Residual Micro- Insects Residual tenacity, % limiting
◦ ◦
tenacity, % organisms After 1000 h at 20 C/10 h at 100 C oxygen
[57], [58], dilute acid dilute alkali index
[75], [76] (LOI), %

Aramids
Poly(m-phenyleneiso- Nomex, Conex fi 180 – 200 /50 + 80 – 100/80 – 100 90 – 100/90 – 100 26 – 30
phthalamide)
Kevlar 29, Twaron, fi 180 – 200 65 – 80/ after 16 (+) + + +
Poly(p-phenylene- weeks

Fibers, 1. Survey
terephthalamide)
Kevlar 49, Twaron, fi/an 180 – 200 65 – 80/ after 16 (+) + + + 29 – 31
(PPTA)
Kevlar 149, weeks
Kevlar 981, Twaron, fi/hd 180 – 200 65 – 80/ after 16 (+) + + + 29 – 31
weeks
Kevlar Hp fi 180 – 200 65 – 80/ after 16 (+) + + + 29 – 31
weeks
Dacron, Diolen, st 120 – 150 60 – 80/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 22
Poly(ethylene Fortrel, Grilene, ap 120 – 150 60 – 80/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 22
terephthalate) (PET) Terylene, Serene, fi 120 – 150 60 – 80/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 22
Trevira,... hd 150 – 160 60 – 80/5 – 15 (+) + 90 – 100/90 – 100 90 – 100/90 – 100 20 – 22
Poly(butylene Trewira 810,...813 st/fi 120
terephtalate) (PBT)
Poly(1,4-dimethylene Kodel st ≈ 200 + 70 – 80 HCl 50 – 70
cyclohexane terephthalate) Na2 CO3 solution
(PDCT ) [59]

Polyarylate Vectran, Ekonol [60] fi 180 – 260 +/96 - 36

Poly(ether ether ketone) Zyex fi 200 – 250 - 99/23-74 selective /95 30 – 35
(PEEK)
Polyimide (PI) P 84 st/fi 260  80 (+) 36 – 38
Novolak Kynol, Philene, st 200 + - 30 – 39
Novoloid
Table 9. (Continued)

Fiber name/polymer Trade names Fiber type a Heat (air) Light/weather b Biological influence c Chemicalsc Fire
◦
up to t, C Residual Micro- Insects Residual tenacity, % limiting
◦ ◦
tenacity, % organisms After 1000 h at 20 C/10 h at 100 C oxygen
[57], [58], dilute acid dilute alkali index
[75], [76] (LOI), %

Poly(amide imide) (PAI) Kermel st 250 - + (+) 31 – 32

Poly(ether imide) (PEI) st/fi 160 – 170 + 95 – 100/ 85 – 100/ 33
Polyurethane elastomers Dorlastan, Lycra,... fi 120 0/0 + + selective; polyether
(spandex) more resistant than
polyester

Polymerizate fibers
Polyethylene (HD)-PE Hiralon, Vegon,,... fi 70 – 90 + − (+) + +
(HM – HD – PE: M̄ r Spectra 1000 hd 80 – 90 + − (+) + +
> 106 )
Polypropylene (PP) Herculon, st/fi ≈ 120 0/0 − (+) + + 19 – 20
Meraklon,...
Polyacrylonitrile (PAN) e.g., Dralon T fi/st 140 60 – 80/50 – 60 (+) + 90 – 100/80 – 100 90 – 100/60 – 100 18 – 20
Copolymerizates with Dolan, Dralon, st/fi 140 60 – 80/50 – 60 (+) + 90 – 100/80 – 100 90 – 100/60 – 100 18 – 20
PAN ≥ 85 % Euroacril, Leacril,...
Modacrylics (50 – 84 % Kanekalon, SEF,... st 120 lower than PAN + + + + 25 – 30
PAN)
Poly(vinyl chloride)
atactic Clevyl, Rhovyl,... st/fi < 65 60 – 90/ + + + + 37 – 46
syndiotactic [61] st + + + + 37 – 46
Kuralon, Mewlon, st 140 (water vapor: better than nylon 20
Poly(vinyl alcohol) (PVA)
120)
Solvron, Vilon,... fi 140 (water vapor: +/(+) (+) (+) better than nylon + 20
120)
6
(HM: M̄ r > 10 ) hd 140 (water vapor: better than nylon + 20
120)
Poly(tetrafluoroethylene) Gore-Tex Fibers,... st/fi 180 + + + +  40
(PTFE)
Poly(phenylene sulfide) Procon, Ryton,... st/fi 190 – 200 - + + +/100 +/100 34 – 35
(PPS)
Melamine resin fiber Basofil st 200 – 220 0 ≈ 70/ 30
Fibers, 1. Survey

a
st = staple fiber, fi = filament, hd = highly drawn, an = annealed ap = antipilling;
b
no UV stabilizers added, one-year exposure in Florida;
c
+ resistant, (+) moderately resistant, − not resistant.
31
32 Fibers, 1. Survey
Table 10. Dyeing behavior of fibers

Fiber name/polymer Trade name Dyes

Natural fibers
Cotton substantive
Wool anionic
Silk anionic, cationic, substantive, reactive, vat
Regenerate cellulose
Viscose rayon Evlan, Fibro,... substantive
Cuprammonium rayon Asahi Bemberg,... substantive
Cellulose acetate Arnel, Celco, Dicel, substantive, disperse
Cellulose triacetate Estron, Silene, Tricel,... substantive, disperse
NMMO fiber Lyocell, Tencel,... substantive, reactive
Polycondensate fibers
Nylon 6 Perlon, Capron, Grilon,... anionic, metal-complex disperse
Nylon 66 Nylon, Antron, Ultron,... anionic, metal-complex, disperse
Poly(m-phenyleneisophtalamide) (aramid) Nomex cationic plus carrier, high-temperature
conditions
Poly(ethylene therephthalate) Dacron, Diolen,... disperse plus carrier, high-temperature
conditions
Poly(1,4–dimethylenecyclohexane) Kodel disperse plus carrier, high-temperature
conditions
Poly(butylene terephthalate) Trevira 810,..813 disperse
Novolak Kynol,... disperse
Poly(ether imide) disperse
Polyurethane elastomers Dorlastan, Lycra anionic
Polymerizate fibers
Polypropylene Herculon, Meraklon,... disperse
Polyacrylonitrile Dralon, Dolan,... cationic, disperse
Modacrylics Kanekalon, SEF,... cationic, disperse
Poly(vinyl chloride) Clevyl, Rhovyl,... disperse
Poly(phenylene sulfide) Procon, Ryton disperse

Figure 8. Specific tenacity (σ/) and modulus (E/) of high-performance fibers ( = density)
 Fibers, 1. Survey 33

Figure 9. Highest temperatures for fiber application without significant loss in tenacity

Values for fiber elongation, fiber shrinkage, (crystal) modulus. The ratio of fiber to crys-
and relative properties such as wet tenacity, loop tal modulus attains about 0.1 for textile com-
tenacity and other parameters are expressed as modity fibers, 0.3 for high-performance fibers
percent. If properties such as fiber resistance to (e.g., from HM-HDPE), especially those with
light, weather, chemicals, or organisms cannot extended chain structure, and as high as 0.8 for
be expressed numerically, they are characterized the LC polymer Kevlar 149 with unfolded, ori-
in a simplified qualitative manner in Table 9. In ented PPTA molecules. The deficit of the fiber
individual cases, the respective conditions and modulus is a consequence of incompletely un-
the type of attack (e.g., by certain kinds of pests coiled and disentangled macromolecules in as-
[57], [58]) are such that widely differing results spun and drawn fibers. The mechanical response
can be expected. of fibers is controlled by the fraction of taut tie
Some promising fibers that are still being de- molecules connecting neighboring crystallites.
veloped have also been included, in particular, This fraction can be estimated from measure-
high-performance fibers made from high molec- ments of the elastic modulus by using a simple
ular mass poly(vinyl alcohol), the thermoresis- rheological model or other methods to be about
tant PEEK, PAI, PI (see Fig. 9, and the polyary- 0.05 – 0.1 for drawn fibers [83].
late “ Ekonol,” an example of a thermotropic Compressibility and lateral compliance in-
polymer [59]. Among the inorganic fibers, apart crease with increasing fiber anisotropy (on draw-
from carbon and glass, the properties of silicon ing) and this is undesirable for reinforcing fibers
carbide, and ceramic fibers have been included. (e.g., Kevlar or carbon fibers) in composites. In
Figure 8 shows the ranges of Young’s moduli and some cases thermal aftertreatment of such high-
tenacities of presently known high-performance performance fibers allows a compromise to be
fibers used mainly for reinforcing organic resins. found between the desired compressibility and
lower tenacity (see also compressive strength of
Although fibers are highly anisotropic com- fibers in Table 4).
pared with other materials and therefore espe- The applicability of industrial fibers at higher
cially strong in the axial direction their Young’s temperatures (see Tables 6 and 7) is of current
modulus is always inferior to the theoretical
34 Fibers, 1. Survey

interest. Figure 9 reviews the thermal long-term Polymeric Substances, Interscience, New
stability in air. York.
This compilation of important data is by no 18. Internat. Baumwoll-Inst. (ed.): Handbuch der
means complete. For further information, see Baumwollstoffe, Frankfurt 1983.
→ Fibers, 4. Synthetic Organic and → Fibers, 19. H. Klare: Geschichte der
5. Synthetic Inorganic. Chemiefaserforschung, Akademie Verlag,
Berlin 1985.
20. P.-A. Koch, (ed.): Großes Textil-Lexikon,
Deutsche Verlagsanstalt, Stuttgart 1966.
9. References 21. H. A. Krässig, J. Lenz, H. F. Mark: Fiber
Technology, Dekker, New York 1984.
General References 22. R. Vieweg, G. W. Becker (ed.):
1. H. Batzer (ed.): Polymere Werkstoffe, Thieme Kunststoff-Handbuch, Hanser Verlag,
Verlag, Stuttgart 1986. München 1965.
2. R. Bauer, H. J. Koslowski: 23. P. Lennox-Kerr: The World Fibres Book, The
Chemiefaser-Lexikon, 10th ed. Deutscher Textile Trade Press, Mancheser, 1972.
Fachverlag, Frankfurt 1993. 24. M. Lewin, S. B. Sello (ed.): Handbook of Fiber
3. J. Brandrup, (ed.): Polymer Handbook , 2nd Science and Technology, Dekker, New York
ed., Interscience, New York 1976. 1983.
4. R. M. Brown, (ed.): Cellulose and Other 25. W. Loy: Chemiefaserstoffe, Schiele und
Natural Polymer Systems, Plenum Publishing, Schön, Berlin 1978.
New York 1982. 26. J. A. Maclaren, B. Milligan: Wool Science,
5. M. E. Carter: Essential Fiber Chemistry, Science Press, Marrickville 1981.
Dekker, New York 1971. 27. H. F. Mark (ed.): Man-made Fibers, Science
6. J. G. Cook: Handbook of Textile Fibres, and Technology, Interscience, New York 1968.
Merrow, Watford 1968. 28. R. Meredith: Elastomeric Fibres, Merrow,
7. H. Driesch: Welche Chemiefaser ist das, Watford 1971.
Franckh, Stuttgart 1962. 29. B. E. Messerli (ed.): Seide,
8. A. A Dembeck: Guidebook to Man-made Textilwerkstattverlag Hannover, 1986.
Textile Fibres and Textured Yarns of the World, 30. L. Miles: Cotton, Wayland, Have 1980.
3rd ed. The United Piece Dyed Works, New 31. R. Moncrieff: Man-made-Fibres, 4th ed.,
York 1969. Heywood, London 1966.
9. H. Doehner (ed.): Wollkunde, Parey, Berlin 32. J. S. Robinson (ed.): Fiber-forming Polymers,
1964. Noyes Data Corp., Park Ridge 1980.
10. H. F. Mark (ed.): Encyclopedia of Polymer 33. J. S. Robinson (ed.): Spinning, Extruding and
Science and Technology, “Plastics, resins, Processing of Fibers, Noyes Data Corp., Park
rubbers, fibres,” Wiley-Interscience, New York Ridge 1980.
1967. 34. J. S. Robinson (ed.): Manufactue of Yarns and
11. B. Falkai (ed.): Synthesefasern, Verlag Fabrics from Synthetic Fibers, Noyes Data
Chemie, Weinheim 1981. Corp., Park Ridge 1980.
12. F. Fourné (ed.): “Herstellung und 35. W. J. Roff: Fibres, Films, Plastics and
Verarbeitung,” Synthetische Fasern, Rubbers, Butterworths, London 1971.
Wissenschaftl. Verlags GmbH, Stuttgart 1964. 36. Z. A. Rogovin: Chemiefasern, Thieme Verlag,
13. B. C. Gaswami, J. G. Martindale, F. L. Stuttgart 1982.
Scardino: Textile Yarns, Wiley-Interscience, 37. H. E. Schiecke: Wolle als textiler Rohstoff,
New York 1977. Schiele und Schön, Berlin 1979.
14. M. Grayson (ed.): Encyclopedia of Textiles, 38. K. A. Schmidt: Technologie textiler
Fibers, and Nonwoven Fabrics, Glasfasern, Zechner, Speyer 1964.
Wiley-Interscience, New York 1984. 39. Textil-Fakten: Markt- und Strukturdaten der
15. F. Happey: Applied Fibre Science, Academic Textil- und Bekleidungswirtschaft, Deutscher
Press, London 1979. Fachverlag, Frankfurt 1983.
16. H. W. Haudek, E. Viti: Textilfasern, Bondi, 40. Textile Faserstoffe, Fachbuchverlag, Leipzig
Wien 1980. 1967.
17. High polymers, a Series of Monographs on the 41. C. A. Tisdell: Economics of Fibre Markets,
Chemistry, Physics and Technology of High Univ. New Castle, New Castle, Austr. 1977.
 Fibers, 1. Survey 35

42. E. Wagner: Die textilen Rohstoffe, 6th ed., (1956) T 530. I. D. Owen, J. Text. Inst., Trans.
Spohr, Wuppertal 1981. 56 (1965) T 329.
43. A. Ziabicki: Fundamentals of Fibre Formation, 65. C. L. Choy, W. P. Leung, J. Polym. Sci. Polym.
Wiley Interscience, New York 1976. Phys. Ed. 23 (1985) 1759 – 1780.
44. A. Ziabicki: High Speed Fibre Spinning, 66. P. A. Koch, G. Feier, B. Hoffmann:
Wiley Interscience, New York 1985. “Untersuchungen über die Quersprödigkeit
45. F. Schultze-Gebhardt, “Survey of the Most neuer Synthesefasern,” Forschungsber.
Important Properties of High-Performance Landes Nordrhein-Westf. no. 2299,
Fibers and their Technical Use,” Westdeutscher Verlag, Opladen 1973.
Chemiefasern/Textilind. 43 (1993) 67. W. Götze, F. Winkler, Faserforsch. Textiltech.
T 194 – 196, E 135. 18 (1967) 119, 385.
68. K. E. Perepelkin, Faserforsch. Textiltech. 25
Specific References (1974) 251.
46. P.-A. Koch (ed.): Großes Textil-Lexikon, 69. G. W. Urbanczyk, G. Michalak, J. Appl.
Deutsche Verlagsanstalt, Stuttgart 1966. Polym. Sci. 32 (1986) 3841 – 3846.
47. H. Batzer, (ed.): Polymere Werkstoffe, Thieme 70. H. Hespe, E. Meisert, U. Eisele, L. Morbitzer,
Verlag, Stuttgart 1986. W. Goyert, Kolloid Z. Z. Polym. 250 (1972)
48. H. Staudinger et al., Phys. Chem. 126 (1927) 797. D. J. Hourston, R. Meredith, J. Appl.
3. Polym. Sci. 17 (1973) 3259.
49. G. Henrici-Olivé, S. Olivé, Adv. Polym. Sci. 71. G. Hinrichsen, Angew. Makromol. Chem. 20
51 (1983) 1. (1971) 121.
50. K.-H. Umbach, Chemiefasern/Textilind. 33 72. R. L. McGee, J. R. Collier, Polym. Eng. Sci. 26
(1983) 85, 136, 204. (1986) 239 – 242.
51. Chemiefasern/Textilind. 37 (1987) 182. 73. H. Böder, D. Gölden, P. Rose, H. Würmseher:
52. J. D. Geerdes: World Fibre Production, Trends “Kohlenstoffasern – Herstellung,
and Outlok, Internat. Conference on Man Eigenschaften, Verwendung,” Z.
Made Fibres, Beijing, Nov. 1985. Werkstofftech. 11 (1980) 275.
53. P.-A. Koch: Faserstoff-Tabellen, 74. DIN 53 814 (1974).
Konradin-Verlag Kohlhammer GmbH, 75. I. A. Ermilova, L. N. Alekseeva, I. I. Šamolina,
Stuttgart 1968, 1977, 1979. V. A. Chochlova, Sowj. Beiträge Faserforsch.
54. E. Kleinhansl, J. Mavely: Denkendorfer Textiltech. 19 (1982) 274 – 276.
Fasertafeln 1986, Textilpraxis int., 76. Y. L. Hsieh, D. A. Timm, J. Merry, Textile Res.
Leinfelden-Echterdingen 1986. J. 57 (1987) 20 – 28.
55. F. Schultze-Gebhard: “Mechanische 77. G. Wu, J.-D. Jiang, P. A. Tucker, J. A. Cuculo,
Eigenschaften,” in B. von Falkai (ed.): J. Polym. Sci.: B: Polym. Phys. 34 (1996)
Synthesefasern, Verlag Chemie, Weinheim 2035 – 2047.
1981, p. 64. 78. F. Schultze-Gebhardt, Chemiefasern/Textilind.
56. DIN 53 835 (1975). 43 (1993) 432 – 433, E 66, E 68.
57. W. Kerner-Gang, H. Kühne in G. Schreyer 79. Chem. Fibers Int 46 (1996) 230. Econom.
(ed.): Konstruieren mit Kunststoffen, Hanser Fiber Bureau, Washington: Fiber Organon,
Verlag, München 1972. Washington 1996.
58. H. Kühne, TPI Text. Prax. Int. 29 (1974) 57; 80. T. F. N. Johnson, Chem. Fibers Int. 46 ( 1996)
30 (1975) 598,718. 280, 282 – 284, 286.
59. E. V. Martin, H. Busch, Angew. Chem. 74 81. S. R. Allen, J. Mater. Sci. 28 (1993) 853 – 859.
(1962) 624. 82. G. J. Hayes, D. D. Edle, J. M. Kennedy, J.
60. Sumitomo Chem. Com., US 4 503 005, 1983 Mater. Sci. 28 (1993) 3347 – 3257.
(K. Ueno, H. Sugimoto, K. Hayatsu). 83. M. Miwa et al., J. Mater. Sci. 31 (1996)
61. C. Mazzolini: The Development of a New 499 – 506.
Fibre from Syndiotactic Polyvinylchloride, 84. F. Schultze-Gebhardt, Acta Polym. 41 (1990)
2nd Shirley International Seminar, Manchester 512 – 513, Chemiefasern/Textilind. 40 (1990)
1970. T 56, T 58, E 49 – E 50.
62. DIN 53 843 (1976). 85. B. Poulaert et al., Polym. Commun. 31 (1990)
63. DIN 53 842 (1976). 48 – 51.
64. R. Meredith, J. Text. Inst., Trans. 45 (1954) 86. C. L. Choy, Y. Fei, T. G. Xi, J. Appl. Polym.
T 489. N. Adams, J. Text. Inst., Trans. 47 Sci. 31 (1993) 365 – 370.
36 Fibers, 1. Survey

87. D. T. Grubb, L. W. Jelinski, Macromolecules Textilber. 78 (1997) 575 – 581.

30 (1997) 2860 – 2867. 89. H. Blumberg, Chem. Fibers Int. 47 (1997)
88. W. Albrecht, M. Reintjes, B. Wulfhorst: 36 – 41.
“Lyocell-Fasern, Faserstoff-Tabellen nach 90. J. M. Kure et al., Textile Res. J. 67 (1997)
P.-A. Koch, 1. Ausg. 1997,” Melliand 18 – 22.
 Fibers, 2. Structure 1

Fibers, 2. Structure
John W. S. Hearle, The University of Manchester Institute of Science and Technology, Manchester, United
Kingdom

1. Introduction . . . . . . . . . . . . . . . 1 3.2. Protein Fibers . . . . . . . . . . . . . . 27

1.1. Fibers as Industrial Chemical 3.2.1. Wool and Hair . . . . . . . . . . . . . . . 29
Structures . . . . . . . . . . . . . . . . . 1 3.2.2. Silk . . . . . . . . . . . . . . . . . . . . . 29
1.2. Structural Types . . . . . . . . . . . . . 3 3.2.3. Regenerated Protein Fibers . . . . . . . 29
1.3. Development of Knowledge of Fiber 3.3. Major Melt-Spun Fibers . . . . . . . 29
Structure . . . . . . . . . . . . . . . . . 4 3.3.1. Chemistry . . . . . . . . . . . . . . . . . 29
2. General Features of Major Textile 3.3.2. Fine Structure . . . . . . . . . . . . . . . 30
Fibers . . . . . . . . . . . . . . . . . . . . 4 3.3.3. PLA Fibers . . . . . . . . . . . . . . . . . 31
2.1. Chemical Forms . . . . . . . . . . . . . 4 3.4. Acrylic Fibers . . . . . . . . . . . . . . 31
2.2. Polymer Characterization . . . . . . 5 3.5. Other Polymers . . . . . . . . . . . . . 32
2.3. Other Chemical Constituents . . . . 6 4. High-Modulus, High-Tenacity
2.4. Fine Structure . . . . . . . . . . . . . . 7 Fibers . . . . . . . . . . . . . . . . . . . . 32
2.4.1. Characterization . . . . . . . . . . . . . 7 4.1. Glass . . . . . . . . . . . . . . . . . . . . 32
2.4.2. Models . . . . . . . . . . . . . . . . . . . 11 4.2. Highly Oriented Linear Polymers . 32
2.4.3. Unified Parametric Approach . . . . . 14
4.2.1. Aramid . . . . . . . . . . . . . . . . . . . 33
2.4.4. Relation to Fiber Properties . . . . . . 18
4.2.2. Polyethylene . . . . . . . . . . . . . . . . 33
2.4.5. Relation to Fiber Formation . . . . . . 19
4.2.3. Other Polymers . . . . . . . . . . . . . . 33
2.4.6. Structural Transitions . . . . . . . . . . 20
4.3. Carbon Fibers . . . . . . . . . . . . . . 34
2.5. Intermediate Structures . . . . . . . . 21
4.4. Ceramic and Other Inorganic Fibers 35
2.6. Gross Inhomogeneities . . . . . . . . 21
2.7. Fiber Shape . . . . . . . . . . . . . . . . 22 4.5. Structure and Properties . . . . . . . 35
2.7.1. Cross-sectional Shape . . . . . . . . . . 22 5. Other Fibers . . . . . . . . . . . . . . . 36
2.7.2. Axial Shape . . . . . . . . . . . . . . . . 23 5.1. High-Toughness Fibers . . . . . . . . 36
3. Particular Textile Fibers . . . . . . . 24 5.2. Elastomeric Fibers . . . . . . . . . . . 36
3.1. Cellulosic Fibers . . . . . . . . . . . . . 24 5.3. Thermally and Chemically
3.1.1. Chemistry . . . . . . . . . . . . . . . . . 24 Resistant Fibers . . . . . . . . . . . . . 37
3.1.2. Cotton . . . . . . . . . . . . . . . . . . . . 25 5.4. Special-Purpose Fibers . . . . . . . . 38
3.1.3. Other Plant Fibers . . . . . . . . . . . . 26 5.5. Nanofibers and Carbon Nanotubes 39
3.1.4. Rayon . . . . . . . . . . . . . . . . . . . . 26 5.6. Smart Fibers . . . . . . . . . . . . . . . 39
3.1.5. Acetate Fibers . . . . . . . . . . . . . . . 27 6. References . . . . . . . . . . . . . . . . . 40

1. Introduction dustrial circumstances of the formation of any

particular fiber type and, in turn, determines the
1.1. Fibers as Industrial Chemical physical and chemical properties of the fiber as
Structures well as its utility.
The Textile Institute [1] defines fibers as units
In two important senses, fibers are structures. of matter characterized by flexibility, fineness,
First, the definition of fibers as a particular form and high ratio of length to width. The geometri-
of matter depends on their gross structural size cal aspects of this definition are paramount be-
and shape. Second, they usually have a rich cause even an inherently stiff and brittle ceramic
complexity of internal structure at several lev- material is flexible in the fiber structural form
els, which is determined by the biological or in- and, at the other extreme, a flexible rubber rod is

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 477.pub2
2 Fibers, 2. Structure

not a fiber. To provide a convenient quantitative g/cm3 ) of the example. The use of the word fiber
marker in units commonly used in the man-made in other contexts may cover other sizes. Even
fiber industry, which can be converted to strict for fibers used in the textile industry, there are
SI units, a typical fiber may be taken to have the no precisely defined limits for the dimensions of
following dimensional parameters: what may be described without qualification as
Linear density 1 decitex (dtex)=10−7 kg/m a fiber. For the natural fibers, which have been
Length 1 cm used for thousands of years, and the first gen-
Density 1 g/cm3 eration of manufactured fibers, which together
account for the major usage of textile fibers, the
The International Organization for Standard- “three ones” are at the lower limit of fineness,
ization (ISO) has accepted tex, defined as grams length, and density. For these commercial fibers,
per kilometer, as a unit of linear density within the practical limits may be roughly given as fol-
the SI system. However, an older unit denier, de- lows.
fined as grams per 9000 m, was widely used in Fineness ranges from about 1 dtex (10−7
the silk and man-made fiber industries. This has kg/m) to 30 dtex (3 × 10−6 kg/m), giving diam-
led to the adoption of decitex (dtex) as a common eters up to about 50 µm. Anything much coarser
industrial unit. than the above limit of 30 dtex would be re-
Other derived parameters, if the fiber is as- ferred to as a thick monofil or bristle. From the
sumed to be a solid with a circular cross section, last quarter of the 20th century onward, there
are has been considerable interest in finer fibers.
Mass 1 µg Polyester microfibers are directly spun down
11.2 µm
to 0.1 dtex (10−8 kg/m) and finer still by us-
Diameter
Length-to-diameter ratio 1120
Surface area 0.351 mm2 ing special techniques, such as the islands-in-a-
Specific surface area 351 m2 /kg sea procedure, in which fine component fibers
are extruded within a removable, soluble matrix
The fineness of the structural division can be [2, 3]. Nanofibers, down to 10−7 dtex (10−14
demonstrated by noting that a small piece (1 m2 ) kg/m) can be made by electrospinning, in which
of a lightweight textile fabric (100 g/m2 ) would polymer melts or solutions are extruded in a
contain a hundred million such fibers. The other strong electric field [4]. Carbon nanotubes are
structural aspect of the definition, the high ratio now being directly spun and collected as yarns
of length to diameter, intensifies the situation [5, 6]. Other terms for finer fibers are ultrafiber,
since fibers can interact, mechanically or other- superfine fiber, fibril, and, for single crystals,
wise, within a structure wherever they cross, as whisker.
shown in Figure 1. Thus the essential fiber struc- The shortest fibers used in the regular tex-
tural element should be taken as having a length tile industry are about 1 cm in length, but
equal to its diameter. The above parameters give shorter fibers are used in papermaking and
the element a length of 10 µm and a mass of 1 in discontinuous-fiber composite reinforcement.
ng, or 1012 fiber elements per kilogram. The longest individual or staple fibers in com-
mercial use are about 10 cm in length; how-
ever, man-made continuous filaments, occasion-
ally produced as monofilament yarns but usually
as multifilament yarns or tows, are effectively in-
finite in length (they can always be made longer
by winding another turn on the package). The
natural “continuous filament,” namely silk, is
about 800 m in usable length.
Density depends on the material, but the
Figure 1. Zone of interaction between two fibers over a lightest common fiber material is polypropylene
distance approximately equal to the fiber diameter with a density of about 0.91 g/cm3 , depending
on crystallinity. Most common textile fibers have
The industrial situation is more complex than densities between 1 and 1.5 g/cm3 , but the newer
indicated by the “three ones” (1 dtex, 1 cm, 1 fibers such as carbon, glass, ceramic, and metal
 Fibers, 2. Structure 3

fibers, used in composites and other engineering a yarn, and yarns will be interlaced to make a
applications, have higher densities. fabric, which is the “material” used in the con-
The structural form, emphasized in the above struction of the final product. Both within the
discussion, is the basis for the industrial ex- fiber and in the arrangement of fibers in the as-
ploitation of fibers. The consequences of the sembly, the multiplicity of levels of structure,
structure manifest themselves in several dif- illustrated in Figure 2, can be exploited by the
ferent ways. Traditionally, the fiber form pro- designer to achieve the required function. In
vides the combination of flexibility and strength simpler materials, many of these choices dis-
needed in textile materials for clothing and for a appear, and some will be missing in various
range of household and industrial uses. In mod- fiber systems.
ern high-performance composites, the crack-
stopping characteristic provides the major ad-
vantage over bulk material. A second important
feature in clothing is the large volume of space
that can be trapped within a fiber assembly to
provide softness and warmth; this is also signif-
icant in filtration and other industrial uses. Re-
lated to this feature is the high accessible surface
area which is utilized in other applications. Con-
tinuity over long lengths is exploited by nature
in nerve fibers and industrially in optical fibers.
Networking deserves more exploration.
Finally, three fundamental, academic aspects
are also of great industrial relevance:
Figure 2. Levels of structure within a fiber and in an assem-
1) Large structural defects, which are a major bly of fibers as a useful product
source of weakness in bulk materials, cannot
occur in fibers. Any defect must be apprecia- Questions of yarn, fabric, or industrial com-
bly smaller than the fiber diameter. posite structure are beyond the scope of this ar-
2) Because fibers are so fine, their internal struc- ticle. The subject of fiber structure includes the
ture can be controlled in ways that cannot external form but concentrates within fibers on
be used for bulk materials. Even a poly- large-scale inhomogeneities (zonal differences),
meric fiber, with relatively poor thermal con- fine structure (molecular packing), and chemical
ductivity, can be heated and cooled at rates structure.
faster than 1000 ◦ C/s. Patterns of crystal-
lization, which would be impossible with
the slow cooling of large volumes, can thus 1.2. Structural Types
give forms of fine structure that can only be
found in fibers (or thin films). Metal fibers Within the increasing diversity of commercial
can be quenched at rates that result in crys- fiber types, the most useful structural classifica-
talline (amorphous) glassy metals. Similar tion is based on the use of the fiber. The follow-
arguments apply to chemical changes, with ing categories are defined and treated separately
fast diffusion through the fiber, and mechan- in the following sections of this article: general-
ical stresses. Thus, the chemical, thermal, purpose textile fibers, high-stiffness fibers, and
and mechanical conditions that determine the special-purpose fibers.
form of fine structure can, in principle and
General-Purpose Textile Fibers For ordi-
to a considerable degree in practice, be con-
nary textile usage, a material is needed which
trolled to a precise sequence, with minimum
can be produced in fiber form; has reasonable
gradients disturbing the structure formation.
mechanical, thermal, and chemical stability, and
3) The third aspect relates to fibers in systems. In
can be colored by dyeing. However, the most re-
use, the fiber is a component in an assembly.
strictive feature in terms of structural possibili-
Typically, a collection of fibers will make up
ties is that the fiber must have intermediate elas-
4 Fibers, 2. Structure

tic extensibility, with a breaking extension bet- than the estimated size of the micelles; this led
ween 5 and 50 % (usually between 10 and 30 % to the fringed micelle model in which the linear
), as well as appreciable recovery from exten- polymer molecules run continuously between
sions near break. This rules out as too inexten- crystalline micelles and the disordered regions.
sible the common brittle materials such as crys- In the 1950s, the simple view was challenged in
tals and glasses, and ductile materials such as three ways: (1) by electron microscope studies
metals; elastomeric rubbers are ruled out as too which showed the presence of fibrils as a basic
extensible. The only class of material structure structural unit in many types of fiber; (2) by new
that meets this requirement consists of partially ideas coming from fundamental studies of poly-
oriented, partially crystalline, linear polymers. mer crystallization, in particular, chainfolding in
High-Stiffness Fibers The new high- polymer single crystals and spherulitic growth in
performance fibers used in advanced composites bulk crystallization; (3) by new thinking about
have more diversity of structure. The forms are the meaning of order and disorder. Some unify-
ing ideas have been proposed, but possibly the
1) very highly oriented, highly crystalline linear
most important point is that different fibers have
polymers;
different structures, so one can be specific only
2) the graphitic, irregular, two-dimensional crys-
in relation to particular cases.
talline form of carbon fibers;
The early development of ideas of fine struc-
3) glass and ceramic structures; and
ture of fibers was reviewed in [9, Chapter 6],
4) crystalline forms.
which also contains more detailed information
Special-Purpose Fibers Fibers for special on many fiber types; this reference was brought
purposes have an even greater diversity of struc- up to date in 1970 in [10]. The understand-
ture, because a variety of materials can be made ing and control of fiber structure is reviewed in
in fiber form when the incentive to exploit partic- [11], which covers both natural and manufac-
ular physical or chemical properties is present. tured fibers and introduces ideas from the sci-
Some of the more important materials are men- ence of complexity, including polymer dynam-
tioned in the Section 5.4. ics, fractals, kinetics of nonhomogeneous pro-
cesses, nonlinear systems, chaos, and the possi-
bility that fiber formation involves quantum ef-
1.3. Development of Knowledge of Fiber fects. Other books and reviews concerned with
Structure various aspects of fiber science and technol-
ogy also include information on fiber structure
Textile fibers were used for thousands of years [12 – 31].
before their structure was studied. During the
first half of the 20th century, many studies by
optical microscopy provided information on the 2. General Features of Major Textile
gross structural features. Much information on a
wide range of fibers is contained in [7] and [8]. Fibers
Only in the 1920s was the polymer
(macromolecular) hypothesis established; it was 2.1. Chemical Forms
also recognized at that time that the natural plant
fibers and regenerated rayons were composed of This section is particularly concerned with the
the linear macromolecule, cellulose and that nat- major textile fibers, which are discussed indi-
ural animal fibers were composed of macromo- vidually in Chapter 3, although the investigative
lecular proteins. This development coincided techniques and some of the general comments
with the first X-ray diffraction studies of fibers, are also applicable to the specialist fibers co-
which demonstrated a combination of ordered vered in later sections. Of the many linear poly-
and disordered material within the fiber. This mers which have been synthesized in the lab-
was first interpreted as a dispersion of separate oratory or occur in nature, these major textile
crystalline micelles within an amorphous ma- fibers of the 20th century consisted of only six
trix. However, in the early 1930s the molecu- basic chemical types. These fibers are listed in
lar length was recognized as being much greater
 Fibers, 2. Structure 5

Table 1, together with some less important ones. as in the aromatic polyesters and aramids, then
Others polymers have been tried for general tex- the melting point becomes too high, with decom-
tile use, and some may still be used in small position occurring first, and the materials are too
quantities. In 2002, the Federal Trade Commis- stiff and intractable for general textile use. How-
sion recognized a new generic fiber type: PLA, ever, the ability of these polymers to form liquid
which is manufactured from poly(lactic acid) or crystals can be utilized to make high-modulus,
poly(lactate) derived from naturally occurring high-tenacity (HM–HT) fibers.
sugars or starch. The commercial fiber has the The other synthetic route to obtain useful
trade name NatureWorks. fibers by modifying the polyethylene molecule is
to add side groups, which either are interactive,
Table 1. Polymers in textile fibers such as the polar −C≡N groups in polyacryloni-
Class Large-volume Small-scale
trile and the hydrogen-bonding −OH groups in
production or experimental poly(vinyl alcohol), or act like the −CH3 groups
production in polypropylene and cause the chain to form
1 Cellulosic cellulose
a coil with greater flexural rigidity. In nature,
secondary cellulose cellulose triacetate more complicated forms occur, such as cellu-
acetate lose which contains a stiff ring and hydrogen-
2 Protein keratin in wool fibroin in silk
bonding −OH groups, and proteins which have
3 Polyamide nylon 6 nylon 4, nylon 7,
nylon 66 and others a variety of possible interactions.
4 Polyester poly(ethylene poly(butylene Although the chemical structure of the syn-
terephthalate) terephthalate) thetic polymer fibers thus seems simple, com-
poly(trimethylene
terephthalate), plexity can be introduced through copolymeri-
poly(ethylene zation. End groups must, of course, be present,
naphthalate), and
others
but other groups can be introduced to improve
5 Vinyl/Acrylic polyacrylonitrile poly(vinyl alcohol), or modify dye affinity or to give other special
poly(vinyl chloride), effects. This is done in specialty polyamide and
modacrylic and others
6 Polyolefin polypropylene polyethylene
polyester fibers to give deep-dyeing effects or
a selective attraction for particular classes of
The desirable features of the polymer dyes. Copolymerization is always carried out on
molecule are (1) it should be regular in order to acrylic fibers, since pure polyacrylonitrile can-
form a crystal lattice, and (2) the stiffness of the not be dyed; thus, considerable diversity exists
chains and the interaction between them should in the chemical composition of acrylic fibers
be high enough to give stability to the crystal, but from different manufacturers, which have dif-
not so stiff as to cause difficulty in formation or ferent trade names, or of different types hav-
excessive rigidity in the fiber. The principles of ing the same main trade name. The modacrylics
selection are illustrated in Table 2 by the various are a more extreme example of copolymeriza-
combinations of four simple groups in repeating tion, containing less than 85 % acrylonitrile and
polymer units. Chains composed only of methy- adapted to give improved flame resistance or
lene (−CH2 −) and ester (−COO−) groups are other special properties.
too inert and flexible to give a high enough
melting point. However, inclusion of the amide
(−CONH−) group, which interacts by hydrogen 2.2. Polymer Characterization
bonding, or of the rigid and electronically inter-
active benzene ring results in commercially suc- In addition to their chemical composition, the
cessful polyamide and polyester materials. Nev- physical form of polymer molecules must be
ertheless, these chains still contain sequences of characterized. With the exception of keratin,
−CH2 − and −COO−, which provide enough which is a complex protein system, the chains
flexibility. Experiments with other polyamides are normally linear with little branching or cross-
and polyesters suggest that six is about the right linking, although cellulose fibers may be cross-
number of main-chain atoms to form such a se- linked by resin treatment of textile fabric to im-
quence. If the flexible sequences are eliminated part crease resistance.
6 Fibers, 2. Structure
Table 2. Various polymer forms

The most important parameters are thus the 2.3. Other Chemical Constituents
degree of polymerization (chain length) and its
distribution. Generally, the longer the chains, the Impurities. In addition to the polymer con-
greater is the fiber strength. However, the max- tent, fibers usually contain within their struc-
imum degree of polymerization is limited by ture appreciable amounts of other substances.
the conditions of formation. In the natural plant In cotton, these include salts and other minor
fibers, biosynthesis within the cell enables a very impurities, but in some plant fibers hemicellu-
high degree of polymerization to be obtained. loses and lignin may also be present in signifi-
However, in the production of rayon fibers the cant amounts. Wool contains various biological
mechanical and chemical attack necessary to get residues, and man-made fibers may contain cat-
cellulose into solution, inevitably reduces the de- alytic residues, low molecular mass analogues
gree of polymerization. Considerable improve- such as dimers and trimers, and other manu-
ment in properties can be achieved by attention facturing contaminants. All of these substances
to detail, so that a high degree of polymerization may be classed as impurities.
is obtained. The elimination of low molecular Pigments and Antistatic Agents. Some other
mass fractions from the distribution is partic- constituents are deliberately introduced. Tita-
ularly advantageous. With synthetic polymers, nium dioxide particles are commonly added to
the attainable degree of polymerization depends man-made fibers as a delusterant, which gives
on the polymerization chemistry: addition poly- a more matt appearance to fabric and increases
mers are generally able to reach high values, but opacity. Carbon black or colored pigments may
condensation polymers are limited by the reac- be added to give a range of “spun-dyed” fibers.
tion equilibrium. Such components are finely distributed within
Although, for ultimate properties, a high de- the fiber, but continuous strands of carbon or
gree of polymerization is desirable, this cannot a colorless conducting polymer may be intro-
be carried too far because the viscosity of the duced to give antistatic fibers.
melt or solution will be too high for extrusion in Water. Most of the polymers used in fibers ab-
spinning. sorb water, which is dispersed within the struc-
The average degree of polymerization may be ture. At an intermediate humidity of 65 %, this
found by standard techniques with measurement gives a moisture content of about 13 % in wool
of viscosity or chemical end-group analysis be- and rayon, 7 % in cotton, 6 % in secondary
ing the most common. In particular cases, char- acetate, 4 % in triacetate and nylon, 1.5 % in
acterization of tacticity, or the form of copoly- acrylic, and 0.5 % in polyester fibers; at satu-
merization, whether random, block, or graft, ration, without liquid water being present, some
may also be useful.
 Fibers, 2. Structure 7

fibers may absorb their own mass of water, giv- to structures found in other forms of the mate-
ing a moisture regain of 100 % or a moisture con- rial, and results from the interaction of physical
tent of 50 % based on total mass. The water will chemistry with the biological or industrial cir-
be absorbed predominantly in the noncrystalline cumstances of fiber formation. This discussion
regions of the fiber structure or on the surfaces is concerned with how the polymer molecules
of crystallites. The absorption may be divided pack together and involves the range from 1 to
between those water molecules that are located 100 nm (10 to 1000 Å).
directly on active moisture-absorbing groups in The linear polymer molecules in all general-
the polymer (particularly −OH and −CONH− purpose textile fibers are oriented preferentially
groups) and those that form secondary layers parallel to the fiber axis to a degree which gives
on top of the directly absorbed molecules. Be- high anisotropy but is well short of perfect orien-
cause of its effects on dimensional swelling, heat tation. The molecules are ordered to about mid-
of absorption, mechanical properties, diffusion way between the perfect order of a crystal lattice
within the fiber, thermal transitions, electrical and the extreme disorder of an amorphous lin-
conductivity, and other properties, moisture is ear polymer, e.g., rubber or glass. The problem
an important element in the structure of many of characterizing fiber structure then has two as-
fibers. pects: (1) a qualitative description of the struc-
Waxes, Lubricants, and Surface Finishes. Fi- tural form which, while still being partially ori-
nally, other substances are commonly present on ented and partially crystalline, can include many
the surface of fibers. Natural fibers, as formed, different models; and (2) establishment of the
contain oils and waxes, which are usually re- numerical values of relevant parameters, which
moved at some stage of chemical processing. may be general and relate to many structural
However, in the production of man-made fibers models or may be specific to a particular struc-
and at various stages in the textile processing tural concept.
of all types of fiber, surface finishes are nor- Although various techniques provide infor-
mally added to change the frictional properties mation relevant to an understanding of fiber
of the fibers, usually to lubricate but sometimes structure, they are all limited in what they pro-
to increase friction; frequently, to control static vide and subject to artefacts, experimental er-
electricity; or for special purposes, e.g., to in- ror, and uncertainty of interpretation. Substan-
fluence other properties such as wettability. The tial, unambiguous information about fiber struc-
constitution of these surface components, which ture cannot be obtained from any single tech-
typically add 1 – 3 % to the total mass, is very nique. One special danger is that if some par-
complicated; they may contain a variety of natu- ticular form of model is assumed, experimental
ral oils, synthetic lubricants, industrial surface- measurement may lead to a precise calculation
active agents, and other substances. Little infor- of some parameter of that model. This will then
mation has been published on this subject, but a reinforce faith in the model; yet if another model
review presents some information from patents has been used as a starting-point, it too could be
[43]. fitted to the experimental results with equal pre-
cision. The approach to understanding is thus a
matter of integrating a diverse set of data from a
2.4. Fine Structure variety of sources into a coherent unity. For some
natural fibers, this has been achieved with con-
2.4.1. Characterization fidence in the results; but for man-made fibers,
a clear picture still does not exist.
The level immediately above the molecules is The analytical techniques that provide al-
the most specialized and significant aspect of most all the information on fiber fine structure
fiber structure in the context of industrial chem- have been used for at least 40 years. Recent ad-
istry. Polymerization chemistry and the use of vances have occurred through some variation of
polymers in other applications are discussed methods, more powerful instrumentation, and
elsewhere. The larger scale features are more a — most important — the use of digital methods
matter of engineering. However, the fine struc- to collect data and computers to analyze data.
ture is characteristic of fibers, is rarely similar
8 Fibers, 2. Structure

Degree of Crystallinity. If the fine structure the interface regions between crystal and amor-
is assumed to be a mixture of crystalline and phous material constitute a substantial part of
amorphous material, the degree of crystallinity the whole, and the densities in these regions are
can be determined in various ways. If the density likely to be different.
of the crystalline material is c , of amorphous Finally, this whole discussion of degree of
material a , and of the fiber , then the degree of crystallinity is based on a tacit assumption that
crystallinity δ cv is the volume fraction of crys- the fiber can be regarded as a two-phase mixture
talline material given by of a crystalline component and an amorphous
component, typically represented by a model of
δcv = (−a ) / (c −a ) (1)
crystalline micelles embedded in an amorphous
The fiber density can be determined most eas- matrix. However, the reality may be a more com-
ily in a density gradient tube containing a mix- plicated distribution of intermediate degrees of
ture of two liquids, graded so that the proportion order or, at the other extreme, a completely uni-
of dense liquid increases from top to bottom of form, partially ordered, structure.
the tube, and calibrated by particles of known The problems arising from the application of
density. Experimental errors may be associated Equation (1), which appears to be a very simple
with such factors as absorbed water in the fibers, statement about fine structure, are discussed here
absorption of the test liquids, entrapment of air, at length because they also illustrate the nature
and the presence of voids within the fiber. Usu- of the uncertainties that arise in other techniques
ally, the dimensions of the crystal unit cell of for investigating structure, which will be dealt
the polymer are known accurately from X-ray with more briefly. The difficulties of interpreta-
diffraction studies, not necessarily on fibers, and tion in relation to models apply universally, but
the mass in the unit cell is known from the chem- many of the more specialized techniques, while
ical composition, so that c is known, although potentially yielding more detailed structural in-
even here values are being challenged and re- formation, are subject to greater errors through
vised. If the polymer can be quenched to an artifacts of specimen preparation and problems
amorphous glassy state, then a direct measure- of interpreting data.
ment of a can be made; otherwise, a value must An alternative definition of the degree of crys-
be estimated by some form of extrapolation. tallinity exists, namely, the mass fraction of crys-
At best, there is some uncertainty about the talline material:
true values of , c , and a ; but the reality is
cm = (Va −V ) / (Va −Vc ) (2)
worse. The best estimate of c is for a unit cell
within a large, perfect, unstrained crystal. Within where V, V a , and V c are the specific volumes,
the fiber, the crystals are very small, may con- which are reciprocals of the respective density.
tain imperfections, and are strained by the pull Since the difference in densities is not large, the
of connecting chains; each of these factors af- two quantities will not differ greatly.
fects the density. Defining the true value of a is Although one must be very cautious about a
even more difficult, because highly disordered precise and absolute interpretation of the degree
structures may be packed with different degrees of crystallinity, the fractions defined in Equa-
of efficiency. Aging of an amorphous structure tions (1) and (2) provide a scale of degree of
enables the thermal vibrations to shake the struc- order in fibers, from poorly ordered to highly
ture down into tighter packing in a more favor- ordered, even if the scale is arbitrary and em-
able energy state. Furthermore, when a direct pirical. This interpretation would only be upset
measure of amorphous density is available, (e.g., in highly exceptional circumstances (e.g., in ice
from a rapidly cooled polyester fiber), it is on a and water) where the ordered crystal lattice had
volume of material which is large in comparison a lower density than the disordered arrangement.
to molecular dimensions and involves the dubi- Other physical and chemical measurements
ous assumption that small regions of disordered can be used to define the degree of order (degree
chains, which connect crystallites by lengths of of crystallinity) by equations analogous to (1)
about ten repeating units, would have the same and (2). These include refractive index, which is
density as the bulk amorphous material. Also, proportional to density; moisture take-up, which
because the scale of fine structure is so small, occurs within amorphous regions but usually not
 Fibers, 2. Structure 9

within crystalline regions, although absorption around this axis, leads to the reflections from par-
will occur on crystal surfaces; other absorp- ticular lattice spacings appearing on layer lines,
tion techniques; and latent heat of melting, al- with the separate orders at increasing distance
though here the fraction would equal the ratio from the meridian. Real textile fibers give pat-
of fiber latent heat to crystal latent heat (L/L c ), terns of the form indicated in Figure 3B (a). The
because of the assumption that the amorphous first-order reflections are easily seen, but higher
material does not contribute. Other techniques orders are usually very faint. The sharp spots are
exist in which the responses X c and X a from diffused, and more general scattering occurs in
the crystalline and amorphous materials can be the form of a halo from disordered material.
separated, so that the relevant fraction becomes The relation between various features of the
X c /(X c + X a ). Such techniques include X-ray X-ray diffraction pattern and structure is as fol-
diffraction, electron diffraction, infrared absorp- lows:
tion, NMR and Raman spectrometry. However, 1) Location of spots: size and shape of unit cell;
the problem here is that the two responses over- arrangement of atoms in crystal lattice
lap, so the separation of X c and X a is uncertain. 2) Radial broadening of spots: increasing with
Provided any errors of experimentation or in- reduced size and perfection of crystals
terpretation directly associated with the tech- 3) Circumferential spread into arcs: decreasing
niques have been eliminated, all the above meth- orientation of crystals
ods give the same value of the degree of crys- 4) Ratio of sharp spots to diffuse scattering: de-
tallinity for a simple model of large crystals dis- gree of crystallinity
persed in amorphous material (like a mixture of
crystals and liquid in an organic compound at the
melting point). However, when the real structure
is not defined so simply, the results will differ be-
cause each technique will be defining a different
scale of the degree of order.
X-Ray Diffraction. One of the most useful
techniques for studying fiber structure is wide-
angle X-ray diffraction, in which a beam of
X-rays is passed through a bundle of parallel
fibers. Specialists should be consulted about the
minimization of errors associated with the X-
ray source and its collimation, specimen prepa-
ration, the method and geometry of detection
(photographic film or solid-state detection), and
the extraction and interpretation of quantitative
data. Because of the inverse form of Bragg’s law,
sinθ = nλ/2d (where θ is the angle of a strong
reflection from a crystal lattice, n is an integer
defining the order of the diffraction, λ is the X-
ray wavelength, and d is the crystal lattice spac-
ing), wide-angle scattering (WAXS) gives infor-
mation at the level of atomic spacing, whereas Figure 3. A: Perfectly crystalline fiber; B: Typical fiber
a) Simplified representations of wide-angle X-ray diffrac-
small-angle scattering (SAXS), which requires a tion patterns; b) Radial scans of intensity I against an in-
different instrument, gives information on larger terval of radius r, showing peaks broadened to a half-width
scale structural features. w, superimposed on an amorphous background A; c) Scans
A perfectly crystalline, perfectly oriented along a circumferential arc of intensity I against polar angle
φ, showing broadening 2 θ resulting from range of orienta-
fiber would give a wide-angle X-ray diffraction tion
pattern of the form shown in Figure 3A (a). The
symmetry of crystals oriented parallel to a sin- In Figure 3 (b) and (c) is illustrated how quan-
gle axial direction, but with random orientation titative parameters can be determined roughly,
10 Fibers, 2. Structure

but much more detailed analysis is needed to to distinguish different areas of a cross section
get precise measures. In principle, the complete and different directions in the fiber.
X-ray scattering contains information from the Other Microscopy Techniques. Since its
complete pattern of packing within the fibers, introduction in the 1960s, scanning electron
including the size, shape, and perfection of the microscopy (SEM) has been used to study the
crystals and statistical features of the amorphous overall form of fibers, and, particularly, the de-
material. The problem is to devise analytical tails of fiber fractures [45]. Recent advances in
schemes to extract this information without mis- high-resolution imaging enable finer structural
interpretation. details down to 1 nm or less to be examined
The small-angle X-ray scattering pattern con- [46].
sists of diffuse spots from which an indication Atomic force microscopy is being used to in-
of long spacings within the fine structure can be vestigate coarser features of fiber structure, such
obtained. as the cell structure in wool, and to measure the
The techniques continue to advance. Digital mechanical properties of individual structural
collection of data and computational analysis in- components. Refinements of the technique are
crease the useful information which can be gen- likely to improve resolution.
erated. The use of intense synchrotron sources Due to limits on resolution and contrast, it is
of X-rays enables information to be obtained in not possible to obtain much information about
much shorter times and allows dynamic studies the internal structure of fibers by conventional
of structure development in a threadline to be optical microscopy. However, the development
performed. of confocal light microscopy now allows coarser
Electron Microscopy. Transmission elec- features, such as the cells in wool, to be ob-
tron microscopy is another source of infor- served. In this technique a small spot of light is
mation, which has proved particularly useful scanned across the specimen at different depths.
where there are well-defined structural units. The resultant reflected or fluorescent light is
Thus the cellulose in cell walls can be shown picked up on a detector and gives images of suc-
to be in the form of fine fibrils, either by dis- cessive cross sections of a fiber.
integration or by taking surface replicas (→ Infrared Spectrometry. Infrared spectrom-
Cellulose); and in wool, transverse and longitu- etry can be used to detect the presence of par-
dinal sections can be cut and stained, and clearly ticular chemical groups, but its relevance to fine
show a fibril – matrix composite structure, with structure results from the fact that the absorp-
dimensions that can be measured (→ Wool). tion frequency changes with the environment of
However, these simple statements hide the great the group. Degree of order can be determined by
skill and care needed to extract useful and re- separating the bonds associated with crystalline
liable information. In man-made fibers, where and amorphous materials. A difference also ex-
the structure is less well-defined, information ists between cis and trans configurations, and
is more difficult to extract, but new techniques crystallographic chain folds may give a charac-
of high-resolution electron microscopy on thin teristic shift. Other information can be inferred
sections show promise. A particularly promis- from the change of frequency with the state of
ing technique is the use of high-voltage electron strain of a fiber. The use of polarized infrared
microscopy on thick sections. By tipping the radiation can yield data on orientation of ab-
specimen, information of the three-dimensional sorbing groups in the material. Infrared absorp-
structure can be obtained and shown by tomog- tion, particularly with high-speed Fourier trans-
raphy. This method has been used by Bryson form techniques, has been very useful in poly-
et al. [44] to determine the helical angles in mer studies, but problems of suitable arrange-
macrofibrils in wool. ment have limited its value in studies of fibers.
Electron Diffraction. Electron diffraction Raman spectrometry. In its simplest form,
generates the same sort of information as X-ray Raman spectroscopy gives information similar
diffraction, but because it is carried out with a to infra-red spectroscopy. However its value has
minute beam on a thin specimen, it can be used been transformed by the introduction of the Ren-
ishaw Raman microscope. Now, in addition to
 Fibers, 2. Structure 11

detecting local differences in molecular envi- Other Sources of Information. In addition

ronments, the shift in bonds can be calibrated to the analytical techniques, two other impor-
to determine molecular strains. tant sources can be used to understand fiber
Nuclear Magnetic Resonance Spectrome- fine structure. The first is a consideration of the
try. Another major analytical technique used to way in which the molecules would be expected
a small extent to obtain information on fibers is to behave under the conditions of fiber forma-
nuclear magnetic resonance. Statton [47] pio- tion. This involves an application of knowledge
neered the use of wide-line NMR, which relates of the movement and deformation of polymer
to mobility of molecular segments within a fiber molecules and of polymer crystallization, and
structure, but the method has not been used much varies with the chemical constitution of the poly-
since his work. mer.
The second is the relation between structure
Refractometry. Use of the refractive index and various physical and chemical properties.
as a measure of density has been mentioned, but For example, a difference in appearance after
the most important use of an optical technique is dyeing is perhaps the most sensitive way of de-
the determination of birefringence as a measure tecting a structural change, but this cannot be
of orientation. This is one of the most straight- interpreted easily. The range of properties re-
forward methods since, apart from any errors re- lated to structure includes diffusion and acces-
sulting from form birefringence, the difference sibility; mechanical and thermomechanical re-
between the refractive index n1 for light polar- sponses, particularly dynamic modulus studies;
ized parallel to the fiber axis and n2 for light electrical properties; and others. Attempts to ex-
polarized perpendicular to the axis is directly plain these properties lead circumstantially to
related to the orientation of groups contributing views about fine structure. Most certainly, if a
to the dipole moment. The Herman’s orientation particular structural model gives good predic-
function f, defined below in terms of n1 and n2 , tions of properties without the use of adjustable
is related to the average angle of inclination of parameters, this is strong evidence in support of
molecular segments, φ: the model.
f = (n1 −n2 )/(n
1 −n
2 ) = 1−3sin2 φ/2 (3)

where n1 and n2

refer to a perfectly oriented 2.4.2. Models
fiber.
The orientation determined in this way relates The first widely used model of textile fiber fine
to the whole fiber, whereas the crystal orienta- structure was the fringed micelle model, illus-
tion is given by X-ray diffraction. The average trated in Figure 4. This model reconciled the
amorphous orientation can be calculated from indications of the presence of both crystalline
the other two values. and amorphous regions with the great length of
the chain molecules by postulating that a given
Dichroism. Dichroism, including fluores- molecule fringed in and out of the crystalline
cence methods, is another optical technique for micelles. In fibers, as distinct from unoriented
determining orientation. Other structural infor- polymer forms, the orientation was assumed to
mation can be inferred from light scattering. be preferentially parallel to the fiber axis. This
Thermal Analysis. The use of latent heat as model was plausible because it might be ex-
a measure of crystallinity has been mentioned, pected to occur if crystallization started at many
but the complete differential scanning calorime- places within the fiber. Furthermore, it gave rea-
try (DSC) or differential thermal analysis (DTA) sonable explanations of many fiber properties.
response contains more information. The pres- When chain folding in polymer crystals was
ence of multiple endotherms indicates the exis- discovered, a modified fringed micelle structure
tence of different structures, with the more sta- was suggested (Fig. 5). This model shows a mix-
ble forms, such as larger crystals, melting at the ture of chain folding and fringing at the edge of
higher temperatures. Generally, any endotherm each micelle, and recognizes that relatively high
or exotherm is an indication of some structural degrees of crystallinity, such as 50 %, can only
change. be accommodated if the micelles are regularly
12 Fibers, 2. Structure

stacked in a pseudofibrillar array. If required by Characterizations such as Figures 4 and 5 are

the crystal lattice, the ends of the micelle will be not explicit theories of structure. They are in-
angled. Models of this sort, proposed by various adequate pictorial representations of poorly de-
scientists, remain the best working models for fined views of structure. They do not attempt
some types of fiber. to be quantitative in terms of size, shape, and
spacing of crystalline regions or of molecular
paths in amorphous regions. Differences in re-
presentation by different authors reflect artistic
skill and temperament more than scientific in-
tention, as well as the limitations imposed by
size and a two-dimensional format.
An attempt by Murthy et al [50] to give a
more quantitative picture of the structure of a
nylon 6 fiber on the basis of SAXS and WAXD
data is shown in Figure 6. The main features of
Figure 5 can be seen, but with more irregularity
in the structure.

Figure 4. Fringed micelle model, as drawn by Hearle [48]

Figure 6. The structure of a nylon 6 fiber, as envisaged by

Murthy et al [50] on the basis of SAXS and WAXD data.
1) Fibrils; 2) Lamellae; 3) Partially extended chains in the
interfibrillar regions; 4) Tie molecules in the interlamellar
regions; 5) Free chain ends; 6) Amorphous segments with
large free volume, which may give rise to voids; 7) Fusion
of adjacent microfibrils. Shaded areas represent the inter-
fibrillar amorphous regions.

In some fibers, evidence suggested that the

Figure 5. Modified fringed micelle model, as drawn by
Hearle [49] crystals might be in the form of long fibrils, and
this led to the suggestion of a fringed fibril struc-
 Fibers, 2. Structure 13

ture (Fig. 7). Fringed lamellar forms, (Fig. 8) are crystallinity exists, at least in some types of fiber,
also possible, but they are more likely to occur and that the structure is amorphous, with a de-
in bulk polymers than in fibers. gree of order introduced by some correlation
between the positions of neighboring molecu-
lar segments.

Figure 7. Fringed fibril structure, as drawn by Hearle [51]

All these models are two-phase structures in

which crystalline and amorphous regions are Figure 9. Dynamic crystalline gel model in oriented fiber,
as drawn by Hearle [10]
clearly differentiated. A radically different ap-
proach is to propose a uniform one-phase struc-
ture of intermediate form. Hosemann [53] in- Adopting a somewhat more localized view,
vestigated the paracrystalline structure in which Reneker [55] has explored the explanation of
the disorder results from a statistical deviation disorder as the result of particular forms of
from the true lattice spacings: this maintains an crystal defect, somewhat analogous to disloca-
approximation to short-range order, but means tions in metals; this is probably a useful re-
that there is no long-range order. Kargin [54], presentation for polyethylene and other chains
from the other direction, suggested that no real with short repeating units. On the other hand,

Figure 8. Fringed lamellar structure, as drawn by Hearle [52]

14 Fibers, 2. Structure

Figure 10. A: Schematic representation of examples of degree of order from amorphous (zero) to the perfect crystal (one); B:
Distributions with different degrees of localization of order
a) Uniform at degree of order of 0.5 (zero localization); b) Perfect crystal plus amorphous (maximum localization);
c) Hypothetical distribution with all degrees equally represented; d) Mixture of high and low order (moderate localization)

Hearle [56], following a thermodynamic con- partially correlated disorder, with the possibil-
sideration of multiple melting in nylon and ity of localized defects in the crystal or localized
polyester fibers, has suggested a dynamic crys- segments in register in the amorphous part, al-
talline gel in which small molecular segments though such a description is too general to add
are in register throughout the material, as illus- much understanding.
trated in Figure 9.
According to another view, amorphous ma-
terial as such might not be present, but the struc- 2.4.3. Unified Parametric Approach
ture may be an assembly of fine crystalline fibrils
with disorder coming from imperfections in the An alternative way of dealing with the problem
packing of the fibrils. The density, for instance, is to try to define a set of parameters that are gen-
would be reduced by the space between fibrils. erally applicable and describe important aspects
Considerable conflict and diversity of view of structure.
about fiber fine structure appear to exist, but two A perfectly crystalline material can be de-
important points must be remembered: (1) dif- scribed by a limited number of coordinates in
ferent fibers have different structures, so differ- a crystal lattice, and a highly amorphous ma-
ent choices of model will give the best repre- terial by a limited number of statistical parame-
sentation for particular fibers; (2) real structures ters. Structures of intermediate order can only be
are likely to be much more complicated than truly described by specifying the location of ev-
the models, which are usually simplified to an ery molecular segment in a region large enough
extreme in an attempt to clarify understanding. to be typical of the whole. This would lead to a
Real fibers are likely to show features from sev- set of parameters approaching Avogadro’s num-
eral models. All the structures can be represented ber, so that one would have to be highly selective
as a distribution of paracrystals in a matrix of in choosing a reduced set!
 Fibers, 2. Structure 15

The most useful parameters appear to be the

following:
1) Degree of order
2) Degree of localization of order
3) Aspect (length-to-width) ratio of crystalline
units
4) Degree of orientation
5) Size of crystalline units
6) Molecular extent
The idea of order is discussed above in re-
lation to measurement of “crystallinity.” Theo-
retically, a degree of order could be defined as
a parameter based on statistical correlation bet-
ween vectors representing neighboring molec-
ular segments. In a perfect crystal, the vectors
would be perfectly correlated in location and di-
rection; at maximum disorder, there would be
no correlation. Practically, a scale of degree of
order can be defined by density or some other
measurable quantity. In a uniform structure, the
degree of order can vary continuously between
the two extremes as illustrated in Figure 10A.
The idea of localization of order is then il-
lustrated by Figure 10B. An average degree of
order at some intermediate value, say 0.5, can
be given by many different distributions. At one
Figure 11. Shapes of crystalline regions of varying aspect
extreme (a), the whole material can be uniform, ratio, decreasing from top to bottom
with zero localization of order. At the other ex-
treme (b), the structure may be completely local-
The different models of structure described
ized with perfect crystals embedded in a wholly
in Section 2.4.2 can then be located on a three-
amorphous matrix. Another form (c), at an in-
dimensional plot, as shown in Figure 12. How-
termediate degree of localization, would have
ever, different models, with subtle differences in
equal regions of all degrees of order. These sim-
molecular packing, can occupy the same place in
ple idealized forms are unlikely to occur in real
the diagram, and a continuous range of structures
fibers; the most common form is likely to be
exist, which merge imperceptibly from one form
some variant of (d), namely, imperfect crystals
to another. The named models are idealizations
mixed with varied disordered material, but cer-
which lead to simple description. Figure 13 in-
tain fibers do tend more to the extremes of very
dicates where different types of fibers lie on such
high localization or complete uniformity.
a plot. The justification for the location, and the
The aspect ratio, or ratio of length to width, is
uncertainty, will become apparent in later sec-
a measure of the shape of the crystalline regions
tions dealing with particular fibers.
(with the assumption that the localized units are
Fortunately, the three parameters plotted are
the highly ordered parts dispersed within a dis-
enough to describe the essential character of a
ordered matrix). This can range from infinity
structure. The other features can be regarded as
to one, through fibrils of great length, limited
superimposed on the basic form.
length, and elongated micelles, and then from
one to zero through short, wide micelles, lamel-
lae of limited width, and very wide lamellae, as
illustrated in Figure 11.
16 Fibers, 2. Structure

orientation of individual molecular segments,

and easily measured. Crystallite orientation is
simply related to the distribution of crystal axis
angles, such as those shown in Figure 4, relative
to the fiber axis. In natural fibers, as discussed
below, genetically controlled mechanisms lead
to helical forms of orientation. For melt-spun
fibers, such as nylon and polyester, it is not acci-
dental that Figures 5 and 6 show perfect crystal-
lite orientation. Orientation is induced by draw-
ing with a typical draw ratio of 4:1. The combi-
nation of high draw and a crystallinity of around
50%, which implies that in each 3D direction
the spacing between the micellar crystals is, on
Figure 12. Representation of models of structure on a average, one sixth of the crystallite dimensions,
three-dimensional plot with axes (1) degree of order, (2) means that a very high degree of crystallite ori-
degree of localization of order, (3) aspect ratio of localized entation is inevitable. Amorphous orientation is
units
Forms are: a) Wholly amorphous; b) Amorphous
given by the distribution of angles of molecu-
with correlation; c) Paracrystalline; d) Perfect crystal; lar segments. Earlier drawings, such as Figures
e) Amorphous with varying correlation; f) Crystalline with 4 and 5, tend to show an almost random distri-
distributed defects; g) Networks of regions of high and bution of angles, but the more specific model
low order; h) Crystalline with concentrations of defects;
i) Fringed fibril; j) Fringed micelle; k) Fringed lamellar
of Figure 6 shows a fairly high degree of amor-
phous orientation. In wholly amorphous poly-
mers, such as rubbers, orientation of molecular
segments occurs during stretching and can be set
by cooling below the glass transition tempera-
ture, only to be released on heating. In the melt-
spun fibers the orientation is induced by the draw
tension and the driving force that pulls molecu-
lar segments into crystallites. On release of the
draw tension, the geometrical constraints of the
structure limit the extent to which de-orientation
of molecular segments in the amorphous regions
is possible.
The size of the crystalline regions in any of
the structures can range from small to large. The
structure may have a fine texture, with small
crystallites close together, or a coarse texture
with large crystallites farther apart.
The first five parameters are all obvious char-
Figure 13. Estimated location of fiber types on the plot of acteristics of fine structure. The concepts are
Figure 12 clear, and qualitative comments and rankings
a) Rubber, glassy polymer; b) Acrylic; c) Melt-spun poly-
ethylene; d) High wet modulus rayon; e) Rayon; f) Nylon,
can certainly be made, although experimental
polyester; g) Aramid, high molecular mass polyethylene; difficulties in measurement can arise and debate
h) Polyurethane (spandex); i) Wool; j) Cotton may occur about the best mathematical forms
of definition and about problems in interpret-
Any of the suggested fiber structures can oc- ing measurements. Any diagram of fine struc-
cur at varying degrees of orientation. As dis- ture includes implicitly the information needed
cussed with relation to birefringence in Sec- to calculate values of each parameter, even if the
tion 2.4.1, the degree of orientation is a quantity diagrams are so simplified that the values are not
which is easily defined as some average of the realistic.
 Fibers, 2. Structure 17

The sixth parameter, molecular extent, is a extreme value E m or to some average of length
less obvious structural feature. It has never been of the folds E a . In principle, molecular extent
measured directly and could not be estimated could be measured in different directions, but in
from a typical diagram because the relevant in- fibers the molecular extent parallel to the fiber
formation is contained in molecular paths over axis is important. As obvious from Figures 14
distances greater than those shown in the dia- B and C molecular extent is closely related to
grams. However, molecular extent almost cer- two frequently discussed structural features: the
tainly ranks equally with the other five parame- number of chain folds and the number of tie
ters in determining important fiber properties. molecules between crystals. In an amorphous
isotropic polymer, it would be related to radius
of gyration.
Reference to the analogous quantity in textile
yarns spun from short fibers like cotton or wool
might be helpful. As the material comes from
carding, the fibers are folded backward and for-
ward, and thus have a limited fiber extent. Var-
ious drafting operations then pull the fibers out
into more extended forms until, in the limit, the
fiber may be fully extended along the yarn with
no loops or folds. This increases yarn strength
because any fold is as much a source of weak-
ness as a fiber end, since both interrupt continu-
ity in the transmission of stress. The fiber extent
can be measured experimentally by incorporat-
ing colored tracer fibers, but an analogous proce-
dure is not possible for the molecules within the
fiber. Neutron scattering of deuterated molecules
might be a way of estimating molecular extent,
but the experiments would be very expensive.
The three different parameters — degree of
order, degree of orientation, and molecular ex-
tent — must not be confused. The problem is that
at the extremes, which never occur in practice,
they do become identical, as shown in Figure
15 A and B. A tendency exists to assume that
they go together through the intermediate states.
However, this is not so, and Figures 15 C – F
give various schematic examples of structures
in which one parameter is high and another low.
Analogous situations will occur in the real struc-
ture of textile fibers.
Figure 14. A: Definition of molecular extent, either as an As stated at the start of this section, specifica-
extreme value E m or an average value, E a tion of six parameters still leaves open an infinite
B: Molecular extent with crystallographic folding range of possible structures, with a large number
C: Molecular extent without crystallographic folding
of forms showing significant differences. Other
features which can be discussed in the context of
Figure 14 A illustrates the basic definition, the structure of particular fibers or which must
with Figures 14 B and C giving examples in be considered in theoretical analysis of the rela-
micellar structures with and without crystallo- tion between structure and properties include (1)
graphic folding. Molecular extent is a measure more detailed specification of the size and shape
of the distance over which the molecule extends. of crystalline regions; (2) the nature of imperfec-
Particular definitions might relate either to the tions within crystals; (3) the form of molecular
18 Fibers, 2. Structure

Figure 15. Schematic illustration of independence of degree of order, degree of orientation, and molecular extent, except at
the extreme values
A: Perfect order gives perfect orientation and maximum molecular extent
B: Maximum disorder gives zero orientation and a low extent
C: High order and zero orientation in a polycrystalline material
D: Low order in a structure with all segments oriented at a small angle to a preferred axis
E: High orientation with low molecular extent
F: High molecular extent with zero preferred orientation of segments

packing in amorphous regions; (4) the relative The degree of localization of order seems to
positions of crystallites on a regular or irregular have little influence on most mechanical and
superlattice; and (5) details of the interconnec- other physical properties. A low degree of lo-
tions between crystallites. calization gives a uniform structure: if this re-
flects the coherence of ordered material, diffu-
sion within the fiber will be resisted; but if, as
2.4.4. Relation to Fiber Properties is more likely particularly in hot or wet condi-
tions, this represents the mobility of disordered
Although the relation between fine structure and material, then the movement of substances such
fiber properties can be discussed in detail only in as dyes will be relatively easy. Generally, low
the context of particular fiber types, some gen- degrees of localization of order will be thermo-
eral trends can be mentioned. dynamically unstable, so that such materials can
Crystallinity tightens the structure and gives be set in a more stable form with an increase in
it greater stability. Consequently, increasing de- the localization.
gree of order usually yields increased strength Crystallite aspect ratio has a major effect on
(unless bad stress concentrations are present) mechanical properties, with a high ratio pro-
and increased stiffness, reduced moisture ab- moting greater stiffness (initial modulus), which
sorption and accessibility to chemicals such as is usually associated with reduced extensibility
dyes, and increased dimensional stability under and greater strength.
changes of temperature and humidity.
 Fibers, 2. Structure 19

Degree of orientation has a major influence its length. The mechanics can be analyzed in
on mechanical properties, as illustrated by the terms of slippage, which occurs at free ends of
family of stress – strain curves in Figure 16. As molecules or at folds, and leads to a lack of con-
indicated below, this is also a parameter that tribution to tension.
can be controlled easily. Increasing orientation
trades extensibility for strength, with the break-
ing points lying on a locus of increased tenacity 2.4.5. Relation to Fiber Formation
T and reduced breaking extension E, which ap-
proximates to a constant value of T E1/2 . The The development of fine structure can also be
initial modulus also increases. For clothing and discussed in detail in relation to particular ma-
household uses, the softer, lower modulus fibers terials and manufacturing methods, but once
are preferred, and the lower strength is adequate. again, a few general comments can be made.
For industrial uses such as tire cords and ropes, An important distinction exists between natural
the more oriented high-tenacity fibers are pre- fibers and man-made fibers. The former, except
ferred [57]. for silk, are laid down very slowly as living cells
over a period of days, weeks, or months, under
the genetic control of mechanisms of biosyn-
thesis of the polymer in living organisms. This
leads to highly specialized structures. In con-
trast, man-made fibers are formed from a melt or
solution of the polymer by high-speed manufac-
turing operations. Typical spinning speeds will
range from 500 to 5000 m/min (ca. 10 to 100
m/s), so that the solidification which establishes
the structure, occurs in a fraction of a second.
The manufacturer is thus left with what hap-
pens in the transition from disorder to partial
Figure 16. Family of stress – strain curves, showing effect order, and this is likely to be a rather poorly de-
of increasing orientation (→ O) or improving structure (→ fined structure. Thermodynamically, the struc-
S) ture will be metastable, so that in the melt-spun
thermoplastic polymer fibers, it can be changed
The size of localized units does not have much by subsequent heat treatment at temperatures ap-
influence on the initial part of the stress – strain proaching the melting point. The structure of
curve, but it does influence the strength. A reduc- fibers, like cellulose or the acrylics which can
tion in value is one way of improving structure, only be spun from solution because they de-
which moves the locus of failure in Figure 16 compose before they melt, will be less easily
further out. This is because a coarse structure changed, since this would require the action of
of larger units tends to give greater stress con- plasticizing or swelling agents, such as caustic
centrations and less effective connections bet- soda which changes the structure of cotton in
ween crystallites, with more free ends and fewer mercerization.
tie molecules. An increase in size also makes A particular example of the difference bet-
the spaces between crystallites greater, and this ween natural and man-made fibers is shown by
increases the mobility of dye molecules. Treat- the degree of order in cellulose fibers. Natural
ments that change structure in this way are thus plant fibers, like cotton, have a crystallinity of
prone to cause unsightly dye streaks in fabrics if about 66 %, but rayon only reaches about 33 %.
they are not well controlled. Rapid crystallization from a disordered solution
Increasing molecular extent is another way or melt leads to crystallinities which are char-
of increasing the strength of a structure, usu- acteristic of the polymer stiffness and complex-
ally associated with some increase in stiffness. ity. Therefore, nylon and polyester will give val-
This will also push the locus of failure in Figure ues of about 50 %, but linear polyethylene can
16 further out, since a high extent means that give higher values. Usually, different treatments
the structure is more strongly connected along will not change the value by more than about
20 Fibers, 2. Structure

± 5 %. However, when a different manufactur- polyester fibers, in which all the orientation is
ing method is available, such as the liquid crystal induced in the initial spinning operation, seems
systems used in aramids or gel spinning for high- to give a structure with larger crystallites than a
modulus polyethylene, much higher values can process of solidification followed by drawing.
be attained. Molecular extent is also not easy to control,
The degree of localization of order is also an except by the use of special techniques such
almost inevitable consequence of the manufac- as gelspinning, or by biological control, which
turing system, although it may be increased by gives a very high value in natural cellulose fibers.
heat treatment of thermoplastic fibers. In manufacturing from solution or melt, the mo-
The aspect ratio of the crystallites depends on lecular extent will depend on the natural config-
the circumstances of crystallization, which are uration of the molecule in the disordered state,
not usually amenable to control in manufactur- represented by a radius of gyration, transformed
ing, with rapid crystallization from a disordered by the elongation during fiber formation.
state tending to give micellar crystals. The con-
trast between natural and regenerated cellulose
fibers is again instructive: the former are fibril- 2.4.6. Structural Transitions
lar, but the latter are usually micellar. By chang-
ing the chemistry of the regeneration of viscose Fiber structure is often pictured in static terms,
rayon, crystallization can be delayed until the like an instantaneous snapshot of some geomet-
fiber is solid and oriented, and this does lead ric pattern. However, the dynamics, particularly
to a more fibrillar form of rayon with a higher the transitions between different degrees of mo-
modulus. bility, also have to be considered.
Degree of orientation is easy to control in The major transitions such as melting and
manufacturing operations, so that the family of chemical decomposition lead to a loss of fiber
products represented by Figure 16 can be gener- identity. In principle, any linear polymer is ther-
ated. Orientation may be increased by increas- moplastic and will melt, but in practice, a distinc-
ing the stretch imposed either between extru- tion exists between those that melt and those that
sion and solidification, provided the spinning decompose and char before a melting tempera-
speed is high enough to limit relaxation, or in ture is reached. The chief thermoplastic fibers
a subsequent drawing operation. In thermoplas- are nylon, polyester, polypropylene, and triac-
tic fibers, orientation can be increased further by etate. Close to the melting point, the structure
hot stretching of yarns or reduced by relaxation develops a degree of mobility, particularly if
and shrinkage. Thus, the fiber manufacturer has it has not been annealed for a long time to
a number of ways at his disposal to adjust orien- develop large stable structures. Consequently,
tation. Technically, no lower limit exists, but the these fibers can have their structure permanently
market only requires products with orientations changed, or heat-set, by high-temperature pro-
above a certain level. An upper limit to what can cessing. The chief decomposing or charring
be achieved without breaking fibers does exist, fibers are cellulose and polyacrylonitrile. Wool
however, usually at around 10 % breaking ex- and secondary acetate tend to liquefy and de-
tension. Other mechanisms are involved in pro- compose simultaneously.
ducing the high orientation of the high-modulus, Below the melting point, glass transitions oc-
high-tenacity fibers. cur which have some of the features of thermo-
Crystallite size is not controlled easily, ex- dynamic second-order transitions. They occur in
cept that it tends to be increased by heat treat- amorphous regions and involve a change in some
ment of thermoplastic fibers. Major changes in feature of the structure from rigidity to mobility.
manufacturing methods also cause differences. Rigidity, which causes the material to be glassy,
Thus a change in the chemistry of regeneration can come either from stiff chains or from strong
of viscose rayon fibers, with the sodium cellu- interactions between chains; either of these will
lose xanthate going through an intermediate zinc prevent relative movement. In a simple poly-
cellulose xanthate before being converted to cel- mer, a single transition will occur from a rigid
lulose, leads to a finer structure than is achieved glass to a flexible, rubbery form; however, in
by direct generation. High-speed spinning of some important fibers, the total change is divided
 Fibers, 2. Structure 21

between multiple transitions. These transitions been removed completely from the fiber. The
cause a major reduction in fiber stiffness, and material precipitates in a spongy form con-
cooling through the transition gives a temporary taining voids filled with solvent. In subsequent
set. processing, these voids collapse as solvent dries
Mobility can also be induced by plasticiza- off, and they become elongated as the fiber is
tion; this is particularly important in moisture- stretched. The void surfaces seem to disappear
absorbing fibers, where the transition tempera- to give a solid fiber, but a vestigial effect will
ture becomes much lower in the wet state. remain with the fiber divided into fibrillar zones
Another form of minor but first-order tran- separated by weaker divisions. This can show up
sition, which occurs in some fibers, is between in ease of fibrillation and in a granular surface
different crystal lattices. in tensile fracture.
Cells. Some natural fibres, such as wool and
2.5. Intermediate Structures plant fibres like flax, but not cotton, which is
a single plant cell, are multicellular. They are
Some textile fibers contain structural entities at a formed by the growth of separate cells, which
scale immediately above the fine structure. Thus are held together by chemical or physical in-
in cotton, which is a unicellular fiber, the fibrils teractions. Between the cells of wool, there is
are arranged in lamellar layers; and in wool, the a cell membrane complex containing lipids and
microfibrils of the basic structure are grouped proteins.
in macrofibrils within the individual cells which
make up the whole fiber. Similar macrofibrillar
associations may be present in man-made fibers, 2.6. Gross Inhomogeneities
but they are not well defined and their reality has
not been established conclusively. The fibrillar Some man-made fibers have essentially the same
strands, which are often seen when fibers are structure over their whole cross section, but
pulled apart, may merely reflect lines of weak- many textile fibers contain major sub-divisions.
ness within the fine structure. A clear example is wool, illustrated schemat-
Spherulites. The slow crystallization of ically in Figure 17, in which the core is bisected
polymers in bulk from the melt usually gives into two components having different chemical
a spherulitic structure as a result of repeated structure and physical fine structure, with a third
branching from widely spaced nuclei, but the form of structure present in the surface layer.
rapid cooling of fibers normally leads to a high Such effects in natural fibers derive from genetic
concentration of nuclei which leaves no room for control.
spherulites to develop. However, certain cool-
ing patterns do allow time for some spherulite
growth to start on a few heterogeneous nuclei
that are stable at a higher temperature. These
spherulites will grow to a certain size, but as
the temperature falls, the spherulite growth will
slow down and many more nuclei will be avail-
able for the final slow crystallization into a typ-
ical micellar fine structure. The spherulites will
be left as occlusions within the fiber and, on
drawing, will be transformed from a spherical
form to a cigar-shaped ellipsoid. Generally, the
conditions of fiber formation are adjusted to Figure 17. Schematic view of subdivisions of wool fiber:
avoid this, but it does sometimes occur and can ortho-cortex (O), para-cortex (C), and surface scales (S)
even be beneficial in some applications as a re-
sult of particular forms of light scattering. In the less deterministic and faster industrial
Voids. In spinning from solution, coagula- production of fibers, differences between skin
tion commonly occurs before the solvent has
22 Fibers, 2. Structure

Figure 18. Orientation of ribbonlike molecules in directions perpendicular to the molecular axis
A) Random; B) Radial; C) Circumferential

Figure 19. Bicomponent fibers

A), B) Side-by-side; C) Sheath-core; D) Islands-in-a-sea

and core are hard to avoid, since they experience However, if a fiber is melt-spun by extrusion
differences in cooling, in evaporation or coag- through a circular orifice, it will have a simple
ulation (if spun from solution), in nucleation, circular cross section. In spinning from solution,
and in stresses. The patterns of crystallization the volume reduction usually modifies the cross
are consequently different. Where molecules or section. First, solidification occurs on the out-
crystal lattices are asymmetric in cross section, side of the fiber; then the skin has to collapse
with a flat ribbonlike form which may be due as solvent is lost from the interior. Various de-
to cyclic groups, the orientation within the cross grees of modification are illustrated in Fig. 20.
section can be random, radial, or circumferential The circular form occurs when there is no loss
as indicated in Figure 18. of volume or when the chemistry of the solidifi-
Man-made fibers can be deliberately pro- cation process is controlled so that it occurs uni-
duced as multicomponent, usually bicompo- formly throughout the fiber. When a skin forms
nent, forms. Side-by-side fibers (Figs. 19 A and first and a subsequent small reduction in volume
B) will develop crimp as a result of differen- occurs, a dog-bone cross section will result; but
tial shrinkage. Sheath-core fibers (Fig. 19 C) are when there is a large volume reduction, highly
used when some special feature, such as bond- serrated forms are produced.
ing on heating, is required in the surface layer.
The islands-in-a-sea fibers (Fig. 19 D) are used
to make very fine fibers by removal of the matrix.

2.7. Fiber Shape

2.7.1. Cross-sectional Shape
The largest scale structural feature of a fiber is Figure 20. Increasing modification of fiber shape
its shape. In natural fibers, this can be special- A) Circular (unmodified); B) Dog bone; C) Serrated
ized as a result of the genetic control of growth.
 Fibers, 2. Structure 23

Modification of fiber shape is often desirable textile processing and gives bulk, warmth, and
to change the luster or other properties of a fiber. softness to the final product. In cotton, the crimp
This can be achieved in melt spinning by ex- is at a low level and somewhat irregular, but wool
truding through noncircular orifices and ensur- has a pronounced helical crimp like a spring.
ing that solidification occurs before the fiber re- Simple industrial production of fibers will give
verts to the equilibrium circular form. For exam- straight fibers without crimp, which has to be
ple, extrusion through a triangular hole will lead introduced for many applications.
to a rounded, three-sided shape, as suggested in For some markets, the need for high crimp
Figure 21 A; but extrusion through a Y-shaped justifies the expense of bicomponent fiber pro-
orifice will give a higher degree of modification duction. Differential shrinkage then causes the
of shape, as in Figure 21 B. The shape of the fiber to develop curvature, as indicated in Figure
fiber can be controlled, within limits, by alter- 22 A. The preferred lowest energy form for the
ing the shape of the hole and by adjusting the fiber would be a tight coil, shown in Figure 22 B;
balance during the cooling of the molten fiber but axial restraint would cause this to open into
between surface tension, which favors a circu- an extended coil (Fig. 22 C). However, torsional
lar form, and viscosity, which resists change of restraint is also present. In order to coil up, as
shape. Octalobal, star-shaped fibers are another in Figures 22 B and 22 C, the end of the fiber
common form produced in this way. would have to rotate. Since such twisting is not
Greater bulk can be achieved in fibers by possible in a long continuous fiber length, the
making them hollow. system accommodates by going into alternating
left-handed and right-handed helices, as shown
in Figure 22 D. The typical form of filaments in
a bicomponent crimped product consists of short
sections of helical crimp in opposite directions
joined by reversals.

Figure 22. Crimp development resulting from differential

shrinkage in a bicomponent fiber
A) Preferred crimp curvature; B) Minimum energy coiled
form; C) Extended coil; D) The real form, namely, alternat-
Figure 21. Fiber shape modification ing helices
A) Moderate shape modification with a triangular hole;
B) Greater modification with a Y-shaped hole
Texturing. Simple multifilament or monofil-
ament yarns can be used in some applications,
2.7.2. Axial Shape as dense, lustrous, silky fabrics, with the fil-
aments remaining straight and without crimp.
Most natural fibers have a natural crimp, namely, However, a substantial part of the textile in-
a waviness in axial shape, which is beneficial in dustry is devoted to changing the axial shape
24 Fibers, 2. Structure

by texturing [58]. In one technique applicable structure in a state of uncertainty, the structure of
to any type of multifilament yarn, the inherent specific materials should be summarized briefly.
fiber shape is not changed, but projecting loops
are formed and trapped within a twisted or in-
terlaced yarn structure. All other techniques in- 3.1. Cellulosic Fibers
volve heat-setting thermoplastic filaments, such
as nylon and polyester, in contorted shapes. The 3.1.1. Chemistry
dominant techniques are false-twist texturing The repeat unit of the cellulose molecule is
for fine textile yarns and jet-screen bulking for shown below, although the possibility that occa-
coarse carpet yarns. Stuffer-box, knit – deknit, sional groups might have a different form (i.e.,
and edge crimping are among the other meth- be derived from a different monosaccharide)
ods that have been tried. cannot be eliminated.
In twist texturing, the yarn is set in a highly
twisted state (Fig. 23 A) and then untwisted
(Fig. 23 B). The filaments thus have a natural he-
lical shape and are also under torsional stresses.
When the untwisted yarn is allowed to contract
by 10 – 20 % (Fig. 23 C), the internal stresses
are relieved by the filaments’ forming alternat-
ing helices, which can be stabilized by a second
heat-setting step if a yarn with high bulk but low
stretch is needed. A single-heater process gives
high-stretch yarn in which the filaments contract The molecule is ribbon shaped but, because
to highly snarled forms in order to relieve torque of the oxygen (−O−) links, has some flexibil-
(Fig. 23 D). ity, at least for bending in one plane and twist-
In the jet-screen process, the yarn is fed into a ing. The hydroxyl (−OH) groups readily form
turbulent steam jet and then impacted on a screen hydrogen bonds, which give a relatively strong
where it is heated and cooled in order to set the attraction between neighboring chains and also
filaments in complex buckled forms. lead to water absorption. In natural cellulose, the
In the manufacture of man-made fibers in- degree of polymerization is very high, but it is
tended for staple yarns, the tows are normally much less in regenerated cellulose.
crimped before being cut into short fibers. One A point of specialized interest is that the chain
method involved passing the hot tow between is directional, as a result of the asymmetry of the
intermeshing gear wheels, so that the filaments ring structure. Crystallization can occur in dif-
were set in an axial shape by the serrations. In ferent forms, and controversy has existed about
stuffer-box crimping in which the tow is forced the precise crystal lattices. The belief now is
into a confined space that causes the filaments that cellulose I, which is the usual form in nat-
to buckle into a tight zigzag form; this leads to ural cellulose, has all the chains aligned in the
a planar sawtooth crimp. same direction (i.e., parallel), whereas cellulose
II, which is formed on mercerization with caus-
tic soda and is also the usual form in regenerated
3. Particular Textile Fibers cellulose, has neighboring chains in opposite di-
rections (i.e., antiparallel). Cellulose III and IV
Although other articles in this encyclopedia deal occur after special treatments.
in detail with different types of industrial fibers The relatively stiff chain and the strong hy-
(→ Fibers, 4. Synthetic Organic; → Fibers, 5. drogen bonding mean that dry cellulose has a
Synthetic Inorganic; → Cellulose; → Wool), the high second-order transition temperature. In-
preceding sections clearly demonstrate the great deed, this temperature is above 200 ◦ C, where
diversity of structure even within the limited measurement is not possible because the fiber
group of general-purpose textile fibers. Conse- chars. However, the absorption of water results
quently, to avoid leaving the subject of fiber in mobility, and in the wet state, the transition
temperature is below room temperature. Wetting
 Fibers, 2. Structure 25

Figure 23. Structural forms in twist texturing

A) Yarn as set; B) Untwisted yarn held to length under tension; C) Yarn contracted by 15 %; D) Yarn fully contracted

and drying thus constitute a mechanism for set- into larger crystals. Beyond the fine structure is
ting. a rich complexity of structural detail.
In cellulose triacetate, the −OH groups are
replaced by acetate (−OCOCH3 ) groups. For
the more common secondary cellulose acetate,
about one-sixth of the acetate groups are more
or less randomly hydrolyzed back to hydroxyl
groups.

3.1.2. Cotton

Cotton [39] is a unicellular fiber in which an

outer primary wall first grows out from the seed
coat to the final dimensions of the cotton fiber
and then is filled in with a secondary wall. Cel-
lulose is synthesized within the cell plasma by
the addition of glucose molecules to growing
chain molecules via an enzyme complex. About
30 molecules grow together and naturally form
crystalline fibrils with chains in the parallel ar-
ray of cellulose I. At the level of fine structure,
the best model is an assembly of microfibrils,
with the disorder coming from a lack of regis-
ter in packing the fibrils together, and the den-
sity reduced by some space between fibrils. The
equivalent crystallinity is about two-thirds. One
unanswered question is what causes the fibrils
Figure 24. Schematic of major features of cotton structure
to retain a clear identity instead of coalescing a) Primary wall; b) Secondary wall; c) Lumen; d) Molecule;
e) Crystal lattice; f) Fibrils; g) Reversal
26 Fibers, 2. Structure

The thin primary wall forms with the fibrils crystallinity of about one-third. In most forms,
wound in a specific array, but the structure is the fine structure is assumed to be fringed mi-
dominated by the thick secondary wall. The de- cellar. The addition of zinc ions to the acid
velopment of structure is shown schematically bath gives improved properties. Two regener-
in Figure 24. The fibrils form lamellar sheets ation routes then occur. On the surface of the
that wind around the inside of the cylinder at an fiber, the zinc salt forms first, followed by reac-
angle which changes slightly through the thick- tion with the acid to give cellulose. This yields
ness, but is about 21 ◦ . At intervals, the helices a fine micellar texture, with small crystallites
reverse from right-handed (Z) to left-handed (S). well-linked by tie molecules, which has good
Daily growth rings are apparent. strength. The zinc ions do not reach the core fast
The structure at all levels is important in de- enough to prevent the direct regeneration of cel-
termining the properties of cotton fibers. Thus, lulose from the sodium salt. The resulting struc-
moisture absorption, swelling, and accessibility ture is coarser in texture with larger crystals fur-
to dyes occur on and between the fibril surfaces. ther apart, which results in a larger proportion of
The stress-strain curve can be explained as a de- free ends to links, and greater stress concentra-
formation of the crystal lattice, with the mod- tions; consequently, it is generally weaker. The
ulus reduced by a factor approximating cos4 θ, collapse of the skin leads to a highly serrated
resulting from the helix angle θ, and additional cross section, with the ribbonlike molecules and
extension occurring because of rotation at the crystals forced into a transverse orientation that
reversals and the straightening out of gross con- is locally perpendicular to the surface. This is
volutions [15]. the common form of textile viscose rayon.
When the zinc concentration in the bath is in-
creased and additives are included in the viscose
3.1.3. Other Plant Fibers solution that slow down the direct regeneration
reaction, the whole fiber can be forced into the
Other plant fibers, such as flax, jute, and ramie, strong, finer textured structure. This, together
which stiffen stems, and sisal, which stiff- with some attention to degree of polymeriza-
ens leaves, are multicellular and may contain tion and the elimination of a low molecular mass
more non-cellulosic impurities [37]. The fibril- fraction, is the basis for the high-tenacity tire-
lar model of fine structure is applicable, but the cord rayons. The more uniform coagulation also
geometry of arrangement in the cells is differ- replaces the serrated cross section by a roughly
ent. Usually, the helix angle is smaller, around circular cross section.
10 ◦ , so that the fiber modulus is higher than in Selection of other additives causes the fiber to
cotton. burst open after forming a skin. This gives a bi-
component fiber with a thicker skin on one side
than on the other. Such fibers naturally crimp on
3.1.4. Rayon drying. The best carpet fibers combine some as-
pects of the high-tenacity route with the crimped
Cellulose fibers can be regenerated through sev- route.
eral solvent systems, and these do produce struc- In all these processes, the coagulation results
tural differences [33]. The most important pro- from the regeneration of cellulose, which crys-
cess is the viscose process in which a solution tallizes into an unoriented fiber. This is then
of sodium cellulose xanthate (−OH replaced by stretched to promote orientation, to a greater ex-
−OCSS− Na+ ) in caustic soda is extruded into tent in industrial fibers than in fibers for clothing.
an acid bath. Viscose rayon is of considerable When the viscose solution is extruded into
structural interest because control of the chem- a weak acid bath, such as sodium dihydrogen
istry of regeneration enables fibers with different phosphate, the sequence changes by first coag-
structure, properties, and uses to be made. Fig- ulating a fiber of the sodium cellulose xanthate,
ure 25 gives a schematic indication of the differ- then orienting it by stretching, and finally regen-
ences. erating the cellulose. This gives the so-called
The degree of order in regenerated cellulose polynosic or high wet-modulus rayons, which
is about half that in natural plant fibers, with a are more cottonlike in character. Crystallization
 Fibers, 2. Structure 27

Figure 25. Schematic of routes to different types of viscose rayon

occurs in what is already a solid, oriented fiber, weaker. The structure is assumed to be micel-
and this results in a fibrillar structure. The fibrils lar.
are not as well defined as in natural fibers; they
consist of long crystalline units, with molecules
fringing off into amorphous regions. 3.2. Protein Fibers
The late 20th century led to another means of
spinning regenerated cellulose fibers, which is The repeat unit in proteins is an amino acid
more environmentally acceptable. Lyocell fibers residue:
are high-DP cellulose fibers spun from solution
in an amine oxide. They also have a fibrillar fine
structure (→ Cellulose, Chap. 3.2).
Table 3 gives a comparative summary of the
various cellulose fibers in terms of important
structural parameters.
Diversity results from the selection of a par-
ticular sequence of side groups (R) from the
3.1.5. Acetate Fibers
usual 20 different types, including two which
Because of their irregular chemical structure, depart from the form shown in the formula. Pro-
secondary acetate fibers are very poorly crys- line, a ring of three −CH2 − groups joined to
talline. This shows up in a low softening tem- the nitrogen atom in place of hydrogen. Cystine,
perature, low resistance to extension, poor re- −CH2 SSCH2 −, which is a bifunctional group
covery, and low strength. Indeed, this oriented linking two protein chains together, is produced
but almost amorphous structure gives properties by the cross-linking of cysteine, in which R is
which would now be inadequate to launch a new −CH2 −SH.
fiber, although acetate remains in markets estab- Keratin — a generic name for the material
lished earlier. in wool, hair, and other appendages — is a com-
Triacetate is more crystalline and is some- plex mixture of different proteins with signifi-
what similar to fibers like nylon and polyester, cant amounts of all types of side groups. Cur-
although it has a lower melting point and is rent understanding identifies a limited number
28 Fibers, 2. Structure

Table 3. Estimated relative values of structural parameters in cellulose fibers

Degree Localization Aspect Orientation Size Molecular

of order of order ratio extent

Cotton high high high medium fine high

Flax high high high high fine high
Ordinary rayon
core low medium low medium coarse low
skin low medium low medium fine low
High-tenacity rayon low medium low high fine medium
High-modulus rayon low medium high medium fine medium
Lyocell low medium high medium fine medium

Figure 26. Schematic representation of levels of structure in wool

a) Chemical repeat unit; b) High-cystine molecular segments; c) Low-cystine molecular segment; d) Protofibril with link to
matrix; e) Microfibril; f) Fine structure of microfibril and matrix; g) Macrofibril; h) Cell; i) Whole fiber showing ortho- and
para-cortex and scale cells

of proteins making up keratin intermediate fil- coiled form with about 3.6 amino acid residues
aments (microfibrils) and a large number of per turn. The lattice is stabilized by hydrogen
keratin-associated proteins in the matrix [36, p. bonds and other interactions between coils in the
72]. same chain. The β-form is an extended chain lat-
Silk fibroin, which contains no cystine, is a tice, with hydrogen bonds between neighboring
simpler protein and a natural block copolymer molecules.
with sections limited to a regular sequence of The matrix of wool and hair is formed from
residues with the side groups −H, −CH3 , and globular proteins with two main families. One
−CH2 OH, and other sections with more diver- family of high-sulfur proteins is rich in cysteine,
sity, including substantial amounts of tyrosine, which is cross-linked to cystine during the kera-
−CH2 −4-C6 H4 OH. tinization stage in the growth of hair fibers. The
Proteins of the type found in fibers exhibit two other family consists of high tyrosine/glycine
different forms of crystal lattice. The α-form, proteins.
a perturbation of Pauling’s simple α-helix, is a
 Fibers, 2. Structure 29

3.2.1. Wool and Hair cortex, with more cystine, gives a bicomponent
fiber. The microfibrils in the macrofibrils of the
Wool [36] and other hair fibers [35] show a se- para-cortex are parallel to the fiber axis, but in
ries of structural features at various levels up to the ortho-cortex the macrofibrils consist of he-
the full-scale fiber, as indicated in Figure 26. lical assemblies of microfibrils [44]. On drying,
The fine structure consists of crystalline mi- the ortho-cortex macrofibrils tend to increase
crofibrils, composed of low-sulfur protein (with- in length, due to the decrease in helix angle as
out cystine), parallel to the fiber axis. This is the macrofibril diameter reduces, but the para-
embedded in a rubbery matrix, which is cross- cortex macrofibrils tend to remain constant in
linked by cystine and connected to the fibrils length. The differential length change leads to
by tails of the low-sulfur molecules. Figure 27 a helical crimp, if the components are side-by-
shows the tensile stress – strain curve of a uni- side, but a straight fiber if they are symmetrically
form wool fiber in the wet state. The crystal lat- distributed [61, 62]. A total model proposed for
tice is normally a coiled chain α-helix; under the structural mechanics of wool and hair fibers
tension it can transform with 80 % extension to covers eight levels between molecules and the
an extended chain β-lattice. The interaction with whole fiber [63].
the matrix in the composite system leads to the The scale cells on the surface, with an escarp-
flat yield region in the stress – strain curve, the ment facing the tip of the fiber, cause directional
stiffer post-yield region, and the characteristic friction.
recovery curve [59, 60].

3.2.2. Silk

Silk [35], which does not form as a living cell

but is an excretion, presumably evolved into a
tough fiber; this would result from a crystalliza-
tion of the regular sections linked in a rubbery
matrix by the less regular sections. The chemical
constitution would control the fine structure in
a fiber which coagulates after extrusion, to form
two triangular filaments held together by gum
(→ Silk).

3.2.3. Regenerated Protein Fibers

Fibers have been made from the proteins in milk

(casein), corn (zein), and other natural products.
Generally, these fibers have a poorly ordered
structure with a weakness that has led to a lack
of commercial success.

Figure 27. Stress – strain curve of wool

3.3. Major Melt-Spun Fibers
The larger scale macrofibril and cell struc- 3.3.1. Chemistry
tures do not have much influence on the proper-
ties, but there may be slippage due to debond- The most important melt-spun fibers [38], dat-
ing at the lipid-rich cell membrane complex bet- ing from the middle of the 20th century, are
ween individual cells. However, the division of the polyamides nylon 66 and nylon 6, and the
the main part of the fiber, called the cortex, into polyester poly(ethylene terephthalate) (PET),
an ortho-cortex, with less cystine, and a para-
30 Fibers, 2. Structure

with the following repeating units (see also → The glass-to-rubber transition in nylon and
Fibers, 4. Synthetic Organic, Chap. 1): polyester occurs in two stages, which is a valu-
able feature. A transition below room tempera-
ture gives a measure of extensibility and tough-
ness to the fiber, while sufficient stiffness is re-
tained. The remaining inevitable transition to a
fully rubbery, amorphous form between crystal-
lites occurs at a higher temperature. The first
transition is associated with the onset of mobil-
ity in rotation around −CH2 − and similar bonds
in the aliphatic sequences. In nylon, the second
transition is associated with the hydrogen bonds
moving into a state of dynamic equilibrium, so
that the chain segments in amorphous regions
become completely free. This transition temper-
ature is much lower in wet fibers. In polyester,
analogous interactions of the benzene rings oc-
cur, but the transition temperature is somewhat
higher and is little affected by water. The ben-
zene rings lead to a higher initial modulus in PET
More recently, the commercially available than in nylon. 3GT with more aliphatic groups is
syntheses of poly(trimethyleneterephthalate) more like nylon, but the double ring in PEN leads
(3GT) and poly(ethylenenaphthalate) (PEN) to a stiffer fiber with a higher melting-point.
have led to the production of these polymers as Another major melt-spun fiber is
textile fibers. isotactic polypropylene [9003-07-0],
Little difference exists between the two —[ CH2 CH(CH3 )— ] n . Because of the bulky side
polyamides: in contrast to nylon 66, nylon 6 has group, the molecule forms a threefold helical
five and five −CH2 − groups, instead of four and coil, which gives it a greater stiffness in the melt
six; has the middle −CONH− group reversed to or in amorphous regions, but a lower axial mod-
−NHCO−; and consequently, has only half the ulus in the crystal. Polypropylene has a single
length of repeat unit. Perhaps the most impor- broad glass transition near room temperature.
tant feature is that the nylon 6 molecule is direc-
tional, so neighboring chains in a crystal must
be in proper relation to each other. This might 3.3.2. Fine Structure
be the reason nylon 6 melts at a temperature ca.
50 ◦ C lower than nylon 66 and PET. Despite their major importance as industrial
All three polymers have a very long repeat- products for about 50 years, surprisingly little
ing unit, which gives fewer choices of location in is known about the fine structure of melt-spun
crystals than in simpler polymers such as poly- fibers. The degree of order corresponds to a crys-
ethylene, and thus leads to lower maximum crys- tallinity of about 50 %, not much changed by dif-
tallinities. The other common characteristic is ferences in processing. The degree of orientation
the presence of a flexible aliphatic sequence with can be controlled within fairly wide limits by the
weak interactions. In between these sequences, speed of windup, subsequent drawing, and hot-
the polyamides have −CONH− groups which stretching or relaxing treatment.
interact by hydrogen bonding, and polyester has As a working model, the structure is assumed
benzene rings which are both stiff and interac- to consist of crystalline micelles, partly folded
tive. and partly fringed at the ends, and linked by
The crystal lattices of these polymers are sim- tie molecules. The crystallites are assumed to
ple extended chain forms and are known. In ny- be stacked in pseudofibrils, as shown in Fig-
lon 6, some complications result from the exis- ure 5. Some authors have suggested significant
tence of two alternative forms. differences between amorphous material join-
ing crystallites within a pseudofibril and amor-
 Fibers, 2. Structure 31

phous material separating pseudofibrils. How- 3.3.3. PLA Fibers

ever, good quantitative information is lacking
about the size and shape of crystallites, their The newest melt-spun fiber is PLA [64], which
arrangement in some form of superlattice, the is produced with the tradename NatureWorks.
relative amount of folds and tie molecules, and There is less structural information available on
the detailed pattern of interconnections between this type of fiber. It can be assumed that it is a
crystallites. Evidence exists that annealing treat- poly(lactic acid) fiber, which has an ester link-
ment leads to the development of larger crystal- age between the −OH and −COOH groups at
lites spaced farther apart. If the fiber is free to opposite ends of the lactic acid molecule. The
contract, chain folding may develop. basic chemical formula is:
Consideration of the change in endotherms
observed in differential scanning calorimetry in-
dicates that rapid “crystallization” leads to a
form I. This has been suggested [56] to be a
more uniform structure (see Fig. 9), with small
neighboring segments in crystallographic reg- The US Federal Trade Commission defini-
ister, but in dynamic equilibrium just below the tion issued in 2002 states that there must be at
almost constant melting point observed for form least 85 % of lactic acid ester units in the chain,
I. Annealing then leads to the formation of small but includes poly(lactate)s, which could contain
separate crystallites, initially with a lower melt- other units. For example, there could be copoly-
ing point but a lower free energy at the annealing merisation with ethylene terephthalate or other
temperature. Prolonged annealing increases the groups.
size and perfection of the crystallites, and raises
the melting point.
Despite many similarities, nylon and
polyester have significant differences. Cooling
3.4. Acrylic Fibers
of an unoriented fiber, being wound up at a low
The remaining major synthetic fiber type has
speed such as 1000 m/min (ca. 20 m/s), leads to
acrylonitrile, −CH2 CH(CN)−, as its principal
crystallization in nylon but not in polyester. Only
repeating unit [38] (see → Fibers, 4. Synthetic
the subsequent drawing causes the polyester to
Organic, Chap. 5). However, for dyeability, up
crystallize. Textile polyester fibers have a higher
to 15 % of a comonomer must be included. Sug-
initial modulus than nylon and split axially at an
gestions abound in the patent literature, along
angle closer to the fiber axis. These differences
with a diversity of practice by manufacturers,
are presumably associated with the stiffness of
about both the type of comonomer and the form
the benzene ring, but the structural implications
of copolymerization. The degree of tacticity of
are not understood in detail.
the polyacrylonitrile [25014-41-9] is also not
When polyester fibers are wound at a higher
well documented but probably atactic. Because
speed, around 3000 m/min (ca. 50 m/s), they de-
of these features, acrylic fibers are rather differ-
velop an incipient crystallinity that makes them
ent in structure from most other types.
more stable and easier to process. These are the
The molecule appears to act as a cylindrical
so-called partially oriented yarns (POY) used as
rod with strong, but not very localized, attrac-
draw-texturing feed yarns. At still higher speeds,
tive forces coming from the dipole in the −C≡N
sufficient orientation and crystallinity can be in-
group. The rods pack regularly side by side,
duced to give fibers suitable for some applica-
like chalk in a box, but are not in register along
tions without drawing. However, the degree of
their length. The fine structure is thus assumed
orientation that can be achieved this way is lower
to consist of such ordered pseudocrystalline re-
than in the two-stage route. The fine structure is
gions mixed with less ordered regions. A big
also different and seems to contain larger crys-
second-order transition occurs around 100 ◦ C,
tallites.
when the segments in the less ordered regions
overcome the interactions and can slide over one
another easily; other transitions then take place,
32 Fibers, 2. Structure

at higher temperatures, until the structure de- strength. Most of these fibers also show high
composes while still solid. temperature and chemical resistance, and some
fibers selected mainly for thermal stability have
high stiffness even if not high strength. The
3.5. Other Polymers choice of category is thus sometimes rather ar-
bitrary, but this section includes fibers selected
Other linear polymers have been used to a lim- mainly for mechanical performance, while Sec-
ited extent in textile fibers. Their fine structures tion 5.4 includes those selected mainly for ther-
have usually not been studied in detail but are mal and chemical stability. The strong fibers are
similar to the most nearly corresponding major reviewed in [34, 66].
fibers. Among melt-spun fibers there has been The advantages of using a material in fiber
some production of other variant polyamides and form are discussed in Section 1.1, but in some
polyesters. Some of these, such as nylon 4 and cases the structure of the fiber material differs
poly(butylene terephthalate), differ only in the little from other forms of the material. In these
length of −CH2 − sequences. Qiana (Du Pont), cases, only brief comments will be given in this
marketed as a luxury fashion fiber but no longer article, and reference should be made to other ar-
made, was a more complicated polyamide. ticles in this encyclopedia for more general and
Polyethylene [9002-88-4], — [ CH2 −CH2 — ] n, detailed information on structure (→ High-Per-
fibers are spun from the melt or, in the spun- formance Fibers).
bonded material Tyvek (Du Pont), are flash-spun
from solution to give a fibrous network. The
structure is highly crystalline, probably with the 4.1. Glass
lamellar form characteristic of crystallization in The structure of glass fibers is essentially the
this polymer; disorder would then arise from same as the structure of bulk glass [34, pp. 191–
the localized defects possible with such a small 238]. Solidification from the molten state gives
repeat unit (see → Fibers, 4. Synthetic Organic, an isotropic three-dimensional network based on
and Section 4.2.2). High-modulus polyethylene a tetrahedron of four oxygen atoms around a sil-
is dealt with in Chapter 4. icon atom, but made irregular and amorphous
Poly(vinyl chloride) [9002-86-2], PVC, by metal ions. A typical composition of E-glass
[CH2 CH(Cl)]n , is similar to acrylic fibers, as fiber intended for electrical insulation is 52 –
are other vinyl and vinylidene copolymers with 56 % silicon dioxide, 16 – 25 % calcium oxide,
chlorine, acetate, or other side groups (see → 12 – 16 % aluminum oxide, 8 – 13 % boron ox-
Fibers, 4. Synthetic Organic, Chap. 6). ide, 0 – 1 % sodium and potassium oxides, and 0
Poly(vinyl alcohol) [9002-89-5], PVA, – 6 % magnesium oxide. Different compositions
[CH2 CH(OH)]n , has special features associ- are used in the newer glass fibers optimized for
ated with hydrogen bonding of −OH groups. other markets; for example, the high-strength S-
In one form, the attraction for water leads to 2 glass fiber is low in alkali and high in magne-
solution on washing, but this can be eliminated sium. Glass fibers are reviewed in [67] and [68];
by appropriate treatment. Full information on see → Fibers, 5. Synthetic Inorganic.
PVA fibers is given in [65] (see also → Fibers,
4. Synthetic Organic, Chap. 7).
4.2. Highly Oriented Linear Polymers
High-tenacity, high-modulus polymer fibers
4. High-Modulus, High-Tenacity have a structure that satisfies the three re-
Fibers quirements of high order, high orientation and
— most important — high molecular extent. In
An important, new generation of fibers has ap- practice, such a structure can be reached only
peared, intended for engineering use either in by specialized routes, and this has not been
flexible systems (e.g., ropes and other tension achieved with such common polymers as nylon
members), in special tires or in rigid compos- and polyester (PET). There are two main produc-
ites, and characterized by high stiffness and high tion methods. The first route requires very stiff
 Fibers, 2. Structure 33

and strongly interactive molecular chains, which crystal solution, but results from drawing and
inhibit chain folding. In most cases, this group heat-treating of fiber coagulated from an ex-
of fibers depends on orientation during extru- truded isotropic solution.
sion of a liquid crystal solution or melt. The sec- Other aramid and related aromatic fibers with
ond route involves a “combing out” of the chain similar structures have been produced in Russia
molecules by some means such as gel spinning [34, pp. 115–132].
or super-drawing and requires very flexible and
weakly interactive molecules.
4.2.2. Polyethylene

4.2.1. Aramid Polyethylene, which has the simple −CH2 − re-

peat unit, can be produced as a high-strength,
The first high-tenacity aramid fiber was in- high-modulus fiber that is highly crystalline and
troduced by Du Pont with the name Kevlar; highly oriented, and has the molecules highly
other manufacturers now also produce aramid extended with a minimum of chain folding. The
fibers [34, pp. 23–61]. It is composed of poly(p- polymer will always be linear, but the degree
phenylene terephthalamide) (PPTA) of polymerization depends on the production
method.
The highest strength and stiffness is produced
by gel spinning from a fairly concentrated solu-
tion of ultrahigh molecular mass polymer, which
a stiff, rodlike molecule with strong hydrogen- allows for a high degree of subsequent elonga-
bonding interactions at the −CONH− groups tion [34, pp. 62–92]. Melt-spinning and super-
and electronic interaction between benzene drawing is a cheaper process but requires lower
rings. In solution, the molecule forms liquid molecular mass, so that the resulting properties
crystals which are easily oriented on extru- are not as good. Solid-state extrusion of a crystal
sion. The resulting fiber has a structure that is mat is another method of achieving the required
very highly oriented and highly crystalline. The structure [34, pp. 132–144]. Three reviews give
molecules are fully extended. The crystal per- many details [72 – 74]; see also → Fibers, 4.
fection persists only for limited distances, with Synthetic Organic.
a packing pattern derived from the rodlike liq-
uid crystals. Suggestions have been made of the
occurrence of pleated sheets arranged radially 4.2.3. Other Polymers
in the structure. However, specialized articles
should be consulted for such details [69, 70], Several other fiber types are produced by the liq-
(→ High-Performance Fibers). uid-crystal route.
Teijin produces another aramid fiber called Vectran, which is melt-spun and then heat-
Technora [71], but this is a copolyterephtha- treated to increase molecular mass, is a fully
lamide of p-phenylenediamine and 4,4 -diami- aromatic co-polyester with the formula:
nodiphenyl ether, and is a 50 mol % copolymer
of

Other research, aimed at superior properties

Evidence exists for the presence of the crys- rather than lower cost, is utilizing some newly
tal structures of both homopolymers. In con- synthesized materials such as stiff-chain aro-
trast to PPTA fibers, the highly-oriented, chain- matic heterocyclic polymers (with the general
extended structure is not formed from a liquid- designation PBZ) based on benzothiazole (PBS)
34 Fibers, 2. Structure

or benzoxazole (PBO) ring structures. Typical Another route that has been applied to poly-
repeat units are ethylene, is virgin polymerization in which the
orientation, crystallinity, and molecular extent
are established at a point of polymerization of
chains.

4.3. Carbon Fibers

When a suitable organic precursor fiber is sub-

PBO is now commercialized as Zylon [34, jected to a sequence of heat treatments, ending
pp. 101–108]. Although the molecules of these with a very high temperature under tension, a
fibers are highly oriented and packed side by high-modulus carbon fiber is produced with a
side in a regular array, they are not necessarily quasi-graphitic structure [34, pp. 156–190]. De-
in crystallographic register along their length. pending on the starting material, usually poly-
Aramid and PBO fibers have relatively weak acryonitrile fibers or pitch fibers, and the details
intermolecular bonding and consequently have of the heat treatments, considerable variations in
low shear resistance and fail in compressing structure occur, which lead to a range of combi-
by internal buckling. Sikkema [34, pp. 108– nations of strength and stiffness.
115], [75] has synthesized the new polymer M5, Pure graphite crystals consist of a stack of
which is made from tetraaminopyridine and di- planar sheets of carbon atoms in a hexago-
hydroxyterephthalic acid, and prepared experi- nal array. Most carbon fibers are turbostratic,
mental fibers. Projecting OH groups lead to hy- with neighboring parallel sheets not in crystal-
drogen bonding in both directions, as distinct lographic register. However, any assembly of
from the planar hydrogen bonding in the para- parallel sheets would be useless in fibers due
aramid fiber, with a resulting improvement in to lack of lateral cohesion, which leads to the
shear and compression resistance in fibers. The use of graphite as a lubricant. Some disorder,
chemical formula is: which links sheets, is needed. Carbon fibers are
a disturbed and distorted assembly of graphitic
crystalline elements, for which many different
pictures have been drawn. The sheets are ar-
ranged in separate layers that are bent and folded
within the structure. It seems likely that the con-
version of the original linear polymers into two-
dimensional sheets may have developed in dif-
There have been reports on studies of ferent regions, which leads to occasional cross-
poly(vinyl alcohol) fibers produced by gel spin- linking C−C bonds between neighboring por-
ning or superdrawing, and other materials are tions of sheets to give a sparse three-dimensional
being investigated. network. An important feature for high modulus
A third special route has been applied to poly- is that the planes should all be aligned closely
diacetylenes, which have the following general parallel to the fiber axis. This still leaves two de-
formula: grees of freedom of local orientation of a plane.
Rotation about axes perpendicular to the plane
allows neighboring planes to be at different an-
gles in a turbostratic structure. Rotation of the
where R represents a large number of possible planes around a line parallel to the fiber axis,
side groups. which must occur cooperatively between neigh-
Single-whisker crystals of the precursor di- boring sheets to maintain close packing, allows
acetylene can be grown, which is then polymer- for a variety of transverse orientations within
ized in the solid state. The resulting fiber is es- carbon fibers. Radial, circumferential and other
sentially a perfect polymer single crystal. patterns occur.
 Fibers, 2. Structure 35

Carbon fibers are dealt with in several chap- micron-sized α-alumina grains occurs and the
ters in [66], as well as in [76] and [77]; see also fibers become brittle. Small grain size is main-
→ Fibers, 5. Synthetic Inorganic. tained in alumina – silica fibers. For example,
Altex from Sumitomo contains 15 % of SiO2 and
consists of 25 nm γ-alumina grains surrounded
4.4. Ceramic and Other Inorganic by amorphous silica. Nextel fibers from 3M con-
Fibers tain B2 O3 and have the composition of mullite.
With 14 % B2 O3 , Nextel 312 is described as
Quartz fibers have a long history in scientific quasi-amorphous, but Nextel 440 with 2 % B2 O3
instrumentation, but the production of fine ce- consists of γ-alumina in silica. The presence of
ramic fibers with diameters of the order of 10 µm silica leads to more flexible fibers, which creep
for use in high-temperature composites was first and lose strength above 900 ◦ C. Nextel 650 is an
commercialised in the 1980s. Ceramic fibers, are alumina – zirconia fiber, which contains 10 % of
covered in several chapters in [26, 51, 80]. The ZrO2 and 1 % of Y2 O3 .
account below is based on the more recent pub- Large diameter ceramic “fibers” can be made
lication [34, pp. 239–258] (see also → Fibers, 5. by vapor deposition on a substrate such as tung-
Synthetic Inorganic, Chap. 4). sten or carbon filament. Another type of ceramic
Since the 1980s, there have been considerable fiber consists of monocrystalline inorganic crys-
development and the market has stabilized with tal whiskers. Ceramic fibers, are covered in sev-
silicon carbide based and alumina based fibers as eral chapters in [26, 66, 77]; see also → Fibers,
the main types. The fibers have a structure which 5. Synthetic Inorganic.
is typical of polycrystalline ceramics, but it has
been shown that small differences in the fabrica-
tion processes lead to considerable differences 4.5. Structure and Properties
in microstructure.
One group of silicon carbide based fibers (see By definition, all the fibers included in this sec-
also → Fibers, 5. Synthetic Inorganic, Chap. 3) tion have a high modulus and most have a high
are made by treatments of organosilicon poly- strength. Although each fiber type should be ex-
mer fibers. A typical Nicalon fiber from Nippon amined separately, a broad generalization is that
Carbide contains 56 % Si, 32 % C and 12 % O. the linear polymers give very high strength but
β-SiC is present in grains of about 2 nm size, somewhat lower modulus; that the carbon fibers
with the remaining 45% of the fiber composed can have high strength and the highest moduli;
of a metastable Si-C-O phase, which impedes that the ceramic fibers have lower strength but
grain growth and allows creep to occur, and free high modulus; and that the amorphous structure
carbon particles. In Hi-Nicalon the oxygen con- of glass leads to lower values of both strength
tent is reduced to 0.5 % or less but the fiber con- and modulus.
tains more free carbon. The SiC grains are 5 However, the structural differences cause big
to 20 nm in size, surrounded by less crystalline differences in some other properties. The highly
SiC and turbostratic carbon. Tyraano Lox fibers oriented linear polymer fibers inevitably have a
from Ube Industries include about 2 % of Ti with low compressive yield stress, since only weak
55 % of Si and varying amounts of C and O and forces exist between molecules and the chains
have microstructures similar to the high-oxygen can buckle within the fibers. They are prone to
Nicalon fibers. Near-stoichometric SiC fibers, splitting into fibrils and usually break by long ax-
which contain more than 95 % SiC, are made by ial splits. By contrast, glass and ceramic fibers,
sintering processes. Grain sizes are of the order which have a three-dimensionally bonded struc-
of 200 nm with pockets of free carbon between ture, and carbon, which is also coherent in all di-
the grains. rections, show similar behavior in compression
Alumina fibers are derived from the extrusion and tension. They usually break cleanly across
of viscous solutions of aluminum salts, which the fiber.
are processed to give over 99 % Al2 O3 fibers. Although the three-dimensional fiber struc-
Up to around 1000 ◦ C grain sizes range from 10 tures are good in compression, the same effect
to 100 nm, but above 1100 ◦ C rapid growth of causes the fibers to be poor in flexibility because
36 Fibers, 2. Structure

they snap easily. On bending, the outside is ex- modulus. The structure of these fibers is de-
tended and the inside is compressed; the small- scribed in Section 3.3; they include the melt-
est radius of curvature R that can be achieved is spun polyamides, polyester, and polypropylene.
given by R = r/e, where r is the fiber radius and e However, the industrial yarns are processed so
the fiber breaking strain. Therefore, the tightest as to maximize the degree of orientation.
achievable curvature is more than 20 times the
fiber radius. In contrast to this, the linear polymer
fibers can be bent back on themselves to nomi- 5.2. Elastomeric Fibers
nally zero values of curvature without breaking,
because yielding on the compression side allows The elastomeric fibers are at the opposite ex-
the neutral plane to move out so that the exten- treme to the high-modulus fibers. Elastomeric
sion on the outer surface does not exceed the fibers are intended for applications in which high
fiber breaking extension. Another benefit, aris- stretch is required; the breaking extension may
ing partly from this and partly from the axial be as high as 500 %, and the modulus is in-
splitting, is that linear polymer fibers are more evitably low.
effective in absorbing energy. They are the best Natural rubber, either in the form of thread cut
materials for ballistic impact resistance fabrics, from sheet or as extruded latex, was the first ma-
in which glass or carbon is useless, and generally terial to be used. It consisted of thick monofila-
show greater damage tolerance in structures. ments or bundles of monofilaments. Their struc-
The other important difference is in thermal ture is the usual cross-linked amorphous net-
resistance, which depends on chemical compo- work formed by vulcanization.
sition. Polyethylene melts at a low temperature, However, modern elastomeric fibers are
and shows excessive creep and loss of mechan- mostly spandex fibers composed of segmented
ical properties even at 100 ◦ C. The aramids and polyurethanes and able to be made in typical
the newer rigid rod polymers do not melt but textile filament diameters. The polymer is an al-
decompose at around 500 ◦ C. Glass begins to ternating block copolymer, in which “soft” seg-
soften at similar temperatures. The ceramic and ments provide the high extension by changing
carbon fibers withstand very high temperatures. from coiled to extended forms, and the “hard”
segments interact and form small crystalline or
quasicrystalline domains to hold the structure
5. Other Fibers together. The fine structure is thus an unori-
ented, fringed micelle form with a low degree
The two major groups of fibers are the general- of crystallinity (high fraction of a rubbery amor-
purpose textile fibers, whose structure is de- phous phase). Under low or moderate tension,
scribed in Chapters 2 and 3, and the high perfor- the mechanism of rubber elasticity will allow
mance engineering fibers, described in Chapter high stretch by the uncoiling of soft segments,
4. However, a miscellaneous group of fibers is but under high tension the alignment of soft seg-
also used for a variety of purposes to be men- ments may lead to some crystallization that re-
tioned in this section. Generally, the main struc- inforces and strengthens the structure.
tural interest is in the chemical composition, and In contrast to natural rubber, in which chemi-
other structural details are either little known or cal cross-links join chains in pairs, the clustering
similar to the most common forms of the particu- of connections in the hard segment domains is an
lar material, which are discussed in other articles important structural feature for good mechanical
in this encyclopedia. properties.
In principle, many possible chemical forms
exist for soft and hard segments, and even with
5.1. High-Toughness Fibers a particular choice of components the propor-
tions may be varied. Couper [78] reports a typi-
Some engineering uses of fibers require high cal monomer for a soft-segment block to be
toughness, shown by a high work of rupture
(energy to break, or area under stress – strain OCN−[A]−NHCO (− O−[B] −CONH−[A] −NHCO)− n
curve), usually accompanied by a fairly high −O− [B]−OCONH− [A]−NCO
 Fibers, 2. Structure 37

where OCN−[A]−NCO is an aromatic di-

isocyanate, O−[B]−OCO is the polyether or
polyester chain of a macroglycol, and n is a small
number varying from molecule to molecule.
This monomer is then linked by bifunctional The shape of the chain makes it easier to form
chain extenders, usually diamines, to the hard into fibers than the p-aramid, and leads to a more
segments. A typical hard segment is reported to extensible fiber with good textile properties.
be Various arimid fibers have been produced
−−
( CONH− [A] −NHCO−NH− [C] −NH−)− m experimentally. The one that is commercially
−CONH− [A] −NHCO available is P84, which was developed by Lenz-
ing but is now produced by Inspec Fibers. Its
where [C] is the aliphatic sequence in a diamine
composition is:
and m is an integer.

5.3. Thermally and Chemically

Resistant Fibers
Apart from polyethylene, all the high-modulus, where R is C6 H4 CH2 .
high-tenacity fibers described in Chapter 4 have Kermel from Rhône-Poulenc is a
good thermal and chemical resistance. This is poly(aramide-imide) fiber. The chemical struc-
particularly so for ceramic and carbon fibers. ture is reported as:
However, other fibers, some of which have only
moderate or poor mechanical properties are used
for insulation protection, filtration, chemical en-
gineering functions, or reduction of fire hazards
[34, pp. 259–324].
Asbestos, which is very brittle and now rec-
ognized to be medically dangerous, was once
widely used. It is an inorganic mineral of struc- A fiber with higher temperature stability
tural interest because its fibrous form derives and high moisture absorption, is poly[2,2 -(m-
from the fact that the unit cell of the crystal is phenylene)-5,5 -bibenzimidazole] or PBI [79],
naturally curved in a small radius. The crystals with the following repeat unit:
grow by forming cylinders of many layers of
rolled-up sheets, limited by the extent of allow-
able distortion as the inner and outer radii de-
part from the preferred value. The space in the
center of the cylinder and between cylinders is This is stabilized by forming a salt with sulfuric
filled with secondary crystallization, in which acid.
the cylinders are incomplete (→ Asbestos). The fine structures of these fibers are similar
Rock wools formed from a melt dispersed to those of other crystallizable polymers spun
into fiber form have a polycrystalline structure. from solution.
Several linear organic polymers are used to If the route to carbon fibers is stopped after
make resistant fibers with reasonable textile the first stage of treatment of acrylic fibers, ther-
properties. One route is to choose rather stiff mally resistant, partially carbonized fibers are
chains with strong interactions, which have a produced. The disorganized structure of Panox
high melting point and a chemical structure se- fibers leads to comparatively low strength, but
lected to avoid flammability and prevent decom- textile properties which give reasonably com-
position at too low a temperature. One such fortable flame-proof protection. Further heat
polymer is the m-aramid, poly(m-phenylene iso- treatment gives improved thermal resistance but
phthalamide) [9016-75-5], marketed as Nomex greater brittleness, as shown by Curlon fibers.
(Du Pont):
38 Fibers, 2. Structure

If good textile properties are sacrificed, ther- PEEK, poly(etheretherketone) is melt-spun

moset resins with a characteristic amorphous, at high temperature by Zyex in a range of cross-
three-dimensional, polymer network structure sections and sizes. The chemical formula is:
provide thermally resistant fibers. The novoloid
fiber Kynol (formerly made by Carborundum
now by Kynol Corporation) is a thermoset phe-
nolic resin, with the structure being a three-
dimensionally cross-linked network, typified by
forms such as:

Basofil from BASF is a melamine-formaldehyde Other polyetherketones have not proved com-
resin. mercially successful.
Polytetrafluoroethylene [9002-84-0], PTFE, Poly(phenylene sulfide) [29] fibers are pro-
is a very inert and stable polymer with the sim- duced by a number of companies. The chemical
ple repeat unit — ( CF2 —
) n . It has good chemi- formula is:
cal resistance at high temperatures. The coiling
of the molecules in shallow turns stiffens the
chains and leads to a high glass transition tem-
perature and stable crystals, which show some Poly(etherimide) fiber is another chemically re-
lattice transitions. The polymer decomposes at a sistant fiber that can be melt-spun. However, its
high temperature before it melts and is insoluble. complicated chain form brings about an amor-
Consequently, it must be spun from a dispersion phous structure. The chemical formula is:
and then consolidated by sintering, which is re-
flected in the structure (→ Fibers, 4. Synthetic
Organic, Chap. 8).
Various other polymers with good chem-
ical resistance can be melt-spun and would
be expected to have structures similar to
other melt-spun fibers; copolymers would have
lower crystallinity. Poly(vinylidene chloride)
(PVDC, −CCl2 CCl2 −) can only be spun when
copolymerized with other vinyl or acrylic 5.4. Special-Purpose Fibers
monomers. Fluorinated polymers, poly(vinyl
fluoride), poly(vinylidene fluoride) and fluori- Many fibers are made for a variety of special pur-
nated ethylene polymers and copolymers are an- poses, but only some brief indications of chemi-
other group of materials. cal and physical structure can be given. A num-
ber of these fibers are described in [27].
 Fibers, 2. Structure 39

Fibers that dissolve in water, possibly hot or mode. The web that is collected is a single fiber
with soap or other common chemicals present, of enormous length. Spinning can be from so-
have some uses. Such fibers can be made lution or melt, so that a wide range of polymer
from poly(vinyl alcohol). — [ CH2 CH(OH)— ] n, nanofibers can be produced. The chemistry and
or from calcium alginate derived from seaweed. fine structure would be expected to be similar
A number of fibers for biomedical applications to that of larger fibers made from the same ma-
are made from linear polymers selected for their terial, though the fact that all the material is as
beneficial interaction with the body [81]. close to the surface as the outer layer of a coarse
Many fibers are naturally absorbent, and this fiber may lead to some differences.
can be enhanced by modifying the chemical or The other type of nanofiber now in experi-
physical structure. A particular example is the mental production consists of carbon nanotubes.
conversion to activated carbon fibers with many These derive from the dsicovery of C60 , in which
accessible microvoids. Unlike the high perfor- carbon atoms are covalently bonded into a spher-
mance carbon fibers, those fibers have not been ical network known as a buckyball. It was then
subjected to high-temperature graphitization. found that hemispherical ends could be linked by
Particular structural features may also occur a tube with a similar network. The basic structure
on a large scale. Hollow fibers, made of a suitable is thus a two-dimensional, covalently bonded
material, can be used for chemical separation sheet of carbon atoms, which wraps around to
processes or the controlled release of reagents. form a tube. Short lengths of multiwalled tubes
Metal fibers may be extremely fine-drawn with diameters of 4 to 50 nm were reported in
wires used for special purposes, such as tungsten 1991 [83]. Long singlewalled carbon nanotubes
filaments in light bulbs or fibers for leakage of with diameters of about 1.5 nm can be produced
static electricity in carpets. A decoratively used in carbon arcs [84, 85] or by laser ablation [86]
fiber is Lurex (Sildorex), which consists of alu- and can be collected in rope form [87]. However,
minum anodized to give color, cut into fine strips these methods are only suitable for producing
from foil, and laminated with plastic protection. minute amounts for scientific study or specialist
These materials have the usual fine structure of uses.
metals. However, a special structure, which can The production of coarse multiwalled carbon
only be found in fibers or thin films, is the amor- fibers by vapor deposition had been known for
phous structure of metallic glasses formed by over 100 years. 21st century research [5, 6] has
rapid chilling [82]. The blocking of defect mo- shown that is possible to grow finer carbon nan-
bility leads to a very high yield stress. otubes by vapor deposition and collect them as
Materials with special electrical or optical long lengths of yarn. Terminology [5] is confus-
properties can be made in fiber form. For ex- ing because this “yarn” is referred to as a “fiber”,
ample, fibers with the structure of electrets are and not as a yarn composed of nanotube fibers.
useful in filtration. The most important appli- The nanotubes may be singlewalled with 1.6–
cation in this category consists of optical fibers 3.5 nm in bundles with a diameter of 30 nm or
for communication. These are usually made of multiwalled with diameters of 30 nm and aspect
specially constituted inorganic glasses, but poly- ratios of 1000:1 [5].
meric fibers have also been tried (→ Fiber Op-
tics).
5.6. Smart Fibers
5.5. Nanofibers and Carbon Nanotubes A major development of the 21st century is
the production of smart fibers [41, 42]. Typi-
Electrospinning [9], which can be carried out cally they are electrically, optically, mechani-
on small-scale equipment, has made it possible cally, thermally, or chemically active and hence
to produce fibers with diameters down to a few respond to external stimuli. It is beyond the
nanometers. It was once thought that the fine- scope of this chapter to go into detail on smart
ness resulted from a splitting of the extruded fibers. From a structural view point, it can be said
fiber, but it is now known that it results from that some fibers may be made of a single active
a massive attenuation of the fiber in a whirling
40 Fibers, 2. Structure

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 Fibers, 3. General Production Technology 1

Fibers, 3. General Production Technology

Werner Stibal, EMS Inventa-Fischer AG, Domat/Ems, Switzerland (Chaps. 1, 3.2, 5, and 7)
Raimund Schwarz, EMS Inventa-Fischer AG, Domat/Ems, Switzerland (Sections 2.1, 2.2, and 2.4)
Ulrich Kemp, EMS Inventa-Fischer AG, Domat/Ems, Switzerland (Section 3.1)
Klaus Bender, EMS Inventa-Fischer AG, Domat/Ems, Switzerland (Chap. 4)
Friedrich Weger, EMS Inventa-Fischer GmbH, Berlin, Germany (Chap. 6)
Manfred Stein, EMS Inventa-Fischer AG, Domat/Ems, Switzerland (Section 2.3, Section 3.3)

1. Introduction . . . . . . . . . . . . . . 3 3.1.4. Superhigh-Speed Spinning . . . . . 35

2. Theory and Mechanisms of Fiber 3.1.5. Draw Twisting and Draw Winding . 36
Production . . . . . . . . . . . . . . . 3 3.1.6. Draw Warping . . . . . . . . . . . . . 37
2.1. Spinning . . . . . . . . . . . . . . . . 3 3.1.7. Horizontal Drawing . . . . . . . . . . 38
2.1.1. General Description . . . . . . . . . . 3 3.1.8. Spin Drawing . . . . . . . . . . . . . . 39
2.1.2. Theory and Mechanism of Spinning 4 3.2. Solution Spinning of Filament
2.1.2.1. Spinnability of Fluids . . . . . . . . . 4 Yarns . . . . . . . . . . . . . . . . . . . 39
2.1.2.2. Flow Processes in Spinning . . . . . 5 3.2.1. Dry Spinning . . . . . . . . . . . . . . 40
2.1.3. Melt Spinning . . . . . . . . . . . . . 10 3.2.2. Wet Spinning . . . . . . . . . . . . . . 40
2.1.4. Solution Spinning . . . . . . . . . . . 17 3.3. Texturing of Filament Yarns . . . 41
2.1.4.1. Dry Spinning . . . . . . . . . . . . . . 17 3.3.1. Development of Texturing Processes 41
2.1.4.2. Wet Spinning . . . . . . . . . . . . . . 19 3.3.2. False-Twist Texturing . . . . . . . . . 41
2.2. Drawing . . . . . . . . . . . . . . . . . 21 3.3.3. Air-Jet Texturing . . . . . . . . . . . . 44
2.2.1. Elongation Properties of As-Spun 3.3.4. Stuffer Box Texturing . . . . . . . . . 47
Yarns . . . . . . . . . . . . . . . . . . . 21 3.3.5. Bistructural Texturing . . . . . . . . . 48
2.2.2. Mechanism of Cold Drawing . . . . 22 4. Manufacture of Tow and Staple
2.2.3. The Drawing Process . . . . . . . . . 23 Fibers . . . . . . . . . . . . . . . . . . 49
2.2.4. Draw Ratio and Tensile Strength . . 24 4.1. Fiber Spinning . . . . . . . . . . . . 49
2.2.5. Ultrahigh-Strength Synthetic Yarns 25 4.1.1. Melt Spinning . . . . . . . . . . . . . 49
2.3. Crimping . . . . . . . . . . . . . . . . 25 4.1.1.1. Conventional Process . . . . . . . . . 49
2.3.1. General Description . . . . . . . . . . 25 4.1.1.2. Compact Process . . . . . . . . . . . . 50
2.3.2. Crimping Processes . . . . . . . . . . 25 4.1.1.3. Continuous One-Step Process . . . . 53
2.3.2.1. Spontaneous Crimping . . . . . . . . 26 4.1.2. Wet Spinning . . . . . . . . . . . . . . 54
2.3.2.2. Deformation Crimping . . . . . . . . 26 4.1.3. Dry Spinning . . . . . . . . . . . . . . 54
2.3.2.3. Bicomponent Crimping . . . . . . . . 27 4.2. Posttreatment of Tow and Staple
2.3.3. Crimping of Staple Fibers and Fila- Fibers . . . . . . . . . . . . . . . . . . 54
ment Yarns . . . . . . . . . . . . . . . 27 4.2.1. Drawing of Tow . . . . . . . . . . . . 56
2.4. Heat-Setting . . . . . . . . . . . . . . 27 4.2.2. Washing and Finishing . . . . . . . . 57
2.4.1. Purpose . . . . . . . . . . . . . . . . . 27 4.2.3. Drying and Heat-Setting . . . . . . . 58
2.4.2. Mechanism . . . . . . . . . . . . . . . 28 4.2.4. Crimping . . . . . . . . . . . . . . . . 59
2.4.3. Shape Retention and Molecular 4.2.5. Cutting . . . . . . . . . . . . . . . . . . 60
Memory . . . . . . . . . . . . . . . . . 30 4.2.6. Packaging . . . . . . . . . . . . . . . . 62
3. Manufacture of Filament Yarns . 31 5. Manufacture of Monofilaments . 62
3.1. Melt Spinning of Filament Yarns 31 6. Process Technologies for Spun-
3.1.1. General Aspects . . . . . . . . . . . . 31 bonded Nonwovens . . . . . . . . . 64
3.1.2. Conventional Spinning . . . . . . . . 31 7. Economic Aspects . . . . . . . . . . 64
3.1.3. High-Speed Spinning . . . . . . . . . 34 8. References . . . . . . . . . . . . . . . 66

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 511
2 Fibers, 3. General Production Technology

Acronyms and Symbols staple fibers). Monofilament is a single conti-

nous fiber, filaments are composed of a certain
BCF bulked continuous filament
number of continous spun and collected single
DSC differential scanning calorimetry
fibers, tow consists of a collection of thousands
FDY fully drawn yarn
of continous filaments, and staple fibers are tow
HE highly elastic
that has been cut into discrete lengths. For a gen-
LOY low orientation yarn
eral description of fibers and their properties, see
NVC nip-controlled vector
→ Fibers, 1. Survey.
PES polyester
Key process steps in fiber production are
PETP poly(ethylene terephthalate)
POY partially oriented yarn 1) Spinning
RFR ribbon-free random wind 2) Drawing
F degree of setting, force 3) Posttreatment
G free energy, polymer throughput per spin- In the first of these steps, spinning, polymers
neret hole are forced by dosing units through small capillar-
K energy of cohesion ies, either as a melt or in solution and then solid-
L maximum thread length ified into fibers by cooling, precipitation, or sol-
m∗ mass flow rate vent evaporation. During spinning, the macro-
M̄ w weight-average molecular mass molecular chains are only partially oriented in a
N normal stress difference preferred direction. (Spinning may also be de-
S entropy, shrinkage fined to include the process in which fibers of
T titer (fineness), temperature finite length, i.e., staple fibers, are combined to
U internal energy form yarn; this is, however, part of a different
v velocity technology and is not treated in this article.)
vL take-up velocity In the second step, drawing, the as-spun fibers
v0 extrusion velocity are often stretched to many times their original
V volume length. Drawing increases the molecular orien-
Vz spin-draw ratio tation along the fiber axis and is frequently ac-
x distance companied by an increase in crystallinity and
α countersink angle fiber strength.
β angle of transition In the third step, posttreatment, the drawn
ε elongation fibers are heated under tension or under de-
ε̇ elongation rate fined conditions of relaxation (heat-setting or
εH Hencky measure of elongation thermosetting). If necessary, filaments, which
γ̇ shear rate after spinning and drawing normally have a flat
θ temperature, normal stress coefficient characteristic, can also be textured, and tow can
η shear (dynamic) viscosity be crimped. Heat-setting changes the fiber mor-
ηD elongational viscosity phology and allows the properties of the filament
σ tensile stress, tenacity at break (based on yarn, staple fibers, or tow to be adapted to end-
titer) use requirements. A finishing oil must be applied
σ0 tenacity based on initial fineness to the fibers to improve their processing proper-
σs surface tension ties. The proper formulation of a finishing oil
σt tenacity based on cross-sectional area requires a balanced combination of lubricating,
τ shear stress, relaxation time cohesive, and antistatic properties.
The classical production of synthetic fibers
involves several separate steps. New technolo-
1. Introduction gies have been developed in the past few years
with the goal of integrating as many production
Man-made fibers are manufactured by convert- steps as possible into a single continous process;
ing high-molecular polymer materials into con- this has improved both the economics of syn-
tinuous fibers (monofilaments, filaments, tow, or thetic fiber manufacture and the quality of the
products.
 Fibers, 3. General Production Technology 3

2. Theory and Mechanisms of Fiber extrusion velocity for some polymers exceeds
Production the take-up velocity (i.e., draw ratio < 1).
The most important characteristic of the as-
2.1. Spinning spun material is the titer T which is a measure of
its fineness and is also called the linear density.
This section deals solely with melt and solution The titer is defined as the mass per unit length
spinning. Other spinning methods such as emul- (grams per meter) and is expressed in tex:
sion and suspension spinning, phase-separation 1tex = 1g per 1000m
spinning, reaction spinning, and interfacial, and
1dtex = 1g per 10000m
surface spinning are described in [1], [2].
By differentiating fiber mass and length with
respect to time, the equation defining the fine-
2.1.1. General Description ness can be rewritten as:

In all spinning processes, a spin pump contin- Massflow rate (g/s)

Titer =
uously forces a fluid spinning mass, sometimes Take − up velocity (m/s)
under considerable pressure, through a spinneret m∗ (g/s)
T (dtex) = ×10000
orifice (the shaping element) into a suitable liq- vL (m/s)
uid or gaseous medium. The resulting filament This equation is frequently used in spinning
is solidified by adjusting the temperature or the technology. The yarn number is obtained by as-
concentration of the medium. The spinning mass suming m∗ to be the throughput of the entire
is converted into a fluid state by melting or by spinneret plate. To obtain the fineness of an in-
dissolution, depending on the properties (ther- dividual filament, the yarn number is divided by
mal stability) of the raw material. If the material the number of spinneret holes. If the spinning
is neither fusible nor soluble, special spinning mass is diluted, m∗ must be corrected appro-
processes are required. As the filament leaves the priately to calculate the fineness. The equation
spinneret, it is narrowed, while still in the fluid shows that the as-spun fineness depends only
state, by drawing off at a constant take-up veloc- on the spinneret throughput and the take-up ve-
ity. The polymer molecules become weakly ori- locity. The diameter of the spinneret hole (and
ented along the longitudinal axis of the fiber as the associated spin-draw ratio) does not affect
solidification progresses. Changes in morphol- fineness but does influence the process of fiber
ogy may occur depending on the process used. formation occurring between the spinneret and
the take-up unit.
Characteristic Variables. An important The fiber diameter d, in millimeters, can be
characteristic of the spinning process is the calculated from the titer with the aid of the vol-
spin-draw ratio V Z which represents the ratio ume density
. For a fiber with a circular cross
of the take-up velocity vL to the extrusion ve- section:
locity v0 , i.e., the speed at which the spinning

mass leaves the spinneret: T
d= 0.02×
π·
VZ =vL /v0
where T is expressed in decitex and
in grams
The extrusion velocity v0 is calculated from per cubic centimeter.
the ratio of the volume throughput (cubic cen-
timeters per second) to the free cross-sectional
area of the spinneret holes (square centimeters); 2.1.2. Theory and Mechanism of Spinning
both parameters are based on either the entire
spinneret plate or on only a single filament (one 2.1.2.1. Spinnability of Fluids
hole). The spin-draw ratio varies with the spin-
ning process; in melt spinning, it may be as high Spinnability, i.e., the ability to form threads, is
as several hundred, but in solution spinning the exhibited by many materials which differ widely
in structure and composition; it is by no means
4 Fibers, 3. General Production Technology

a unique property of macromolecules. Chain- Depending on prevailing conditions, the fil-

like macromolecules are, however, a prereq- ament will fail by the mechanism that predicts
uisite for the production of useful fibers with failure at the shorter filament length. By plotting
good mechanical properties. According to Zi- theoretical curves for both models, a region of
abicki [1], the maximum thread length attain- spinnability becomes apparent which coincides
able on application of tensile stress is a measure with that observed in practice (see Fig. 2).
of spinnability. The maximum thread length L
depends not only on the material, but also on
the spinning conditions. For a given substance,
L depends primarily on the product v · η, where
v is the pulling velocity in meters per second and
η is the shear viscosity. As shown in Figure 1, L
passes through a maximum at intermediate v · η
values where it is affected to some extent by the
ratio of surface tension to viscosity.

Figure 2. Superposition of theoretical curves of capillary

wave failure (− − −) and cohesive failure (. . . .).
The maximum length L of a fluid filament is plotted as a
function of the product of the extrusion velocity v0 and the
shear viscosity η; d 0 = initial diameter; ξ = d ln (v/v0 )/dx =
axial deformation gradient; σ s = surface tension; K = energy
of cohesion; τ = relaxation time, time for the stress (stored
energy) created by a sudden deformation to decay to the
(1/e)th part [4].
The arrows show the direction in which the theoretical curves
Figure 1. Maximum length L of a fluid thread as a function
shift when the indicated parameter increases
of the product of pulling velocity v and shear viscosity η.
A thread was pulled by a rod from solutions containing the in-
dicated concentrations of cellulose acetate in weight percent;
intrinsic viscosity [η] = 1.92 dL/g in an 85 : 15 (vol : vol)
acetone – water mixture [3] 2.1.2.2. Flow Processes in Spinning
A fluid, as-spun filament is thought to break Internal and external flow processes occur dur-
by two mechanisms [4]. The first of these is co- ing fiber spinning. The flow of the spinning mass
hesive failure in which fracture occurs when the toward the spinneret and its passage through the
tensile stress exceeds the tensile strength of the spinneret holes are termed internal processes.
material at some point along the path of filament The external processes include the behavior of
formation. Tensile strength depends on the en- the jet of spun material on leaving the spinneret
ergy of cohesion (critical elastic energy) of the hole, as well as drawing and solidification of the
material. Tensile stress can build up if the fluid, fiber. The flow processes occurring inside and on
in contrast to ideally viscous Newtonian media, leaving the spinneret are governed by the shear
is able to store energy of deformation, i.e., if it flow properties of the spinning mass under the
is viscoelastic. The second failure mechanism prevailing extrusion conditions (i.e., shear vis-
is termed capillary wave failure and depends cosity η and shear rate γ̇). Subsequent flow pro-
on the ratio of surface tension to viscosity. The cesses are characterized by drawing properties
larger the ratio, the more rapid is the increase in and conditions (extensional or elongational vis-
the amplitude of initially minute waves on the cosity η D and elongation rate ε̇). These two types
filament surface. After a certain distance, the of flow are shown schematically in Figure 3.
capillary filament is divided into droplets and
breaks (a fine stream of water also exhibits this Flow Properties of Fluids. In contrast to
type of behavior). solids, liquids begin to flow continuously when
 Fibers, 3. General Production Technology 5

Figure 3. Schematic of flow processes in fiber spinning

A) Laminar shear flow shown as simple shear between horizontal layers and as tubular flow with telescopic shearing; B)
Monoaxial, steady-state elongational flow
F = force; A = area; x = coordinate axis; r = radius; v = velocity

a force is applied. If the force is applied tan- In Newtonian fluids, η is constant over the
gentially to a given plane, an equal and opposite entire range of shear rate (i.e., η is a material
force must act on the opposing interface, and constant). However, polymer melts and poly-
shear flow occurs. Infinitely thin laminar lay- mer solutions used in fiber production gener-
ers are displaced in parallel and exhibit a ve- ally exhibit a more complex behavior. They
locity profile; the energy brought into play is are pseodoplastic (η decreases as the shear rate
converted to frictional heat. In tubular flow, the increases, i.e., non-Newtonian) or viscoelastic
layers are concentric and the driving force is ap- (viscosity is time-dependent), and also display
plied to the circular face. The opposing force rubber-like elastic deformation. Gleissle disco-
is created by friction against the tube wall. The vered that all three phenomena can be attributed
layers shown in Figure 3A must be imagined to the elastic behavior of polymers [5]. Thus,
as being infinitely long in the direction of flow. the steady-state viscosity function η (γ̇) can be
In the steady-state, the fluid leaving the element used to deduce the time-dependent behavior of
under consideration is constantly replaced. The a viscoelastic fluid under stress (mirror rela-
following terms are defined in laminar, linear tions). At the molecular level, the high elas-
shear flow: ticity of polymers, in contrast to solids, cannot
Shear rate γ̇ =dv (x) /dx for a planar
be explained by interatomic forces (with corre-
surface, spondingly low elongation). In macromolecular
or chains, the restoring force is instead produced
dv (r) /dr for a tube
Shear stress τ =F/A by entropy effects which are based on the rel-
Shear viscosity η = τ /γ̇ atively unhindered rotation of the main single
(also called Newtonian
viscosity or dynamic
valence bonds and the nonextended bond an-
viscosity) gles. The most entropically favorable (i.e., most
where x = coordinate axis, v = velocity, r = tube radius, F = applied probable) conformation is that of a ball with ran-
force, and A = area.
domly coiled chains [6]. In the absence of an
external elongational force, the macromolecular
Thus, to achieve a given average flow rate, a polymer chains will adopt this conformation.
force must be applied which is proportional to Elongational flow occurs when a force acts
the shear viscosity of the material used. perpendicular to an area with a finite cross sec-
6 Fibers, 3. General Production Technology

tion (see Fig. 3B). Because the volume of an im- elongated threads; consequently, the flow resis-
compressible fluid must remain constant, elon- tance drops.
gation is accompanied by a simultaneous trans-
verse contraction. Hence during steady elonga- Flow Processes in the Spinneret and Fila-
tional flow, an infinitely small volume of fluid ment Formation. The most obvious evidence
with an initial cross section A0 accelerates in the for the elastic behavior of polymers and their
direction of flow under the action of the elon- solutions during spinning is the fact that the ex-
gating force. In the steady state, the outflow is trudate leaving the spinneret has a larger diam-
continuously replaced by inflow through the area eter than the spinneret hole (see Fig. 5A). This
A0 . The following terms can be defined and are effect is called die swell, onion formation, or the
analogous to those already given for shear flow: Barus effect. The ratio of the maximum diameter
of the extrudate to the diameter of the spinneret,
Elongation rate ε̇= dv (x) /dx
Tensile stress σ =F/A (x)
d max : d 0 , is called the die swell ratio or swelling
(also called elongational factor.
or normal stress)
Elongational viscosity ηD =σ/ε̇
(also called extensional
or Trouton viscosity)

Figure 4. Steady-state shear and elongational viscosity as a

function of the rate of deformation
Measurements were performed on branched polyethylene
at 150 ◦ C [7] (η = viscosity; ηD = elongational viscosity;
η 0 = limiting viscosity at zero shear)
Figure 5. Spinneret flow and die swell ∗
For an incompressible Newtonian material A) Deformation of a cylindrical fluid element during extru-
the following relation holds: η D = 3 η (analogous sion through a spinneret; B) Flow of fluids out of a tube
to the material parameters during the deforma- d 0 = capillary diameter; d max = maximum diameter of the
extrudate
tion of a solid). For non-Newtonian materials ∗ Reproduced with permission from [8].
this relation is valid only at low rates of deforma-
tion (see Fig. 4); under these apparently Newto- There are two reasons for die swell:
nian conditions, the steady-state viscosity does 1) The inflowing mass in front of the spinneret
not change (i.e., η = η 0 , where η 0 is the limit- capillary is subjected to an elongating de-
ing viscosity at zero shear). As shown in Fig- formation in addition to shear. The resultant
ure 4, further elongation is at first accompanied elastic stress partially relaxes during flow
by consolidation, i.e., η D increases. The shear through the spinneret capillary, the resid-
viscosity η simultaneously decreases, however, ual elasticity increases with decreasing resi-
because the shearing force increasingly orients dence time (i.e., lower ratio of the capillary
the randomly coiled, ball-shaped molecules into length l to the capillary diameter d 0 ). Once
the mass has left the spinneret, its diameter is
 Fibers, 3. General Production Technology 7

not limited by the capillary walls; the resid- reduced by the shear rate γ̇. The importance of
ual elasticity recovers, and this leads to ex- normal stresses is illustrated by the fact that, for
pansion. The l : d 0 ratio usually varies from 1 the polymers used in the manufacture of man-
to 3. Values for d 0 range from 0.1 to 0.4 mm made fibers, N 1 is greater than τ , even at low
with residence times of 10−4 to 10−2 s; poly- shear rates γ̇ = ca.10−1 −10−2 s−1 ).
mer relaxation times can be as high 1 s.
2) Even polymer melts or solutions which
emerge from a long tube without an ori-
fice exhibit an increase in diameter (Fig. 5B).
As mentioned previously, this is because
shear flow produces entropy – elastic molec-
ular orientations, as a result of the radial ve-
locity field; a persistent tensile stress is thus
created which is a function of the shear ve-
locity (dynamic orientation).
For non-Newtonian fluids, the sum of these
two elastic deformations causes the emerging fil-
ament to contract. The contraction in length is
proportional to the square of the simultaneous
swelling (die swell) factor. Under normal con-
ditions, the filament diameter expands to 1.1 –
2.5 times the capillary diameter. For a viscous
Newtonian fluid, however, the diameter of the
emerging strand is approximately 14 % smaller
than that of the capillary (see Fig. 5B).
For a complete description of the deforma-
tion of non-Newtonian materials during shear
flow (such as die swell), normal stresses oc-
curring along the three major coordinates must
also be considered [8]. In the limiting case of
incompressible fluids, rheology is not affected
by absolute hydrostatic pressure; only the differ-
ences between the normal stresses are important.
These are defined as follows (see also Fig. 6):
N1 =τ1 −τ2 (firstnormalstressdifference)
N2 =τ2 −τ3 (secondnormalstressdifference) Figure 6. State of normal stress in a fluid element
p = hydrostatic pressure acting on all sides; τ 1 , τ 2 and
where τ 1 , τ 2 , and τ 3 are the normal stresses act- τ 3 = normal stresses acting on the areas perpendicular to
ing on the areas perpendicular to the three space the coordinates x 1 , x 2 , and x 3 , respectively
coordinates. Shear rates at the walls of spinneret capillar-
In the case of simple, linear shear, N 2 = 0 ies are usually 102 – 105 s−1 . If the ratio N 1 : τ
and N1 =θ· γ̇ 2 , where γ̇ is the shear rate and becomes too large (i.e., if the shear rates are too
θ is the normal stress coefficient for the steady high), melt fracture occurs. Melt fracture is a
state. The parameter N 1 has the same effect on form of unstable flow that is produced by oscil-
a fluid stream as an externally applied tensile lating elastic deformations. This instability is not
stress. The resultant phenomena are called nor- related to the Reynolds criterion for turbulence
mal stress effects or the Weissenberg effect. used in hydrodynamics. Melt fracture can be rec-
The mirror relations derived by Gleissle [5] ognized by the fact that the filament emerging
can be used to calculate θ directly from the vis- from the spinneret is not smooth: its diameter
cosity function η · (γ̇). The parameter θ is the is irregular and varies more or less periodically
greater, the more the shear viscosity has been
8 Fibers, 3. General Production Technology

Figure 7. Velocity profile of an extruded, tapering filament

d 0 = capillary diameter; d max = maximum filament diameter; γ̇ = shear rate; ε̇ = elongation rate; x = distance from the spinneret
orifice

Figure 8. Schematic of the spinning process [12]

[9], [10]. Gleissle [11] discovered a universal within a distance of 1 – 3 mm, the tensile force
critical value of the ratio N 1 : τ for different begins to act on the fluid thread. The radial ve-
polymers, above which melt fracture occurs: locity over the whole cross section is constant;
hence, the jet of spun fluid is accelerated and be-
(N1 /τ )crit = 4.6 ± 0.2
gins to taper. Under normal spinning conditions,
The spinneret hole diameter is the major fac- the axial velocity gradient is ca. 10 – 70 s−1 , the
tor affecting the shear rate and therefore the first largest deformation occurring within the first
normal stress difference N 1 . The diameter must 20 – 30 cm. Spinnability is stabilized by the on-
therefore have a suitable minimum value; its up- set of coagulation or solidification and, at least in
per limit is determined by the fact that the spin- the initial region, by the increase in elongational
draw ratio and elongation rate must not be too viscosity shown in Figure 4.
great if excessive preorientation and cohesive The typical behavior of several fiber param-
failure are to be avoided. eters during spinning is depicted schematically
Under steady-state conditions, the extruded in Figure 8. Consolidation of the filaments, in
filament exhibits the velocity profile shown in the sense of solidification, is achieved by cool-
Figure 7. A parabola-shaped, shear flow profile ing (quenching) or coagulation in a spinning
develops in the spinneret capillary. After the ma- medium and is associated with an increase in
terial leaves the spinneret, the profile flattens out the limiting viscosity at zero shear η 0 . Since re-
because frictional force is no longer exerted by laxation is slower in a viscous mass, the buildup
the capillary walls and deceleration results si- of tension resulting from the elongating forces
multaneously due to swelling. Once the max- and increased viscosity is accompanied by an
imum filament diameter is reached, normally
 Fibers, 3. General Production Technology 9

increase in molecular orientation along the fil- ever, crystallization is difficult to predict because
ament axis. This orientation can be measured the interaction of polymer properties, spinning
by birefringence and remains in the as-spun fil- conditions, orientation, and crystallization are
ament after it has solidified at its glass transi- complicated.
tion temperature. The glass transition temper- During spinning, a filament is subject to the
ature corresponds to the softening point of the balance of physical forces shown in Figure 9.
amorphous polymer regions; the melting point The first detailed investigation of the forces op-
of a polymer, however, is defined as the melting erating during spinning was carried out by Zi-
point of its crystallites, above which the melt abicki [13]. At any given distance x from the
is thermoformable. Once the solidification point spinneret, the retarding forces are balanced by
has been reached and deformation is complete, the deformation forces:
the stress continues to increase because of exter-
nal friction between the thread and the spinning Frheo (x) =
medium. Fext +Fgrav (x) −Finert (x) −Ffric (x) −Fsurf (x)

where
F rheo = rheological (viscous) force, tensile
force
F ext = external take-up force (constant along
the entire threadline)
F grav = force of gravity (weight of filament sus-
pended from point x) – if the fiber is spun
vertically upward F grav is negative; if it
is spun horizontally, F grav is zero
F inert = force of inertia (due to acceleration to
vL , the velocity at the end of the spinning
path)
F fric = frictional force between the surface of
the filament and the spinning medium
F surf = force due to surface tension (tends to
minimize surface area of the filament by
shrinkage)
At the solidification point (x = x s ) and there-
after, F inert is zero; in addition, the surface
and interfacial tension are often negligible. At
the end of the spinning path (x = x L ), F grav (in
downward spinning) and F fric also equal zero;
at this point, the tensile force applied to the fil-
ament, F rheo , is therefore equal to the external
take-up force. Complicated mathematical proce-
dures are, however, required to predict the course
Figure 9. Balance of forces in a spun filament (direction of of filament formation (i.e., decrease in diameter)
spinning is downward) from the elongational viscosity and the calcu-
d = filament diameter; d 0 = capillary diameter; lated force components on the right-hand side
d max = maximum filament diameter; x = distance of the above equation.
from spinneret; v = filament velocity; θs = solidification
temperature; subscripts S and L indicate solidification
point and end of spinning path, respectively (see text for
definition of forces) 2.1.3. Melt Spinning
Partially crystalline regions may be formed Melt spinning is the simplest spinning process.
during spinning, depending on how rapidly the It is applied to polymers that can be melted and
polymer tends to crystallize. In general, how- which do not decompose or change substantially
10 Fibers, 3. General Production Technology

when maintained in the molten state for several where

minutes at a temperature up to 300 ◦ C (e.g., poly-
esters, polyamides, polyolefins). The highly vis-
= polymer density
cous melt is forced through a spinneret at a high A= cross-sectional area of filament
pressure (ca. 10 – 20 MPa), therefore the spin- v= filament velocity
neret plate has to be quite thick (ca. 10 mm). G= polymer throughput per spinneret hole
Figure 10 shows the geometry of a spinneret hole (e.g., grams per minute)
used in melt spinning.
If the filament cross section is circular and
A=πd2 /4
(d = filament diameter), it follows that


4G G
v (x) = or d (x) = 2×
π d (x)2 π v (x)

Hence, the decreasing diameter of the as-spun

filament is a direct measure of the increasing
speed during spin elongation. Because frictional
forces are relatively low when spinning is per-
formed in air, take-up speeds of 8 – 25 m/s are
obtained in classical melt spinning; speeds up
to 100 m/s or more are possible in high-speed
spinning [14].

Mathematical Models. Melt spinning is the

spinning process most easily described by the-
oretical models and mathematics. Terms have
been derived for the force and heat balance re-
quired to quantitatively describe filament forma-
Figure 10. Vertical section through a spinneret hole used tion during melt spinning [13], [15]. The heat
for melt spinning balance is necessary to calculate the tempera-
α = countersink angel; β = angle of transition; ture-dependent elongational viscosity. Hamana
d 0 = capillary diameter (ca. 0.2 – 0.4 mm, permissi-
ble variation = ±0.002 mm); D = prechannel diameter; [16] derived a coupled system of three first-order
l = capillary length (ca. 2 d 0 ) differential equations containing the filament
variables velocity v (x), tensile force F rheo (x),
After leaving the spinneret, molten filaments and temperature θ (x). The equations and both
are cooled (quenched) in air as a spinning the initial and boundary conditions also take
medium; cooling is usually accelerated by blow- into consideration the physical properties of the
ing the air across the filaments. In special cases, polymer and air, as well as the spinning pa-
a liquid is used as a spinning medium to acceler- rameters (diameter of the spinneret hole, extru-
ate cooling even further (see also production of sion temperature, throughput per hole, take-up
monofilaments, Chap. 5). This is not to be con- speed, and velocity of blown air). The mathe-
fused with wet spinning, which is dealt with in matical solution of this system of equations is
Section 2.1.4.2. difficult because it requires numerical integra-
The key characteristic of melt spinning is that tion and knowledge of the initial value of the
the filaments are extruded from a melt and solid- filament tensile force at the spinneret, F 0 . The
ified by heat exchange with a spinning medium. parameter F 0 is defined indirectly by the bound-
Since no exchange of material occurs, under ary condition that the filament speed must equal
steady-state conditions the equation of continu- the take-up velocity when the filament reaches
ity (the simplest form of material balance) ap- the take-up unit or is at its glass transition tem-
plies at every distance x along the filament: perature. Hence, the solution requires several it-
·A (x) ·v (x) =G= constant
erative integrations in which an estimated initial
 Fibers, 3. General Production Technology 11

value of F 0 is fitted until it meets the boundary effect of spinning parameters on filament for-
condition. mation can be simulated easily, but this does not
make spinning experiments superfluous.

Figure 11. Temperature variation along a bundle of filaments

during melt spinning of poly(ethylene terephthalate) (PETP)
[17]
Spinning path, ca. 1 m long; 70 ◦ C isotherm = solidification
Figure 12. Change in the cross section of nylon filaments
curve at the glass transition temperature (T g )
spun from a spinneret with star-shaped holes [18].
Spinning length indicates distance between spinneret and
liquid cooling bath
Computer Simulation. Hamana [16] was
the first to write a computer program for sim- The program used by Hamana [16] has the
ulating the melt spinning process. His measure- drawback that it can only be used to simulate the
ments on the variation of temperature and diame- formation of individual, isolated filaments under
ter of poly(ethylene terephthalate) PETP and ny- defined quenching conditions. In practice, fibers
lon 6 filaments confirmed his theoretical calcu- are spun in bundles which contain up to 3000
lations. Poly(ethylene terephthalate) has a high individual filaments, and quenching conditions
glass transition temperature and does not de- varying considerably from filament to filament.
velop any significant crystallinity during spin- Since air is blown from one side, cooling condi-
ning up to medium speed. The birefringence, de- tions can be very poor for filaments furthest from
termined as a measure of molecular orientation, the air source for two reasons: (1) air reaching
is proportional to the tensile stress calculated by the rear filaments is already preheated and (2)
the program. Furthermore, the birefringence of the velocity of the transverse stream of air de-
the quenched, as-spun filament corresponds to creases because the front filaments entrain part
the tensile stress at the glass transition tempera- of the blown air in their aerodynamic boundary
ture. Mathematical simulation can thus be used layer [1]. Therefore, the program for individ-
to predict the properties of as-spun PETP fila- ual filaments has been extended to include the
ments as a function of spinning conditions. The heat and mass balance of air so that calculations
12 Fibers, 3. General Production Technology

Figure 13. Tenacity versus take-up speed for PETP

filaments of two different intrinsic viscosities [20], Figure 14. Birefringence versus take-up speed for PETP fil-
∧
1 cN/dtex = 0.8839 g/den aments of two different intrinsic viscosities [20]

can be applied to the entire filament bundle. Fig- perature is reached. The spinning temperature
ure 11 shows the isotherms obtained from such must not be too close to the polymer melting
a simulation. The cooling path in the first row point because the swelling factor increases sig-
of filaments is quite short and corresponds to nificantly just above the melting point, which
that obtained for individual filaments. However, makes the emerging filament rounder. Cooling
filaments in the fifth and subsequent rows take conditions are most difficult to prescribe for hol-
about twice as long to solidify. In practice, this low fibers spun from spinnerets that usually con-
can lead to undesirable sticking when the fila- sist of a ring slit that is divided into one or more
ments come into contact with one another. Fiber segments by fillets (see Fig. 67); individual seg-
quality data and the filament-yarn bundle sim- ments must then flow together before solidifica-
ulation program have been used to show how tion occurs. The external pressure is higher than
air blowing and quenching can be improved and that inside the hollow filament cavity and thus
standardized without having to reduce the num- reduces the size of the cavity. As a result of this
ber of filaments [17]. pressure difference, the air which later fills the
hollow filament flows into or is sucked into the
Filament Shape. Noncircular spinneret filament immediately below the spinneret; it en-
holes may be used to shape the filament profile ters at the fillets between the circular segments,
and thus modify the properties of the product before the filament closes up. Expensive spin-
(e.g., luster, touch, coloration). The cross section neret designs have been patented in which this
of the spun filaments generally differs from that problem is overcome by spinning the hollow fil-
of the spinneret holes because surface tension ament from a closed ring and blowing an inert
tends to minimize the surface area of the fila- gas into the center of the hollow internal cavity
ment. For any given length, a minimal surface [19].
area is achieved when the cross section is a solid
circle. This change, however, does not occur Filament Formation in Melt-Spinning
instantly because it is retarded by viscosity. An Processes. In the 1970s a new fiber manufactur-
example of the change in cross section along the ing process was developed that combined draw-
spinning path is illustrated in Figure 12. ing and texturing. With this new process, un-
A well-developed profile is obtained by spin- drawn, partially oriented yarn (POY) is still pro-
ning at a low temperature, with rapid quenching; duced today. In the case of poly(ethylene tere-
the viscosity then increases rapidly and the pro- phthalate), PETP, the spinning speeds of this
file is “frozen” when the glass transition tem-
 Fibers, 3. General Production Technology 13

process is between 2700 and 3500 m/min, de- sponds to higher intrinsic viscosity, are shifted
pending on the desired product. However, higher to lower spinning speeds, and the maximum
spinning speeds are disadvantageous for the pro- heights of the curves are different. For a higher
ducer because of the increase in orientation intrinsic viscosity (0.95 dL/g) the onset of the
and crystallinity, which deteriorate the required strong increase in molecular orientation starts at
properties of this pre-yarn. At spinning speeds lower velocities, but the maximum attained by
above 3500 m/min the textile physical properties the low-viscosity PETP is higher (Figs. 13, 14,
of the textured yarn are negatively influenced. 15). Therefore, by varying the intrinsic viscosity,
Especially the draw ratio in the texturing process it is possible to shift the molecular orientation at
is much lower than that of conventional POY, so a given spinning speed to lower or higher values.
that the productivity would be reduced. Because But this adjustment is limited. Not every molec-
the draw ratio is lower and the final titer (fiber ular mass is suitable for all kinds of end prod-
diameter) is fixed, the POY titer must also be uct. However, polymer modifications can also
reduced. Hence, if a conventional PETP is used, be used to influence the POY textile physical
typical limits exist which are attributable to the properties (see page 16).
inherent properties of the spin polymer or the
corresponding polymer physics.
Which factors influence the fiber formation
process? For two different intrinsic viscosities
(IVs), Figures 13, 14, and 15 show the tenac-
ity, crystallinity, and birefringence as a func-
tion of spinning speed [20]. For an intrinsic
viscosity of 0.95 dL/g, which corresponds to
high molecular mass PETP for the production of
tire cord, molecular orientation (birefringence),
crystallinity, and tenacity already increase at rel-
atively low spinning speeds.

Figure 16. Fine-structure model for a spinning speed of

10 000 m/min [24]

Morphology of the As-Spun Fiber. Fig-

ure 16 shows the morphology of a semicrys-
talline PETP fiber. Between the crystallites,
which are always more or less highly oriented,
are the noncrystalline regions, which begin to
orient themselves at a certain spinning stress.
When a critical molecular orientation is attained,
the intermolecular forces are so high that crys-
tallites are spontaneously formed (Fig. 17) [21].
In high-speed spinning, the structure-forming
process is so fast that inter- and intrafibrillar
Figure 15. Crystallinity versus take-up speed for PETP fil- voids are generated. This can be detected by
aments of two different intrinsic viscosities [20] the positron-annihilation method, whereby the
For both IVs a maximum exists in all three lifetime of the positron is used to detect voids
diagrams, but to a first approximation the curves in the polyester [22]. Positrons and electrons
for the higher molecular mass, which corre- can form a positronium atom, the annihilation
14 Fibers, 3. General Production Technology

characteristic of which can be used to measure coiled amorphous polymer chain arrangement
the microvoids in the polyester [23]. and a highly ordered structure which launches
the crystallization process above a critical degree
of orientation. Figure 18 shows the development
of the molecular orientation, beginning with the
free-fall yarn directly under the spinneret to the
oriented meso phase, the necklike deformation,
and ending with the semicrystalline end state of
this spin yarn [25], [26].
The amorphous orientation can be measured
by different methods. Beside the investigation by
the birefringence method [27], the amorphous
orientation of PETP can be measured directly
by detecting the natural intrinsic fluorescence
of its benzene rings [28]. Crystallite sizes, in-
trafibrillar distances, and crystallite orientation
are detectable by X-ray investigations [29].

Radial Distribution of Molecular Orienta-

Figure 17. Model for PETP crystal growth under high ten-
tion. The higher the spinning velocity at a given
sile stress [21] fiber diameter, the more inhomogeneous is the
F and F∗ are forces (F∗ > F) radial distribution of the molecular orientation
in the as-spun fiber [30], [31]. A synonym for
Because of the different fiber morphology this morphology is skin – core structure.
that results from high-speed spinning as com- This characteristic morphology can be clearly
pared to conventional low-speed processes, dye observed in yarns which were spun at very high
pickup is drastically improved. velocities, e.g., speeds higher than 7000 m/min.
The molecular chain alignment at which the This molecular structure can be measured by the
fiber is still noncrystalline is called the amor- birefringence method as a function of the fiber
phous orientation or oriented meso phase. The diameter (Fig. 19) [32–35]).
meso phase is intermediate between a totally

Figure 18. Changes in fiber structure during high-speed spinning [25], [26]
 Fibers, 3. General Production Technology 15

products. So mostly these are not suitable for

the conversion to end products.
Beside chemical polymer modifications [41],
also polymeric additives are used, for exam-
ple, to influence the orientation of the molecular
chains in the fiber. The resulting polymer blends
can be classified as two-phase, one-phase, or in-
termediate systems. Where phase separation oc-
curs, the components are incompatible.
A polymer blend consisting of
polystyrene/polypropylene and polystyrene/high-
density polyethylene yields a decrease in melt
Figure 19. Radial distribution of birefringence at different
viscosity [42], [43], and a decrease in melt vis-
take-up speeds (Take-up velocity in km/min) [32] cosity was observed for polyethyleneterephthal-
ate/PA66 blends [44]. Interesting fiber proper-
ties were obtained by adding a liquid-crystalline
copolymer to polyethyleneterephthalate as a
Figure 20 illustrates the radial distribution of modifier. At a given take up velocity the molec-
the polymer (fiber) velocity gradient, the tem- ular orientation could be drastically reduced
perature in the filament, the corresponding spin- so that the elongation at break (extension) was
ning stress, and the resulting distribution of the substantially increased (Fig. 21) [45], [46].
molecular orientation (birefringence) [36]. The addition of liquid-crystalline polymers
At extreme spinning velocities with very fast is very effective with regard to the elongation
cooling of the filament, the orientation process increase, but the advantages in production cost
can only take place at the outer parts of the limited because of the high price of such addi-
fiber [32], [24]. So at ultrahigh spinning speeds, tives.
e.g., 10 000 m/min, the spinning stress is concen- The elongation increase on adding a further
trated in the boundary layer. However, a certain polymer can be attained also in the case of
minimum spinning stress and enough orienta- nylon and other matrix polymers. Poly(methyl
tion time are required for development of high methacrylate) was also effective, but concentra-
molecular alignment and crystallinity. Hence, tions of more than 2 % are required to give a suf-
the molecules in the skin part of the fiber, which ficient increase in elongation increase at higher
are oriented first, are frozen before the spinning velocities, for example, at spinning speeds of
stress can propagate through the whole thread. 5000 m/min [46]. Additionally yarn breaks were
The result is a very inhomogeneous radial orien- observed at high velocities.
tation distribution. The skin part is much more An additive consisting of 50 – 90 % imidized
highly oriented than the molecules in the middle polymethacrylic acid alkyl ester [48] can be used
of the fiber. This characteristic form is generally concentrations of less than 1 wt % for the above
called skin/core structure. applications. The additives are mostly used for
Further investigations of the development of the production of yarns which can be directly
the skin/core structure in fiber spinning can be used (fully drawn yarn). The advantage of this
found in [37–39], [40]. kind of modifier is its high effectiveness; the
disadvantage is the high price of such copoly-
Polymer Modification. Polymer additives mers. A further copolymeric additive consisting
can be favorably used to influence the develop- of two of the monomers A, B, and C, where A is
ment of the fiber morphology. Chemical modi- polystyrene or methyl-substituted polystyrene;
fication is performed by several producers. But B is imidized maleic anhydride; and C is maleic
these chemical modifiers have limits because anhydride or maleic acid is described in [49].
the high concentrations which would have to be For POY processes which run at high speeds
used to strongly influence the fiber properties of, for example, 5000 m/min Stibal [50] de-
deteriorate the textile physical properties of the scribes an investment cost advantage of 25 %
and the corresponding production cost saving for
16 Fibers, 3. General Production Technology

Figure 20. Radial distribution of take-up speed, viscosity, Figure 21. Fiber elongation with different modifiers (Santi-
spinning stress, and molecular orientation [36] cizer, X7G, Cloth, Central) [45], [46]

a melt modification process in continous poly- sures (ca. 0.5 – 4 MPa) are used than in melt
merisation plants. The fiber forming process is spinning because the dissolved, diluted polymer
in general an elongation process. So when in- flows more freely than a polymer melt. Poly-
compatible polymeric additives are added to a mers with a very high molecular mass (generally
polymer melt, additional shear forces occur bet- up to a weight-average molecular mass M̄ w of
ween the matrix and the additive [45], and rota- 250 000) can also be spun. This is not possible
tional components are developed during the fiber in melt spinning because the limiting viscosity
forming process (Fig 22), [51]. At the same time at zero shear η 0 , and thus the spinning pressure,
the morphology is frozen by fast cooling, so that increase in proportion to M̄ 3.4
w . In solution spin-
the orientation of the resulting fiber is reduced. ning, the effect of molecular mass on viscosity
The orientation decrease can be measured by an can be compensated for by appropriate dilution
increased elongation at break and/or by a reduc- [1], [53]. However, the concentration should not
tion in birefringence (Figs. 23 and 24), [52]. be too low since this reduces polymer through-
put and increases the cost of solvent recovery.

2.1.4. Solution Spinning

2.1.4.1. Dry Spinning
Polymers that do not meet the requirements for
melt spinning may be spun if they can be dis- In dry spinning, the polymer solution is spun into
solved in a suitable solvent. The polymer swells a hot gas whose temperature is higher than the
when dissolved and may form a completely ho- normal boiling point of the solvent. The solvent
mogeneous solution, depending on prevailing thus evaporates, most of the heat of evaporation
bonding forces and interactions. Polymers pre- being supplied by the drying gas which also re-
pared by solution polymerization (e.g., poly- moves solvent vapor. Evaporation of the solvent
acrylonitrile) can be spun directly without inter- along the spinning path is determined mainly by
mediate processing. Much lower spinning pres- its rate of diffusion through the filament, which
 Fibers, 3. General Production Technology 17

Figure 22. Structure-formation process related to the reduction of molecular orientation resulting from a polymer additive
[51]

Figure 24. Birefringence versus spinning speed for physi-

Figure 23. Fiber elongation versus spinning speed for physi- cally modified (HP5000 PETP) and unmodified PETP poly-
cally modified (HP5000 PETP) and unmodified PETP poly- mer [52]
mer [52]

decreases as solidification progresses. Solidifi- which remains in the interior is thus hindered by
cation occurs as a result of the decrease in solvent the already solidifying skin. If evaporation from
concentration and the associated increase in vis- the surface is very rapid, the skin becomes so
cosity; the filament passes through a gel form solid that its circumference remains practically
into the solid phase. Since the heat supplied to constant. Further diffusion of solvent from the
the filament by the drying gas is largely dissi- core results in a loss of mass from the interior,
pated by solvent evaporation, the temperature of with formation of cavities and negative pressure;
the filament does not change significantly. The the skin then collapses and folds inward. The re-
temperature increases only toward the end of the sulting filaments display cross sections that have
spinning path. Solidification by means of mate- the appearance of wrinkled lobes, almost like a
rial transport (i.e., diffusion of solvent from the peanut.
interior of the filament to the surface and sub- In dry spinning, the filament always has a
sequent evaporation) leads to pronounced radial residual solvent content of 5 – 25 wt %, which
inhomogeneities, particularly in spinning solu- exerts a plasticizing action. This is desirable be-
tions with low polymer concentrations. Since so- cause it facilitates subsequent drawing of the fil-
lidification proceeds more rapidly at the surface ament; therefore the residual solvent is removed
of the filament than inside, a typical sheath – later in the process.
core structure is formed. Diffusion of the solvent
18 Fibers, 3. General Production Technology

The spin-draw ratio based on the extrusion tion (which necessitates a subsequent reverse
rate of the spinning solution ranges from 1 to 10 reaction). In wet spinning, the polymer solution
and is thus substantially lower than that found is spun into a liquid coagulating bath. Heat ex-
in melt spinning which may be as high as sev- change with the spinning medium is not respon-
eral hundred. The ratio is lowered by a factor sible for solidification of the filament. Instead,
of 1/cp due to dilution alone (cp is the polymer solidification occurs as a result of coagulation
concentration). caused by phase separation. Phase separation is
induced by a component of the spin bath which
is incompatible with the polymer (i.e., a non-
solvent). The polymer, solvent, and nonsolvent
constitute a ternary system, and processes occur-
ring during wet spinning can best be explained
by using a triangular diagram as shown in Fig-
ure 25. The pure components A, B, and C are
represented by the corners of an equilateral tri-
angle. Point M then represents a mixture with
the composition x A + x B + x C = 100 %. If M lies
on an edge of the triangle, the mixture is binary.

Figure 25. A triangular diagram representing a ternary mix-

ture.
Points A, B, and C represent the pure components; point
M represents a mixture with composition x A + x B + x C ; the
dashed lines pass through M and are parallel to the sides of
the triangle

Although general physical laws and models

of material transport are applicable to dry spin-
ning, a mathematical description is even more Figure 26. Phase diagram of a ternary system during wet
difficult to derive than for melt spinning [1], [54]. spinning
A simple model for the upper part of the filament Points: P = polymer; S = solvent; N = nonsolvent;
SF = spinning solution; PB = inflow into coagulating bath;
(where diffusion is not limiting) is based on the M = composition of mixture (on mixture line according
assumption that the ratio of the material trans- to the law of leverage); G = gel-like filament after phase
fer coefficient to the heat transfer coefficient is separation (in thermodynamic equilibrium); PB = outflow
constant. For an overview of the dependence of from coagulating bath (located opposite G on the binodal
curve)
fiber properties on dry-spinning parameters, see a) Binodal curve (limit of miscibility gap); b) Mixture
[55]. line; c) Line of phase equilibrium (passing through M);
d) Two-phase region (miscibility gap, shaded); e) Path
of change in composition of the spun filament in the
2.1.4.2. Wet Spinning coagulating bath (diffusion-controlled)

Wet spinning is used if the polymer is dis-

solved in a nonvolatile solvent or if the poly-
mer dissolves only after chemical transforma-
 Fibers, 3. General Production Technology 19

The situation in the coagulating bath is de-

picted in the form of a triangular phase diagram
in Figure 26. The most important feature is a
rather broad (shaded) immiscible region under
the so-called binodal curve. Any mixture which,
based on its average theoretical composition, lies
in this region separates into two immiscible, liq-
uid phases. The composition of these two phases
is given by the points at which the equilibrium
line passing through M intersects the binodal
curve. (Any two opposing points on the binodal
curve are connected by such a line.)
The nonsolvent N (frequently water) must be
chosen so that it is miscible with the solvent S
in all proportions. When the spinning solution
SF enters the coagulating bath with an initial
composition PB , the total mixture can be repre-
sented by the point M; the position of M on the
line connecting SF and PB is such that the ratio
of the distance SF– M to the distance PB  – M
is the same as the ratio of the amount of PB
to the amount of SF (law of leverage). By us-
ing point M as an aid in graphic construction,
points PB (final composition of the coagulat-
ing bath) and G are obtained which correspond to
thermodynamic equilibrium. Point G represents
Figure 27. Filament formation during wet spinning [2] the final state of a swollen gel fiber; its surface
The stippled area indicates coagulation
corresponds to the interfacial boundary with the
spin bath. The route by which G is attained, if
at all, primarily affects the structure of the gel

Figure 28. Representative stress – strain curves of spun filaments

A) T g  T , crystalline – oriented; B) T g = T , low orientation (cold drawing) – movement of the draw shoulders or neck is
illustrated; C) T g T , plastic
T = temperature of measurement which increases from left to right if material used in A, B, and C is identical; T g = glass
transition temperature; σ∗ = critical stress
a Elongation ε = ∆l/l where ∆l is the increase in length of a filament with an original length l ; b Tensile stress based on
0 0
the initial fineness (titer)
20 Fibers, 3. General Production Technology

fiber being formed, it depends on the kinetics of change, i.e., a change in composition would pro-
solidification and on the residence time. ceed along a straight line starting at SF and run
parallel to the side S – N of the triangle. Figure 26
shows a general route (e) which corresponds to
S∗ : N∗ > 1. Phase separation begins at the point
of intersection with the binodal curve; the fila-
ment coagulates and becomes gel-like. Its com-
position continues to change along the binodal
curve in the direction of G, and the concentration
of P increases.
As in dry spinning, well-developed sheath –
core structures and cavities are also formed in
wet spinning due to radial diffusion. In wet-spun
polyacrylonitrile fibers, for example, this leads
to filaments with kidney-shaped sections. Fig-
ure 27 represents the formation of a wet-spun
filament. The composition of the spinning solu-
tion within the diffusion boundary has not yet
changed. The coagulation boundary indicates
the position of the binodal line. The spinneret
holes have a characteristic shape and are about
0.1 mm in diameter. The thickness of the spin-
neret is only a few tenths of a millimeter.
In wet spinning, the spin-draw ratio is usu-
ally less than 3, and occasionally even less than
1. Spin elongation still occurs, however, due to
the increased concentration of polymer in the
spinning jet. High frictional forces in the fluid
limit the spinning speed to about 0.8 m/s, which
can be compensated for by a large number of
spinneret holes. A survey of common solvents
and coagulants used in wet spinning is given in
[2].
A mathematical formulation for wet spin-
ning is even more difficult than for dry spinning.
White and Hancock [56] were the first to carry
out precise analysis and model calculations.

Figure 29. Draw point (bottleneck) and molecular orienta-

tion obtained during cold drawing 2.2. Drawing

2.2.1. Elongation Properties of As-Spun

Two types of material transport occur during Yarns
wet spinning, their rates are determined by diffu-
sion constants. First, a flow of solvent S∗ occurs As-spun polymer filaments normally exhibit a
from the spinning jet into the spin bath. Second, low degree of molecular preorientation and crys-
a stream of nonsolvent N∗ diffuses into the spin- tallization; they can therefore still undergo con-
ning jet. The ratio S∗ : N∗ determines the change siderable elongation in the cold state which may
in composition of the original spinning solution be as high as five times their initial length. De-
SF [1]. If, for example, S∗ : N∗ = 1, the poly- pending on the properties of the material and the
mer concentration in the spinning jet does not temperature used for testing, elongation or draw-
 Fibers, 3. General Production Technology 21

ing produces one of the characteristic stress – 2.2.2. Mechanism of Cold Drawing
strain curves shown in Figure 28.
If the glass transition temperature far exceeds Cold drawing can be explained at a molecu-
the temperature of testing or if the filament is lar level (see Fig. 29). In the undrawn filament
already crystalline, the tensile force (stress) in- the molecular chains are largely disordered and
creases rapidly but the filament breaks at low coiled but are immobile just below the soften-
elongation (strain) (Fig. 28A). Conversely, the ing point. Since the filament is extended be-
filament can exhibit a high plastic elongation yond the region of reversible elongation, the ir-
with a slow increase in force if the testing tem- reversible part of the mechanical work of ex-
perature far exceeds the glass transition temper- tension is converted to heat [1], which is con-
ature (Fig. 28C). Figure 28B represents an inter- centrated in the zone of flow where deformation
mediate stress – strain curve, where the testing takes place. This local heating can lead to melt-
temperature is close to the glass transition tem- ing if the rate of elongation is too high; it pro-
perature and which is typical of cold drawing ; vides the molecules with the mobility required
this term was coined in the early days of syn- for rearrangement and sliding during extension.
thetic fiber development to signify that drawing Once the flow process has begun, the stress –
occurs far below the melting point. Cold draw- strain curve in the zone of flow begins to change
ing proceeds as follows: in the initial stage of due to heating, so that a maximum loading at
low elongation, deformation is elastic and re- the stationary point of draw no longer has to be
versible, i.e., the molecules retain their mutual overcome.
points of cohesion. At a certain critical stress The heat liberated during extension consists
σ∗ (elongation = ε1 ), the yield point is reached of two parts: (1) internal frictional heat and (2)
where the tensile force passes through a max- heat produced by thermodynamic changes re-
imum. A constriction (bottleneck) then begins sulting from orientation of the molecules under
to form at a random point along the drawn fila- stress. The thermodynamic changes can be ex-
ment. As elongation proceeds, this constriction plained as follows. Extension results in paral-
wanders along the filament in both directions at lelization of the chain segments and a decrease
constant yield force, resulting in the formation in entropy. Neighboring molecules can never-
of a draw shoulder (telescope effect). In this re- theless still interact with one another because
gion, drawing is heterogeneous. At an elonga- of their temporary mobility. They thus assume
tion ε2 , the draw shoulder occupies the whole a more energetically favorable crystal structure
length of the filament. Since a criterion of math- in which atoms of parallel molecular chains oc-
ematical instability is met [1], filament regions cupy the lattice points of a highly ordered, com-
of varying diameter will always exist between pact crystal lattice. The associated release of
elongation values ε1 and ε2 . The constricted re- enthalpy thus results in an overall more favor-
gion exhibits a reduced diameter, corresponding able thermodynamic state than that of the frozen,
to a local elongation ε2 ; the remaining sites are amorphous, as-spun filament. Since the filament
still not drawn, however, because they lie in the cools or coagulates during spinning, it does not
elastic region below the yield point. These un- have enough time to assume the most stable
drawn sites disappear only when the filament is thermodynamic state permitted by the temper-
elongated to ε2 . The remarkable drawing fac- ature of the surroundings, i.e., that of unordered
tor 1 + ε2 is called the natural draw ratio and crystallites, in which small crystals, also called
equals the ratio of the fineness of the undrawn re- micelles, are embedded in an amorphous ma-
gions to that of the constricted regions. Once ε2 trix. A partially crystalline, as-spun filament
is exceeded, deformation again becomes homo- would, however, have a lower residual drawabil-
geneous with increasing force (up to the break ity because the crystallites stabilize its morpho-
point). If the material has a higher preorienta- logical structure. Only those crystallites whose
tion, ε2 is lower and the yield force is higher. molecules are aligned at right angles to the fiber
axis can be broken up and rearranged during
drawing [57]. The polymer macromolecules are
too long to be present in crystallites in extended
form; they are usually folded several times and
22 Fibers, 3. General Production Technology

arranged in lamellar planes which are perpen- perature T g (with plasticizers, swelling agents,
dicular to the molecular axes (i.e., at right an- oligomers, or residual solvent) or by increasing
gles to the filament axis in the oriented state). the drawing temperature. Softening also leads to
Some molecules are anchored in two or more disappearance of the telescope effect. For exam-
lamellae and are called tie molecules. They thus ple, PETP (T g = 70 ◦ C) no longer forms a neck
connect different crystalline regions in the longi- when drawn at 75 ◦ C. If it is drawn in water,
tudinal direction of the filament, which are sep- the plasticizing action of water begins to dom-
arated by amorphous regions. Apart from the tie inate at 50 ◦ C, so that the drawing tension ap-
molecules, the amorphous regions contain only proaches zero above 90 ◦ C [61]. Water is a good
free chain ends and loosely folded loops. To- conductor of heat and thus prevents overheating
gether with chain loops, the tie molecules thus of the flow zone which would otherwise increase
provide for force transfer within such microfib- the drawing force. When drawing takes place
rils [58]. above the glass transition temperature, however,
the relaxation time of the molecules diminishes
rapidly, which means that stresses decay quickly,
2.2.3. The Drawing Process especially during slow drawing, and the original
internal orientation is then reestablished. Thus
If filaments (e.g., PETP) with a uniform diam- only part of the filament extension has an orient-
eter are to be obtained by a continuous cold- ing effect; the remainder produces flow. This fact
drawing process, a draw ratio greater than the can be exploited in extreme cases to produce su-
natural draw ratio must be used. This is accom- perfine filaments. The as-spun filaments are first
plished with two sets of rollers running at dif- drawn without orientation in a hot-water bath or
ferent peripheral speeds; the ratio of these two some other swelling agent (just below 100 ◦ C in
speeds is the machine draw ratio. The number the case of PETP); orientation is then increased
of yarn loops on each roll must be sufficient to in a subsequent draw. This method permits very
prevent slippage according to the formula for high elongations, which may be as much as 20
rope friction, taking into account the drawing times the original length [62].
tension. Since a small proportion of the draw-
ing deformation is elastic, the effective draw is
slightly less than the machine draw ratio. When
a draw point (bottleneck) appears in cold draw-
ing, it must be stabilized locally within the field
of drawing by frictional or thermal measures to
maintain steady-state drawing [this is not nec-
essary for plastic drawing (see Fig. 28C) at an
approximately uniform rate of elongation].
The dynamics of drawing can be simulated
mathematically [1]. As in melt spinning, the
equation of continuity applies, but simulation is
more difficult because of thermal and viscoelas-
tic peculiarities. The drawing process can, how-
ever, be investigated on a laboratory scale by car-
rying out creep experiments in which the time-
dependent change in length is measured under
constant tensile force [59], [60]. The length of
the drawing field (i.e., the distance between the
sets of rollers) required at a given feed velocity
can be calculated from these experiments. Vari-
ous approaches can be used to reduce the draw- Figure 30. Stress – strain curves of poly(ethylene terephthal-
ate) (PETP) filaments drawn at different draw ratios [12]
ing force and/or improve drawability; they all Stress shown in the curves (σ 0 ) is based on the initial fine-
have the same objective – to soften the as-spun ness; open circles indicate σ, the effective tenacity at break
material by lowering its glass transition tem- based on the actual fineness
 Fibers, 3. General Production Technology 23

2.2.4. Draw Ratio and Tensile Strength when the tie molecules are fully extended. When
the filament leaves the drawing zone, the chains
Any material being spun can be subjected to in the amorphous regions recoil to some extent.
varying degrees of draw. The draw ratio selected As explained previously, the value of the
depends on the textile properties desired and draw ratio used depends on the preorientation
the existing preorientation. As illustrated in Fig- of the as-spun material which, in melt spinning,
ure 30, the higher the draw ratio, the greater is is largely governed by the take-up speed. Fig-
the tenacity at break. At a higher draw ratio, ure 31 illustrates the decrease in residual draw
the modulus of elasticity and the crystallinity ratio with increasing take-up (spinning) speed,
increase, whereas the elongation at break is re- corresponding to a higher spinning orientation.
duced. However, this decrease is less pronounced than
The tenacity at break is equal to the force the concomitant increase in spinning speed. As
applied at break divided by the fineness. Since a result, the spinneret throughput, and thus the
the actual fineness of the fiber at break is lower productivity of a given spinning position, in-
than its original fineness, the effective tenacity crease with increasing spinning speed, provided
at break based on the actual fineness (σ) will that the final fineness remains constant. (Only
be higher than the tenacity based on the initial for polyamide does no advantage result from in-
fineness (σ 0 ). The two tenacities are related as creasing the spinning speed in the range from
follows: 33 – 50 m/s.)
σ=σ0 (1+ε)
where ε is the elongation and is equal to ∆l/l 0 ,
∆l being the increase in fiber length and l 0 the
initial length. In the case of low draw ratios close
to the natural draw ratio, the effective tenacity is
almost constant (see Fig. 30). A high draw ratio
is required to obtain a large increase in tenacity.
The maximum fiber strength is obtained
when the macromolecules are largely straight-
ened out during drawing and are aligned along
the longitudinal axis of the filaments so that they
can crystallize. Since a molecular chain which is
embedded and laterally anchored in the crystal
lattice almost totally resists being pulled away
along its axis, any subsequent tensile loading
will put the greatest stress on the tie molecules
which bridge the amorphous regions (cf. Sec-
Figure 31. Total spinneret throughput and residual draw ra-
tion 2.2.2). If the load per tie molecule becomes tio as a function of winding (spinning) speed in melt spinning
too great, the filament breaks due to the rup- [64]
ture of the main bonds (C – C) of these force- PA = polyamide; PES = polyester [poly(ethylene terephthal-
transmitting chain segments. Because only a ate)] ; —- Throughput; – – – – Residual draw ratio
Final yarn fineness = 167 dtex; Elongation at break = 25 %
small fraction of the molecular chains (shown in
the cross section of the drawn part of the filament
in Fig. 29) act as force transmitters, the resultant
High-speed spinning has become an impor-
strength is a fraction of that which is theoreti-
tant processing variant of melt spinning because
cally possible. Appropriate processing and use
only a low postdraw is then required, which
of a higher draw ratio increase the number of tie
is usually integrated into one of the other pro-
molecules and thus the tenacity at break up to a
cessing steps. High-speed spinning also reduces
certain point by improving molecular uncoiling
shrinkage due to formation of oriented crystal-
and alignment and preventing chain refolding.
lites [65].
Two-step drawing may be important in this con-
text [63]. The upper limit of drawing is reached
24 Fibers, 3. General Production Technology

2.2.5. Ultrahigh-Strength Synthetic Yarns The process used to impart a suitable texture
to synthetic fibers which are processed into sta-
Maximum fiber strength would be obtained if ple fiber or filament yarn is thus an important
very long (theoretically, infinitely long), com- part of fiber manufacture.
pletely extended polymer chains were to form The term texturing means the production of
an ideal, flawless crystal because they would a permanent crimp in an initially straight fiber
then be in their most compact form and all or filament yarn. Crimping is the result of local
be able to transfer force. In such a fiber, the changes in the intermolecular interactions oc-
macroscopic modulus of elasticity would cor- curring in the polymers from which the fiber is
respond to the modulus of individual molecu- made. The crimp is maintained to a greater or
lar chains (i.e., the strength of the C – C bonds). lesser degree during deformation or is stored as
Theoretical tenacities of various polymers have a type of memory [55], [70].
been calculated [66]. Polyethylene is theoreti-
cally the most suitable polymer for obtaining Crimp Rating. Many proposals have been
fibers with very high strength because its chains made for rating crimp [71–74]; these include
have the smallest cross-sectional area. High- optical, mechanical [75], and thermomechani-
performance fibers with a very high molecu- cal [76] methods like those prescribed in DIN
lar mass (M̄ w > 106 g/mol) have been obtained 53 840. Some important parameters for stuffer
from polyethylene by wet spinning (cf. Sec- box crimped fiber are illustrated in Figure 32,
tion 3.2.2.) [67]. The fibers have a tenacity of others are:
3.5 GPa (35 cN/dtex), which far exceeds that of
steel, but this still corresponds to only about KK = (lg −lz ) /lg = crimp contraction
10 % of the maximum theoretical value. Inge- KG =lg /lz = crimp degree
nious drawing processes have been developed
KB = (lg −lb ) / (lg −lz ) = crimp stability
in an attempt to approach maximum theoretical
values more closely [68], [69]. Very high tenac- where
ities have been achieved with liquid-crystalline,
anisotropic polymer melts although their theo- l g = length of elongated (noncrimped) fiber
retical strength is distinctly lower than that of l z = length of crimped fiber
polyethylene. l b = length of crimped fiber after stress appli-
When different materials are being com- cation
pared, conversion of the textile tenacity σ in
centinewtons per decitex to the tenacity σ T in
gigapascals (1 GPA = 109 N/m2 ) may be useful:
σT = 0.1· ·σ

where
is the fiber density (in g/cm3 ). The term
σ T is commonly used for construction and rein-
forcement applications.

2.3. Crimping Figure 32. Structure of a crimped fiber (stuffer box)

α = buckling angle; l = buckling length; s = length of double
arc
2.3.1. General Description

Natural fibers, unlike synthetic fibers, have a so-

2.3.2. Crimping Processes
called texture, which means that they are not
straight but are crimped in three dimensions
Various types of crimp and crimp stabilities can
along their axes. This basic geometric property
be obtained depending on the crimping process.
has shaped the design of fiber-processing ma-
Three main types are used: spontaneous, defor-
chinery and largely determines the characteris-
mation, and bicomponent crimping.
tics of yarns and fabric made from fibers.
 Fibers, 3. General Production Technology 25

Figure 33. A) Bicomponent spinneret for side-by-side (left) and sheath – core (right) filaments; B) Transverse and longitudinal
sections through a side-by-side (upper) and sheath – core (lower) filament

2.3.2.1. Spontaneous Crimping

Spontaneous crimping is caused by the

anisotropy of various fiber properties such as
density, molecular orientation, or crystallinity
both in its cross-sectional plane and along its
axis. Anisotropy can be obtained or reinforced
by applying appropriate measures during spin-
ning and drawing. In melt spinning, for example,
the filament can be cooled on one side just be-
low the spinneret by pulling it past a cooled body
[77]. Alternatively, a swelling agent may be ap-
plied unilaterally in the spinning and/or drawing
region. The resulting anisotropy causes differ-
ential stresses to be “frozen” into the filament
which, when liberated (e.g., in hot water without
tension), produce limited differences in shrink-
age and, thus, irregular crimping of the material.

2.3.2.2. Deformation Crimping

In deformation crimping, crimp is produced by

application of an external mechanical force. De-
formation crimping is currently the most im-
portant method for texturing both staple fibers
Figure 34. A) Crimper with weighted swivel flap; B)
Crimper with adjustable stuffer box
and filament yarns. Various techniques have
a) Incoming tow; b) Crimping rollers; c) Plug of material; been developed. The fibers can be crimped in
d) Stuffer box; e) Crimped tow; f) Pressure applied to stuffer a stuffer box (cf. Section 2.3.3) by knit-de-knit
box technique, or by feeding them through a pair
26 Fibers, 3. General Production Technology

of gears (gear crimping). In another technique

called edge crimping, the heated filaments are
continuously drawn over a sharp edge. Mechan-
ical force can also be applied by means of torsion
(false-twist texturing cf. Section 3.3.2) or by al-
lowing the filaments to pass through an air jet
where the turbulence blows them together into a
random structure (cf. Section 3.3.3).

2.3.2.3. Bicomponent Crimping

In bicomponent crimping, two polymers which Figure 35. Tow with two-dimensional, sawtooth crimp
usually differ in their chemical or physical prop-
erties are coextruded from a single spinneret cap- Many processes have been developed for tex-
illary (Fig. 33A). turing filament yarns, which include filament
By using a suitable spinneret, the polymer deformation, setting, and restoring of deforma-
components may be arranged side by side or in tion in a continuous cycle. Different processes
the form of a sheath – core structure. Figure 33B are used depending on the type of polymer and
shows the structures of the resulting filaments. the filament fineness; they are described in Sec-
A stable, three-dimensional crimp is formed as tion 3.3.
a result of the different shrinkage and viscoelas-
ticity of the polymers; it depends on the distribu-
tion of the polymer mass (e.g., 1 : 1 in the side- 2.4. Heat-Setting
by-side arrangement or 3 : 7 in the sheath – core
structure with an eccentric core). 2.4.1. Purpose

Drawn polymeric filaments have a high strength

2.3.3. Crimping of Staple Fibers and and elasticity, but when heated they begin to con-
Filament Yarns tract (i.e., shrink) at a certain temperature. This
effect is enhanced in the presence of swelling
The stuffer box principle dominates in the crimp- agents such as water. These filaments are not
ing of staple fibers. Tow of up to 6 × 106 dtex is generally suitable for use or further processing
fed through two feed rollers at speeds of up to due to their lack of dimensional stability. Fab-
8 m/s into a closed chamber called a stuffer box. rics made from such filaments display, for ex-
This box may be equipped with a swivel flap to ample, poor crease resistance and poor shape re-
which a load can be applied (Fig. 34A), or en- tention during dyeing or washing. Therefore, the
tire upper and lower cover flaps can be closed drawn filaments must be heat-set with or with-
pneumatically about a hingepoint (Fig. 34B). out a swelling agent and with or without tension.
Two delivery rollers push the tow into a cham- Shrinkage occurs during heat-setting and is ac-
ber, and a folded plug builds up due to the forces companied by a simultaneous change in the fine
and friction in the chamber. The fibers kink bet- structure mechanical properties of the filament.
ween the plug and the pinchpoint of the tow Since internal stresses are relieved, the fiber will
in the delivery rollers; a two-dimensional, saw- not shrink during subsequent processing as long
tooth crimp is thus produced (Fig. 35). Crimp as the conditions are milder than those used for
formation is determined by the roller and cham- setting. However, a fiber should not be “heat-set
ber geometry, the chamber pressure, and fric- to death” because while it is being processed into
tion. Crimp stability is also affected by the tem- yarn, fabric, and finally, clothing, more extreme
perature control of the feed material, the delivery setting conditions must be used so that the arti-
rollers, and the chamber. cle retains each new geometric shape imposed
on it.
 Fibers, 3. General Production Technology 27

Definitions. If a filament or fiber of initial length σ V ln (l/l 0 ) = σ V εH = stress energy

l 0 is shortened to a length l by heat-setting or by
(V = volume and εH = Hencky measure of
the conditions of use, its shrinkage S and degree
elongation related to the stress-free length l 0 ).
of setting F expressed in percent are defined as
Stress energy is negative with respect to pres-
follows:
sure energy because external energy is supplied
S = [(l0 −l) /l0 ] ×100 to the system when the fiber length is extended
(l> l 0 ), whereas the system must do compres-
F = (l/l0 ) ×100 = 100−S
sion work on the surroundings if expansion oc-
The degree of setting characterizes the dimen- curs in all directions.
sional stability of the fiber product under certain When changes in state occur at constant pres-
conditions of treatment and is, of course, greater sure, the amount of heat exchanged with the sur-
if more presetting has occurred. roundings is represented by ∆H; according to
convention, ∆H is negative if heat passes from
the system to the surroundings. For example, in
2.4.2. Mechanism the isochoric extension of a rubber band, the
work of extension is liberated as heat and the
The dimensional stabilization of a synthetic fiber rubber is temporarily warmed.
by heat-setting is made possible by the partial Hence, when a drawn polymeric fiber is
crystallinity of the polymers and the rearrange- heated above its glass transition temperature, it
ment of some of the crystalline regions in the tends toward a more stable state by reducing
amorphous matrix. The crystallites act as physi- its free enthalpy. This can be accomplished ei-
cal cross-links and are able to rearrange when the ther by an increase in entropy (recoiling of chain
mobility of the molecular chains increases suf- segments) or by a decrease in enthalpy (by lib-
ficiently during setting. Permanent, irreversible erating heat due to crystallization, whereby U
setting could otherwise only be produced by and pV decrease). Contrary to [80], however,
cross-linking the chains with covalent bonds as the work of shrinkage performed in response to
is the case, for example, in the vulcanization of a tensile stress does not contribute to a decrease
rubber. in enthalpy; on the contrary, in so doing the fiber
After being drawn, the fibers are generally would take up an equivalent amount of heat from
not in thermodynamic equilibrium since stresses the surroundings (Gough – Joule effect).
and thermally less stable crystallites are “frozen” The amorphous matrix between the larger,
in a colloidal structure. When this colloidal more stable crystallites contains many small
structure is heated to a temperature above the crystallites with some defects in ordering. Since
glass transition temperature (i.e., has a certain stabilization can be achieved in two opposing
degree of thermal mobility), its thermodynamic ways, heat-setting entails a disproportionation of
equilibrium is characterized by a relative mini- the colloidal structure (see Fig. 36) [80], and the
mum in the free energy G. According to the laws amorphous matrix separates into two structural
of thermodynamics, G consists of the variables regions. On the one hand, the amorphous regions
H (enthalpy) and S (entropy) [79]: loosen due to relaxation of blocked stresses in
the molecular chains (recoiling and displace-
G (T ,p,σ) =H (T ,p,σ) −T ·S (T ,p,σ) ment of segments); this is connected with the
where T, p and σ are the independent variables breakup of the least thermally stable, stressed
temperature, pressure, and (for a stretched fiber) crystallites and a certain amount of shrinkage.
tensile stress, respectively. The enthalpy H, in On the other hand, the more stable crystallites
turn, consists of the internal energy U and the grow to form larger, more ordered regions which
work content of the system: prevent further fiber shrinkage. An increase in
the short-range order and/or degree of crys-
H (T ,p,σ) =U (T ) +pV − σV ln (l/l0 ) tallinity can be measured by following the in-
crease in average fiber density, which represents
where an interpolation between the density of the amor-
p V = pressure energy phous and crystalline regions. This two-phase
28 Fibers, 3. General Production Technology

Figure 36. Colloidal structure of a polymeric filament

Crystalline regions indicated by thick lines

model is not, however, completely accurate be- Effect of Stress on Heat-Setting. The min-
cause the packing density of the two phases can imum free energy, and hence optimal thermal
vary. stability, at the heat-setting temperature is ob-
tained if the fiber can yield to the retractive force
(∂G/∂l)T and is able to shrink freely [80]. The
disadvantage of this alternative, however, is that
the loosening of the amorphous regions flattens
the stress – strain curve of the fiber (see Fig. 37).
Tenacity at break decreases and elongation at
break increases by approximately the amount of
free shrinkage. In addition, the height of the elas-
tic region is reduced by the formation of a flow
saddle.
This deterioration of mechanical properties
can be avoided by heat-setting the fiber at con-
stant length under a force that opposes the
shrinkage force (e.g., by setting on hot rollers
immediately after continuous drawing). The ori-
entation (i.e., entropy) and the stress – strain
curve then remain practically unchanged [81].
Figure 37. Stress – strain curves of poly(ethylene terephthal-
ate) (PETP) filaments shrunk freely at different temperatures Even without external shrinkage, the fiber can
[12] relax by means of internal creep due to its vis-
Filaments were heat-set without tension, shrinkage obtained coelastic properties [82]. Crystallization then
during setting is indicated in parentheses remains unaffected [81] or may even be en-
hanced if the applied stress is low because the
 Fibers, 3. General Production Technology 29

enthalpy – elastic portion of the restoring force Effective Temperature and Effective
is negative in the initial phase of extension [80]. Stress. The effective heat-setting temperature
However, because stresses applied at constant T eff corresponds to the melting temperature
length do not completely relax to zero, a small of the crystallites formed in the matrix, which
amount of shrinkage takes place on unloading are relatively unstable compared to the main
[80]. Because the heat-setting equilibrium at- micelles. As discussed above, T eff does not nec-
tained under stress has a higher free enthalpy essarily correspond to the actual temperature of
than that of the stress-free system, a certain treatment. At thermodynamic equilibrium of the
residual shrinkage occurs when fibers are used crystalline – amorphous phase change (∆G = 0),
or tested under stress-free conditions. The total the melting temperature T m equals ∆H m /∆S m
shrinkage obtained after heat-setting under ten- (∆H m and ∆S m being the enthalpy and entropy
sion and heat treatment without tension is, how- of fusion, respectively). The enthalpy of fusion
ever, much smaller than that obtained after heat- and hence the melting temperature are lower
setting without applied tension [62], because the than for the overall melting of the fiber because
crystallites created under stress evidently stabi- the crystallites which are influenced by heat-
lize the anisotropic composite structure more ef- setting are under tension; the internal energy
fectively. However, since the structure is only of the matrix system is therefore not reduced
slightly loosened, properties such as dye uptake fully during crystallization. Since melting of the
are also reduced. crystallites is always associated with shrinkage,
T eff of a material can be determined in two
Other Important Variables. If setting takes ways: (1) by determining the onset of shrinkage
place in a medium which also acts as a swelling on a shrinkage – temperature curve, and (2) by
agent, the glass transition temperature is low- using differential scanning calorimetry (DSC).
ered by ∆T g . This means that the temperature In addition to a major peak, the DSC diagram
T at which setting is performed corresponds to exhibits a smaller melting peak which appears
an effective heat-setting temperature T eff in an at the effective temperature [83]. The heat of
inert medium: melting measured by DSC is also a measure
of average crystallinity. Furthermore, stresses
Teff =T +∆Tg locked into the fiber and hence the effective
stress of heat-setting, σ eff , can also be deter-
Thus, for polyamides saturated with water, mined by measuring the equilibrium shrinkage
∆T g is approximately 80 ◦ C [80]. This means force [78], [83].
that polyamide fibers must be heat-set in hot air
without tension at a minimum temperature of
180 ◦ C to be free of shrinkage when boiled in 2.4.3. Shape Retention and Molecular
water without applied tension. Conversely, heat- Memory
setting in water at 100 ◦ C provides resistance to
shrinkage in hot air up to 180 ◦ C. (For PETP, Every solid with elastic properties is charac-
∆T g in water is ca. 30 ◦ C [61].) Hence, drying terized by a stress-free reference state which
can have a simultaneous heat-setting effect. is in thermodynamic equilibrium. Perturbation
Other variables that affect the degree of ther- of this equilibrium by a mechanical strain ε
mal stabilization are the rate of heating (e.g., at a temperature lower than the effective heat-
greater with saturated steam) and the residence setting temperature T eff creates a restoring force
time. If the rate of heating is too high, the set- which strives to reestablish the equilibrium. The
ting shrinkage increases because disintegration stabilized structure, which represents a molec-
of the unstable regions is more rapid than con- ular memory of the equilibrium shape, has
solidation of the structure by postcrystallization. been called a setting system; the nonequilibrated
At higher setting temperatures, equilibrium is at- shape with the perturbed molecular interaction
tained more quickly. has a been termed a stressed system because it
generates stresses which strive toward the orig-
inal shape [80]. Shape is not restricted merely
to fiber length but includes all three dimensions,
30 Fibers, 3. General Production Technology

e.g., crimp in the form of bends. If a fiber is

bent forcibly, the outer, convex side is extended
locally, whereas the inner, concave region is
compressed. Because the fiber “remembers” its
straight form (setting system 1, F 1) it normally
straightens out when the force is removed. If de-
formation is conducted at a temperature higher
than T eff , the stressed system (stressed system 2,
S 2) can be converted to molecular setting sys-
tem 2 (F 2) by heat-setting (described in Sec-
tion 2.4.2). At a higher temperature, sufficient
energy of activation is available to obtain a min-
imum in the free energy; this transformation is Figure 38. Stress – strain diagram for PETP produced at dif-
thus irreversible and the memory of F 1 is erased ferent production (winding) speeds
a) Undrawn yarn; b) Medium-oriented yarn; c) Partially ori-
and replaced by F 2. When the crimp is stressed ented yarn; d) Highly oriented yarn; e) Fully drawn yarn
mechanically, F 2 is transformed into a stressed
system 3 (S 3). As long as deformation is re- According to the application, yarns are pro-
versible, crimp will later be restored. Even crimp duced in different counts and with different num-
which has been extended severely at a temper- bers of single filaments (Table 2).
ature below the glass transition temperature re-
covers when heated to a temperature higher than
T g but lower than T eff because of its imprinted 3.1.2. Conventional Spinning
memory [80].
Spinning systems are generally arranged to give
a vertical downward process flow over several
3. Manufacture of Filament Yarns floors, as shown in Figure 39 [61]. In the chips
spinning process, polymer chips are brought to
the required state of dryness by batchwise or
3.1. Melt Spinning of Filament Yarns continuous drying. They are then fed pneumati-
cally to the chips silo (a) from where they fall by
3.1.1. General Aspects gravity into the feeding opening of the extruder
(b). The chips are transported by the rotating
Multifilaments of polymeric materials were first extruder screw (feeding zone) and melted bet-
produced by melt spinning in 1940. Subsequent ween the electrically heated barrel and the screw
developments have led to much higher operating (melting zone). Adequate pressure and uniform
speeds, throughputs, and product quality [84]. output of the polymer is obtained by means of a
Spinning processes are categorized accord- progressive increase in the core diameter of the
ing to the processing speed and type of end prod- screw (metering zone). The speed of the screw
uct (Table 1). Speciality products may require is controlled to ensure that the melt is fed to the
speeds other than those listed here. distribution line (d) at constant pressure even if
Depending on their production speed, the the consumption of the spinning machine varies.
yarns have different properties, as can be seen In the direct spinning process, the liquid poly-
in the strain – stress diagram (Fig. 38). mer is fed from the polycondensation stage di-
According to end use requirements, the luster rectly to the distribution line (d) via a pressure
of filaments is changed by modifying the cross pump; the solid-phase stages of chips cutting and
section or by varying amount of dulling agent in drying are omitted.
the polymer. Spin dyeing by adding a suitable Polymer of insufficient purity is prefiltered
dye to the polymer prior to spinning is another by means of a main melt filter (c). The filter in-
possibility. serts can be changed semi- or fully automatically
when their service life is over without disturb-
ing the spinning process. Metal filters, sintered
metals, and powdered metal, or silicic materials
 Fibers, 3. General Production Technology 31
Table 1. Classification of spinning processes

Yarn type Description Processing speed, m/s Processing speed, m/min Product

UDY undrawn yarn 8 – 30 500 – 1800 intermediate

MOY medium-oriented yarn 28 – 43 1700 – 2600 intermediate
POY partially oriented yarn 43 – 83 2600 – 5000 intermediate
HOY highly oriented yarn 83 – 100 5500 – 7500 final
FDY fully drawn yarn 75 – 83 4500 – 6500 final

Table 2. Classification of yarns

Class of filament Titer per single filament, dtex Number of filaments Total filament count, dtex

Monofil (textile) 7 – 20 1–3 10 – 22

Regular 2–6 7 – 72 22 – 167
High-count 1–2 48 – 120 55 – 167
Microfilament 0,5 – 0.99 48 – 192 55 – 167
Superfine filaments < 0.5 120 – 384 55 – 167

with a defined pore size are used as filter media; two groups. Several spinning positions produc-
a combination of woven and nonwoven metal ing the same product are combined into a spin-
filters is usually preferred. ning machine (cf. Fig. 40). The spin packs have
The melt distribution line (d) carries the poly- a limited service life and can be changed after
mer with equal residence times to the spin heads stopping the relevant spin pump.
in the spin beam (e). Each spin head contains The liquid filaments emerge vertically from
all the elements for the preparation of the melt the spinneret and are cooled to room temperature
and formation of the filaments. Individual spin by using transverse or radially blown air with a
heads can be shut down by means of freezing or temperature of 18 – 26 ◦ C and a relative humid-
mechanical valves if servicing of the spin pump ity of 50 – 70 % (i). Depending on the process
is required. The spinning system is vapor-heated and the production schedule, the length of the
(g) using a mixture of diphenyl – diphenyl ox- blow-air zone is 25 – 180 cm and the air veloc-
ide (bp = 256 ◦ C). For different temperatures, a ity ranges from 0.25 to 1.2 m/s. The cooled yarn
corresponding over- or underpressure is main- ends are guided vertically to the take-up by the
tained. The vapor is generated by an electrically conditioner (j). The take-up (Fig. 40) contains all
heated boiler which may be separate or inte- the elements needed for the posttreatment and
grated into the lower section of the spin beam. winding of the yarn.
In the spin beam, the melt stream is carried A film of finish is applied either after the
to multiple gear pumps (f) where it is metered yarn is cooled in the quenching duct [Fig. 39
and conveyed to the spin pack (h) at a spinning (i)] or when it leaves the conditioner [Fig. 39
pressure of 5 – 40 MPa. In the spin pack the melt (j)] at the take-up [Fig. 39 (k)]. The finish con-
is filtered, homogenized, and transported to the sists of a mixture of mineral and/or ester oils
spinneret which contains the desired number of and emulsifiers which improve the cohesion of
capillaries (3 – 350) with a circular or shaped the filaments, as well as their electrostatic and
cross section. Depending on the polymer, fila- frictional properties. The yarn is covered with a
ment fineness, and spinning speed, the diameter film of finish by running it tangentially over a
of the capillary holes is 0.15 – 0.8 mm and the ceramic roller which rotates at a constant speed
capillary length one to five times their diameter. in a trough containing the finishing oil [Fig. 39
Filtration is performed with the same filter me- (k)]. Several yarns can be finished simultane-
dia as described above for the main melt filter, a ously with one roller. A more precise method
combination of different filter media may also be of applying finish involves metering the finish
employed. As a rule, at a single spinning position for each yarn by means of a gear pump and a
several yarn ends (2 – 16) are spun, quenched, ceramic applicator pin. The amount of finish ap-
finished, and wound up either together or in plied is determined by the speed of the rollers
32 Fibers, 3. General Production Technology

Figure 39. Schematic of melt spinning Figure 40. Take-up unit for undrawn yarn (UDY) with 16
a) Chips silo; b) Extruder; c) Melt filter; d) Melt distribution ends per spinning position (only one position is shown)
line; e) Spin beam; f) Spin pump; g) Vapor-heated jacket; a) Filament yarn; b) Finishing-oil roller; c) Godets; d) Fric-
h) Spin pack; i) Quenching duct; j) Conditioner; k) Finish tion roller; e) Traversing unit; f) Chuck with eight yarn pack-
applicator; l) Godets; m) Traversing guide; n) Spin bobbin; ages
o) Blow air Courtesy of Barmag, Remscheid, Germany

and pumps. The finishing oil can be emulsified ward motion of the winding head with the fric-
in water, dissolved, or used neat. tion roller or of the chuck bearing the wound
As shown in Figure 39, the finished yarn ends yarn. Traverse motion is usually performed by a
pass over two godets (l), which determine the simple cam-shaft traversing systems that moves
spinning speed, and are then led to the winder. a ceramic guide along the bobbins stroke. The
The yarn is wound by means of a traversing traverse speed is modulated at frequent intervals
guide (m) onto cylindrical cardboard or resin to prevent slippage of yarn layers when pack-
tubes to form spinning bobbins (n). A friction age patterns are formed due to an even-number
roller ensures that the speed of the tube with its ratio between the rates of bobbin rotation and
wound yarn remains constant. The increase in traverse. The yarn is threaded into the take-up
diameter of the bobbin is compensated by back-
 Fibers, 3. General Production Technology 33

by means of a movable injector gun powered by

compressed air.
Undrawn yarn (UDY) is wound at 8 – 30 m/s
and has a low orientation (LOY). It can only be
stored for short periods and must be drawn three
to four times in a subsequent drawing process to
obtain a product with properties that are suitable
for its end use [2], [61], [84]. To attain high yarn
strength for industrial uses, the yarn is passed
through a heated tube with a length of ca. 30 cm
(hood heater) after the spinneret.
Auxilliary plants are necessary to provide
auxilliaries, raw materials etc. in the required
quality neccesary for production of the fila-
ments:
– Chips drying to adjust water content (if ex-
truder spinning is used)
– Spin-pack, spin-pump, and melt-filter clean-
ing and servicing
– Spin-finish make-up
– Winder maintenance
– Quality control for raw material and final
product

Figure 41. Spinning machine for partially oriented yarn

3.1.3. High-Speed Spinning (POY) with S-wrap-around godets (8 ends per spinning po-
sition)
a) Melt distribution line; b) Motor for spin drive pump;
Since 1970, spinning at conventional wind- c) Spin pump; d) Spin head; e) Blow duct; f) Spin pack;
ing speeds of 8 – 30 m/s has been replaced in g) Conditioner; h) Take-up unit; i) Godets j) Winder; k) Au-
many areas by high-speed spinning with wind- tomatic doffing system
ing speeds of 43 – 75 m/s. High-speed spinning Courtesy of Barmag, Remscheid, Germany
yields a partially oriented yarn (POY) which After quenching, a finish is normally applied
subsequently has to be drawn 1.2- to 2.2-fold at a variable distance (50 – 200 cm) below the
for further use. Since POY has a higher degree of spinneret to control yarn tension. Finish is usu-
orientation than UDY, it has a longer storage life ally applied by means of applicator pins and me-
and further external processing (e.g., texturing) tering pumps.
is thus possible. In general, a higher productiv- The yarn is frequently interlaced immediately
ity per spinneret is achieved (see Fig. 31). The before winding to improve yarn take-off from
higher initial modulus makes POY less delicate the package. The individual filaments are entan-
than UDY; higher operating speeds and yields gled by directing the yarn past a nozzle made of
are therefore possible in subsequent processing. sintered ceramic which emits a jet of compressed
High-speed spinning proceeds basically as air at a pressure of 0.3 – 0.6 MPa [2], [86].
described in Section 3.1.2; a typical spinning The yarn is finally wound on specially devel-
unit is shown in Figure 41. As a result of the oped high-speed winders which nowadays usu-
high operating speed, higher demands are made ally are equipped with automatic doffing (chang-
on the polymer itself, its handling, its filtration, ing) devices (Fig. 42). Automatic winders op-
and the equipment. The increased take-off speed erate practically without waste and are labor-
results in a comparatively high yarn winding ten- saving. Often they are combined with an au-
sion so that godets may be required to control tomatic doffing system which removes the full
winding tension especially for high count and
low-dtex single yarns.
34 Fibers, 3. General Production Technology

Figure 42. Automatic doffing system for unloading the full bobbins from the winder
Coutesy of Toray Engineering Co., Ltd.

bobbins from the winder and replace them with verse speed by means of a microprocessor [89].
empty tubes. Typical winding speed is 50 m/s for PETP POY,
The bobbin chuck is usually driven directly with modified polymer 83 m/s, and for Nylon
by a motor (axle drive). The peripheral speed POY 70 m/s.
of the bobbin is kept constant by controlling
either the number of revolutions of a friction-
driven sensor roll or by means of the yarn wind- 3.1.4. Superhigh-Speed Spinning
ing tension (godet machines only). The yarn is
distributed over the traverse stroke by means of Since about 1980, yarn with increased orienta-
a shuttlelike moving traversing guide onto cylin- tion has been obtained by increasing the winding
drical cardboard or for higher speeds with the aid speed above 83 m/s to 133 m/s; 117 m/s is the
of two or more opposing rotors over the width of maximum speed used commercially. The prod-
the traverse (Fig. 43)[88]. One winder is capable uct is a flat yarn which usually requires no fur-
of simultaneously producing two to ten pack- ther drawing. The yarn displays a lower strength,
ages on one chuck with a weight of 8 – 40 kg, lower initial modulus, and higher elongation in
depending on the number of ends. comparison to mechanically drawn yarn. In the
To ensure good package formation and un- case of PETP the boil-off-shrinkage of the yarn
winding conditions, traverse modulation (see is much lower, too. The modified yarn proper-
Section 3.1.2) can be supplemented by a step ties result in a limited application window for
precision winding unit which changes the tra- this product.
 Fibers, 3. General Production Technology 35

Production is basically the same as that de- To ensure good unwinding conditions, tra-
scribed in Sections 3.1.2 and 3.1.3, but greater verse modulation (see Section 3.1.3) can be
demands are made on the equipment and the supplemented by a step precision winding unit
polymer because of the extremely high operat- which changes the traverse speed by means of a
ing speeds. The yarn is spun without mecanical microprocessor [89]. To improve cohesion and
drawing, and final elongation is determined by take-off properties, the yarn is commonly inter-
take-up speed and the titer of single filaments. laced as described in Section 3.1.2. Because of
Tension control with godets is necessary if a the high speeds involved, manual string up is
spinning machine of conventional height is used. performed at lower speeds by means of an in-
In compact spinning [85], omission of the con- jector, after which operating speed is reached
ditioner between the quenching zone and the automatically, and an automatic doff is used to
winder reduces the height of the spinning unit segregate yarn with unsuitable operating speed.
from ca. 12 m (conventional height) to ca. 6 m. Further doffs are carried out automatically at full
This decrease, mainly in the thread-pass length, operating speed [2].
reduces yarn tension by lowering the air drag, so
that godets can be dispensed with.
3.1.5. Draw Twisting and Draw Winding

The final properties of low-oriented yarns, pro-

duced as described in Section 3.1.2 and 3.1.3,
are established by subsequent drawing. Draw-
ing results in higher strength, lower elongation at
break, and in some cases, lower boil-off and hot-
air shrinkage (drawing is discussed in detail in
Section 2.2). The final product is a flat yarn with
suitable properties for weaving, knitting, and in-
dustrial applications. In draw twisting, the yarn
is simultaneously drawn and twisted, whereas in
draw winding it is simply drawn and wound.
In many areas drawing machines have been
replaced by integrated, high-speed processes
due to their lower labor costs and their higher
yarn quality and outputs, as described in Sec-
tion 3.1.8.
The path of the yarn in the drawing machine
can differ depending on the polymer used. Fig-
ure 44 shows the path for PETP, for which the
hot plate (g) and the second godet (e) are heated,
while the other godets are cold. For nylon 6 and
Figure 43. Eight-end winder with an automatic doffing sys-
nylon 66, which are drawn cold [84], [90], the
tem for 2500 – 6000 m/min with rotating traverse system hot plate and second godet are omitted. A draw
Courtesy of Murata Machinery Ltd., Osaka, Japan ratio of 1/1.2 to 1/5 is applied between rollers
(a), (c), and (e) for PETP, and between (a) and
The yarn may also be reheated in a heating (c) for nylon. The yarn is directed onto the cop
tube 1 – 3 m in length immediately after quench- (i) by a ring (j) that moves up and down and
ing to obtain a further increase in orientation holds a traveler (k). The traveler is pulled along
[87]. Two open, looped godets are used in this the ring by the yarn-winding tension. The dif-
case to control yarn tension. Due to the very high ference between the speeds of the traveler and
yarn speed, only winders with a rotating traverse the cop twists the yarn while it is being wound
system are in use for this process (cf. Fig. 43) (draw twisting). Yarn buildup on the cop (i) is
[88]. programmed, the most common patterns being
36 Fibers, 3. General Production Technology

differential, cop, and parallel winding. The take- tion 3.1.3) is often used to improve cohesion,
up speed is 12 – 24 m/s for textile yarn [2]. especially in draw winding.
Industrial yarns are processed on draw wind-
ing machines of reinforced design, similar to that
illustrated in Figure 45. Depending on the end
use of the yarn, the machine may have up to
three drawing zones, three hot draw rollers, three
drawing pins, and two hot plates in the drawing
fields. The total draw ratio can be as high as
1/7. Take up of the yarn and interlacing is as de-
scribed above. The take-up speed is 3 – 13 m/s
[2].
Most industrial yarn nowadays is produced
by one-step processes; speciality products are
still produced by draw winding or draw twist-
ing.

3.1.6. Draw Warping

Undrawn or partially drawn textile filament

yarn, produced as described in Sections 3.1.2
Figure 44. Draw twisting of PETP yarn and 3.1.3, is subjected to integrated drawing and
a) Feed roller; b) Pressure roller; c) First draw roller (godet); warping to produce section beams for use in
d) Idler; e) Second draw roller (godet); f) Idler; g) Hot plate;
h) Pigtail guide; i) Cop; j) Ring; k) Traveler; l) Spindle knitting and weaving. The drawing process de-
scribed in Section 3.1.5 is then omitted. The feed
yarn must be of above-average quality to min-
imize machine stops and any resultant dyeing
defects.
Draw warping is illustrated schematically in
Figure 46. The yarn is taken off 600 – 1400 bob-
bins arranged in a creel (a) and fed into the draw-
ing unit as a warp via yarn brakes and a reed with
eyelets (f). A series of seven to ten sets of rollers
with S loops are arranged in three groups (b) –
(d) to form a drawing zone (draw ratio 1 : 1.2
to 1 : 5) and a relaxation zone. Drawing can also
be assisted by incorporating a heated water bath,
a heated draw pin, or heated feed rollers in the
Figure 45. Draw winding machine with two godets and a drawing zone. The yarn warp is then heat-set
hot plate, two ends per position by guiding it over a hot plate (e). Yarn defects
Courtesy of Zinser Synthetic Systems, Germany
(slubs) are located by means of optical detectors
Draw winding is carried out similarly, but in- (g); the unit is stopped automatically so that de-
stead of being twisted the yarn is wound onto fects can be removed. To minimize damage to
cylindrical packages rather than biconical cops the yarn during machine stoppage, the hot plate
by using a winder at each drawing position. The is swung out of the way, the heated rollers are
wound yarn is practically free of twist. Take-up cooled, and the draw pins are rotated so that the
speed is 20 – 28 m/s; on some machines up to yarn is in contact with the unheated side. Yarn
33 m/s is possible. The temperature of the draw cohesion is improved by applying a finishing oil
rollers and heaters is monitored by scanners. In- by means of a wetted roller rotating in a trough
terlacing of the yarn before winding (cf. Sec- (h). Yarn cohesion is further improved by inter-
lacing the yarns with an entangling reed (f) be-
 Fibers, 3. General Production Technology 37

Figure 46. Schematic of a draw-warping unit

a) Creel; b) Feed rollers; c) Draw rollers; d) Relaxing rollers; e) Hot plate; f) Tangle reed; g) Slub detector; h) Finish applicator;
i) Beam
Courtesy of Karl Mayer, Obertshausen, Germany

Figure 47. Yarn take-up unit with 216 tension-controlled winders and an automatic doffer
Courtesy of Barmag, Remscheid, Germany

fore the oil is applied; the filaments of one yarn very low shrinkage are obtained due to the com-
end are interlaced as they pass a jet supplied with paratively high residence time in the machine’s
compressed air at a pressure of 0.3 – 0.6 MPa. heater.
Some machines are equiped with a sizing pro- The yarn ends are drawn off a large number of
cess instead to improve yarn cohesion further for bobbins placed in a creel and are then fed into the
delicate yarns that are to be woven. The finished drawing unit as a warp. The drawing unit con-
yarn is wound under constant winding tension at sists of five to nine open, heated feed rollers and
speeds up to 10 m/s to form a section beam (i). a subsequent, similarly constructed set of draw
Sized yarn is wound at speeds of up to 3.3 m/s rollers with 1.2 – 7-fold greater surface speed.
[93–96]. The warp is looped around the two sets of rollers
and drawn as a result of their different speeds.
Hot-air shrinkage of the yarn is reduced to the
3.1.7. Horizontal Drawing desired value by heating it in a channel between
the draw rollers. The yarn is then looped around
Undrawn or partially drawn yarn [92], produced
a third, unheated set of draw rollers with three
as described in Sections 3.1.2 and 3.1.3, can also
to seven open, looped feed rollers; these rollers
acquire its final properties in the form of a warp
run at a slower speed than the previous set and
on a multi-end drawing machine rather than a
thus permit a defined relaxation of the yarn. The
draw twister. Horizontal drawing is used primar-
yarn is cross-wound on cylindrical bobbins in a
ily to process industrial yarn. Since a relatively
bobbin creel. The speed of the winders is con-
low drawing speed is used (2 – 8 m/s), yarns with
38 Fibers, 3. General Production Technology

trolled by yarn tension. A yarn take-up unit is with an idler roll or around a pair of godets. The
shown in Figure 47. If necessary, yarn cohesion feed godet may be heated inductively if neces-
can be improved by interlacing individual yarn sary (e.g., in the case of PETP). A second, simi-
filaments or by applying a finishing oil as de- larly constructed drawing unit runs 1.2 – 4 times
scribed in Section 3.1.6. faster (the draw ratio), at a temperature of 130 –
180 ◦ C. This unit draws the yarn, relaxes it, and
allows thermal shrinkage to be adjusted to the
3.1.8. Spin Drawing desired value.
If processing speed is sufficiently high, the
In spin drawing, the spinning and drawing pro- godets do not necessarily have to be heated, re-
cesses described in Sections 3.1.2, 3.1.3, and laxation of the yarn prior to winding (e.g., by
3.1.5 are combined into a one-step process means of steam) is sufficient [97].
which produces a flat, ready-to-use, fully drawn In the production of industrial yarn, the spin-
yarn (FDY) for textile or industrial purposes. ning speed is usually 7 – 12 m/s. Three to four
Spin drawing has largely replaced the conven- sets of godets are needed so that a total draw ra-
tional two-step process because it is less labor- tio of 1/5 to 1/7 is obtained in two drawing steps.
intensive, quality control costs are lower, and a The temperature of the godets is between 80 and
better quality yarn is produced. A spin-drawing 220 ◦ C. A final drawing zone with a draw ratio
machine is shown in Figure 48. between 1/0.85 and 1/1.05, serves as a relaxation
zone. The yarns are interlaced as described in
Section 3.1.4 to improve their cohesion for fur-
ther processing [2]. For the production of indus-
trial yarn according to the HMLS (high-modus,
low-shrinkage) process, spinning speed is bet-
ween 30 and 38 m/s. Three to four sets of godets
are used for a total draw ratio between 1.18 and
1.22. Winding speed is between 93 and 108 m/s.

3.2. Solution Spinning of Filament Yarns

The basic principles of solution spinning are
described in Section 2.1.4. Examples of poly-
mers which are spun commercially into filament
yarn from solutions are polyacrylonitrile and its
copolymers [98], poly(vinyl alcohol) [99], and
aramids [2]. Filament yarns with high heat resis-
tance, a high modulus of elasticity, and/or a high
strength (tenacity) have also been introduced.
These yarns are made from polybenzimidazole,
Figure 48. Spin-drawing machine for industrial yarns, with poly(amide – imide), polyoxydiazole, polytria-
four ends per spinning position
Courtesy of Rieter, Winterthur, Switzerland
zole, and other special polymers [2] and can be
produced only by solution spinning.
For textile application spinning is carried out Economic preferences for wet or dry spin-
as described in Sections 3.1.2 and 3.1.3. In the ning cannot be generally defined because pro-
1970s conventional spinning speeds of up to cess economics depend strongly on use of the
17 m/s and winding speeds of ca. 67 m/s were optimal solvent. The required properties of the
used. Today, high-speed spinning at 37 – 75 m/s filament yarn may also influence the choice of
with winding speeds of 70 – 83 m/s is preferred; process. In the case of poly(vinyl alcohol), for
this results in higher throughput and more uni- example, silklike yarn is obtained by dry spin-
form quality. After finish has been applied, the ning [100], whereas wet spinning produces high-
yarn is looped several times around a feed godet strength, high-modulus yarns [101].
 Fibers, 3. General Production Technology 39

an inlet and an outlet for the drying gas. The dry-

ing gas (air or an inert gas) is heated to a tem-
perature corresponding to the boiling point of
the solvent; gas flow is either cocurrent or coun-
tercurrent with respect to the spun filaments. To
avoid fluctuations in quality of the filament yarn,
all spinning parameters must be kept constant
within a narrow range. Optimal recovery of sol-
vent is an extremely important economic factor
in fiber production. The filaments emerging from
the dry-spinning shaft are rerouted by take-off
rolls, coated with finish, and wound at speeds
of up to 17 m/s. Further processing of the spun
material is analogous to that described in Sec-
tion 3.1.5. As a rule, 12 to 64 dry-spinning shafts
are arranged side by side in series and constitute
a unit known as a spinning machine.

3.2.2. Wet Spinning

The principles of wet spinning are described in

Section 2.1.4.2. Preparation and purification of
the highly concentrated spinning solution are
similar to dry spinning. The viscosity and there-
fore the concentration of the polymer are se-
Figure 49. Schematic of a dry-spinning shaft lected to suit the requirements of the spinning
a) Spin pump; b) Spinneret; c) Filament yarn; d) Drying
chamber; e) Take-up roller; f) Inlet for drying gas; g) Outlet
units and to give a pressure at the spin pump
for drying gas and solvent vapor of ca. 1 – 2 MPa. The spinning solution is fil-
tered and conveyed to the spinnerets; a number
of spinnerets generally spin into a common co-
3.2.1. Dry Spinning agulating bath. The coagulation conditions are
an extremely important factor in determining
Strict requirements are placed on the solvents the solidification of the swollen, gel-like fila-
used in dry spinning. In addition to being excel- ments and therefore the filament quality. Im-
lent solvents for the polymer in question, they mense know-how is required to maintain a con-
must be nontoxic, and must have a low heat of stant concentration and temperature in the coag-
evaporation, and a low risk of explosion. The ulating bath during spinning. The residence time
spinning solutions can be prepared continuously of the yarn in the coagulating bath is affected by
or batchwise in commercial solubilizers, knead- a number of factors, such as speed of injection
ers, or screws. Solutions should be as concen- and drawoff, and must be optimized to ensure
trated as possible and may contain up to 45 wt % uniform, flawless coagulation of the yarn.
of solid material, depending on the polymer and In older units, yarn from the coagulating bath
its degree of polymerization. The highly viscous is subjected to drawing and posttreatment in sep-
spinning solution is filtered and degassed; it is arate processes, but modern integrated units op-
then conveyed, if necessary in heated pipes, to erate continuously in a one-step mode, as shown
the spin pumps and the spinnerets by means of in Figure 50. Filament yarns from many neigh-
extruders or gear pumps. The spin pumps and boring spinnerets are drawn from the coagulat-
spinnerets are located in the upper part of a spin- ing bath and stretched by warp drawing. They
ning shaft, which is shown schematically in Fig- are then posttreated and wound at speeds of
ure 49. The shaft is 4 – 8 m long and consists of a 2.5 – 15 m/s on cylindrical bobbins on individ-
vertical, double-jacketed, heated duct fitted with ual winders combined in creels. Posttreatment
40 Fibers, 3. General Production Technology

such as drying, drawing, and heat-setting differs and improves the elasticity of the yarn. Only
depending on the polymer being processed and a few of the many texturing processes devel-
the desired properties of the filament yarn. The oped during the 1950s and 1960s have survived
drawing unit for warp drawing shown in Fig- on a commercial scale [2], [105]. For textile
ure 50 is designed for the production of high- titers in the range 22 – 330 dtex, false-twist tex-
strength, high-modulus poly(vinyl alcohol) yarn turing is now used for more than 90 % of all
[102]. polyesters and polyamides; twist texturing, air
texturing, and bicomponent technology are only
Gel Spinning. Gel spinning is a type of so- of minor importance. During the past ten years,
lution spinning that has been defined as as dry textured polyester filament yarns have been pri-
spinning at a very high polymer concentration marily responsible for the growing popularity
(up to 80 %), that is, a cross between dry and of friction false-twist texturing. Worldwide pro-
melt spinning. However, the term is also used duction of textured polyester yarn is anticipated
because of the gel-like appearance of the result- to be 3.0 × 106 t/a by 1993, which is much more
ing filaments [67], [103]. than the total annual worldwide consumption of
This spinning technology was developed at wool. Further strong increases up to the year
the end of the 1970s [104] for the production 2000 are only expected in Asia. In 1997 about
of high-performance polyethylene fibers and fil- 79 % of 179 176 friction false twist texturing
ament yarns which are distinguished by high spindles were shipped to Asia [20].
strength and high modulus of elasticity. These Until the early 1970s, three separate process
special properties are achieved because gel spin- steps were required to produce textured filament
ning orients the macromolecular polymer chains yarn. The yarn was melt-spun conventionally at a
along the fiber axis with a high degree of par- draw-off speed of 13 – 25 m/s; it was then drawn
allelism. Polyethylene with an extremely high on draw twisters or draw winders and, finally,
molecular mass (M̄ w > 106 g/mol) is used and textured on special machines. Since 1972, how-
must be spun from solutions at a relatively ever, the combined one-step draw-texturing pro-
low concentration. Under these conditions, the cess has become increasingly important world-
molecular chains uncoil and can orient them- wide. Compared to the conventional three-step
selves along the fiber axis before crystalliza- process, this technology results not only in re-
tion sets in. The polymer solution (ca. 20 wt %) markable improvements in the quality of the
is prepared in a hydrocarbon solvent such as textured yarn but also in substantial financial
Decalin (decahydronaphthalene [91-17-8]) and savings. The pneumatic stuffer box has increas-
then forced through the spinnerets at 120 – ingly replaced the mechanical stuffer box in the
130 ◦ C and spun in a dry-spinning shaft. Spin- production of textured yarns with a fineness
ning is followed by hot drawing at 70 – 150 ◦ C. of 1000 – ≥ 4000 dtex; these so-called bulked
High-performance polyethylene fibers pro- continuous-filament (BCF) yarns are used for
duced by gel spinning are being introduced com- carpets and for decorative or upholstery fabric.
mercially under the trade name Dyneema [103].
Other polymers, such as polyacrylonitrile, are
also assumed to be accessible to gel spinning and 3.3.2. False-Twist Texturing
the manufacture of high-performance fibers.
In false-twist texturing, thermoplastic multifila-
ments are twisted by torsion, the twist is heat-
3.3. Texturing of Filament Yarns set, and the yarns are subsequently detwisted
in a continuous process. Textured yarns are ob-
3.3.1. Development of Texturing Processes tained which exhibit good bulk but are almost
completely free of twist. Also since 1972, false-
In many applications, the original smooth mul- twist texturing on spindles has largely been re-
tifilament yarns must be textured (crimped) in placed by texturing in which twist is imparted by
two or three dimensions so that they acquire the friction. Friction texturing allows considerably
optimum properties required for their end use greater productivity because drawoff speeds of
(cf. Section 2.3). Texturing increases the bulk
 Fibers, 3. General Production Technology 41

Figure 50. Schematic of a wet-spinning – warp-drawing machine

a) Coagulating bath; b) Wet – cold drawing; c) Neutralization bath; d) Washing bath; e) Lubrication; f) Drying; g) Hot drawing;
h) Final finishing; i) Winding of filament yarn

Figure 51. Draw-texturing process

A) Sequential draw texturing; B) Simultaneous draw texturing

10 – 20 m/s can be obtained; texturing on spin- reduced by thermal treatment, the yarns are
dles only allowed a maximum draw-off speed divided into non-heat-set, highly elastic (HE)
of 5 m/s. The rapid development of friction tex- yarns with a crimp of 35 – 50 % and heat-set
turing would not have been possible without the yarns with a 20 – 25 % crimp. Since worldwide
commercial introduction of high-speed spinning capacity for conventionally spun polyamide
and draw texturing [108]. yarns with a low orientation (LOY) is still exist-
Draw texturing may be either sequential or ing, these polyamide yarns are usually crimped
simultaneous (see Fig. 51). In sequential draw by sequential draw texturing. New installations
texturing, the yarn is drawn in a drawing zone for the manufacture of polyamide yarn employ
which precedes the texturing zone; in simulta- high-speed spinning so that the resultant POY is
neous draw texturing, drawing and texturing are also subjected to simultaneous draw texturing.
integrated in a single zone. Commercial frictional draw-texturing ma-
High-speed spinning of partially oriented chines are based on a similar design. They all
yarn (POY) in combination with simultaneous contain the following essential elements: a sup-
draw texturing has made its mark worldwide ply creel, heater, cooler, friction-texturing unit,
in the manufacture of polyester yarns. Depend- and winding unit. A typical draw-texturing ma-
ing on whether the crimp of textured yarns is chine is depicted in Figure 52.
42 Fibers, 3. General Production Technology

Figure 52. Double-heater draw-texturing machine

a) Rotary creel; b) Yarn cutter; c) Feed system; d) Threading device; e) Primary heating; f) Cooling plate.; g) Ringtex texturing
unit; h) Yarn break sensor; i) Yarn aspirator; j) Secondary heating; k) Take-up unit; l) Tube holder; m) Reversing shaft; n) Drive
rollers; o) Traversing yarn guide; p) Yarn guide elements; q) Yarn oiler
Courtesy of Barmag/Saurer Group, Remscheid, Germany

Yarn runs from the POY bobbins mounted polyurethane, as well as steel or aluminium,
on the supply creel (a) to feed rollers (c), over coated with different materials. These different
the primary heater (e) and cooling plate (f) to disk materials have different advantages and dis-
the frictional texturing unit (g) and a second set advantages which are summerized in Table 3.
of feed rollers (c). In the case of heat-set yarn, A draw-texturing machine is shown in Fig-
the drawn and textured filaments pass over a sec- ure 54.
ondary heater (j) before being wound in the take- The number of disks on a draw texturing unit
up unit (k). To attain favorable properties for depends on production speed, yarn thickness,
further processing, the cohesion of the textured disk surface and spin-finish content. Usually this
yarn must be improved. For economic reasons, number varries from four to eight. Sometimes
textured yarns are interlaced rather than twisted also polished disks are used at the top and the
immediately after draw texturing. end of a disk arrangement.
Two alternative twisters based on the princi-
Table 3. Advantages and disadvantages of disk materials
ple of nip-controlled vector (NCV) drive have
Ceramic disks Polyurethane been developed by Murata Machinery (Japan)
disks and Barmag (Germany). In these machines, twist
Tenacity of textured yarn lower higher is imposed on the yarn by two elastic surfaces
Sensitivity to spin finish lower higher running in opposite directions. Only Murata Ma-
Snow generation higher lower
Crimp lower higher
chinery has commercialized the texturizing unit
Lifetime long shorter with crossed belts and one large disk with two
Costs lower higher belts (one on each side of the disk).
The Murata system uses small intersecting
Disk-friction units with three axes, (see elastic belts (Fig. 55), and the Barmag Ring-
Fig. 53) are commonly used to impart twist, tex system textures the yarn between two inter-
the disks can be made of pure ceramic or secting, ring-shaped friction surfaces (Fig. 56).
The NVC false-twist systems are said to per-
 Fibers, 3. General Production Technology 43

mit higher texturing speed, reduce abrasion loss, 400 ◦ C as opposed to the temperature of standard
improve yarn strength, and be generally gentler. contact heater of about 200 ◦ C. The high-tempe-
However, because of its better process stability rature noncontact heaters are shorter and so the
the frictional draw-texturing process has more yarn tension caused by friction is much lower,
widely established in the textile industry. especially at high speeds. With such heaters spe-
cial care must be taken with the spin finish, since
small deposits of heat-cracked spin finish in the
heater can limit the operation drastically.
To guarantee a uniform and failure-free qual-
ity of the textured yarn, new machines are
equipped with an online quality inspection sys-
tem. Such systems monitor the yarn tension of
each yarn path and classify each bobbin into dif-
ferent levels of quality. In combination with an
automatic doffing system, such systems reduce
costs by decreasing labor requirements and al-
lowing night shifts without personnel.

Figure 54. Draw-texturing machine (Mach Crimper 33H)

Courtesy of Murata Machinery, Japan

Attempts are also being made to produce

Figure 53. Disk-friction false twister with three axes POY-bobbins with better runoff properties. Bar-
mag has, for example, introduced the ribbon-free
Typical lengths of heating zones are about random wind (RFR) system [109].
2 – 2.5 m each. To minimize the machine height
and to improve the operation of the machine, dif-
ferent yarn paths have been realized. Figure 52 3.3.3. Air-Jet Texturing
shows a so-called collapsed or folded yarn run-
ning path. However, rerouting the yarn can be Widespread use of air-jet texturing was hindered
detrimental to yarn quality, especially in the case by its high consumption of air and the rela-
of profiled or very fine filaments. To improve tively low production speed (ca. 2 m/s). In the
the texturing performance, different machine de- 1970s, however, production speed was success-
signs are available, as shown in Figure 57. fully increased (7 – 10 m/s) and air consumption
Attempts are being made to obtain even reduced. These developments, together with the
higher texturing speeds for economic reasons. trend to yarn with a character more like that of
Therefore, noncontact high-temperature heaters staple fibers, have led to increased use of air-jet
were developed. Such heaters operated at about texturing.
44 Fibers, 3. General Production Technology

Figure 56. Disk-friction false twister (Ringtex system)

A) Small twist angle, low degree of twisting; B) Large twist
angle, high degree of twisting

Figure 55. Double-belt false twister

In air-jet texturing, one or more multifilament ing machines (see Section 3.3.2), but an air-
yarns are fed into the texturing jet where they texturing jet replaces the false twisting unit.
are swirled in a turbulent stream of air and form Since air-jet texturing machines can be fed with
loops and curls. This process is illustrated sche- both drawn and undrawn (POY or LOY) fila-
matically in Figure 58. The basic mechanism of ment yarns, they are equipped with one or two
air-jet texturing involves mechanical deforma- drawing zones that precede the texturing zone
tion of individual filaments [110]; it can there- [111–113].
fore be used to texture both thermoplastic and The crimp character of an air jet textured yarn
nonthermoplastic filaments. is much different to that of a friction false twisted
The construction of air-jet texturing ma- textured yarn. The two types of textured yarn are
chines is similar to that of false-twist textur-
 Fibers, 3. General Production Technology 45

Figure 57. Different designs of friction false twisting machines

Courtesy of Barmag/Saurer Group, Germany

Figure 59. Mechanical stuffer-box crimping

Figure 58. Schematic representation of loop formation in an a) Incoming yarn; b) Feed rollers; c) Heated stuffer box;
air jet d) Closing device with changeable weight
Courtesy of Heberlein, Wattwil, Switzerland
46 Fibers, 3. General Production Technology

used in different fields of application in the tex- cessed simultaneously at each machine position,
tile industry. i.e., in each draw-texturing unit. One- and two-
end operations are carried out commercially at
up to 67 m/s, but the speed must be reduced to
3.3.4. Stuffer Box Texturing 42 – 50 m/s in four-end operations.

In the mechanical stuffer box process (shown

schematically in Fig. 59), texturing is achieved
by using a set of rollers to feed the filament yarn
into a heated, pressure-controlled stuffer box.
The yarn undergoes buckling deformation, and
a sawtooth, two-dimensional crimp is formed
[114]. Stuffer-box crimped yarns up to 330 dtex
are of minor commercial importance for textile
applications. The pneumatic stuffer box has al-
most completely replaced the mechanical stuffer
box for texturing coarser yarns with a fine-
ness of ca. 500 – 3300 dtex, which are primar-
ily made of polyamides or polypropylene. The
major reasons for this are probably the substan-
tially higher texturing speed of up to 67 m/s and
the three-dimensional crimp which is far supe-
rior in bulk and volume to the sawtooth, two
dimensional crimp. The basic principle of the
pneumatic stuffer box was described in a patent
application in 1957 [115]. The system is shown
schematically in Figure 60.
Two different process variants are available
for the production of textured BCF yarn with a
fineness of 1000 – ≥ 4000 dtex for the carpet and
upholstery industries: discontinuous draw tex-
turing and continuous spin-draw texturing [116–
118].
Discontinuous draw texturing consists of
two steps. The undrawn filaments are first spun
on conventional spinning units and wound to
give cylindrical bobbins with weights of ca.
20 – 50 kg. In a second step, the spun bobbins Figure 60. Pneumatic stuffer box crimping [115]
are then placed in supply creels, and the individ- a) Yarn; b) Heated air; c) Injection tube; d) Stuffer box;
e) Partition for separating air flow; f) Cold gas; g) Setting
ual filament yarns are conveyed to the individual zone with air-permeable walls; h) Crimped yarn
positions of the draw-texturing machine via yarn
guides and brakes. A typical draw-texturing ma- The discontinuous, two-step process is par-
chine is shown in Figure 61. ticularly suited to the manufacture of speciality
The draw unit of the machine consists of a BCF yarns. Various spun-dyed filament yarns of
system of heated godets formed either by pairs different fineness or different dyeing properties
of rollers or by feed rollers with idler rolls. Af- can be plied and processed together in a single
ter being drawn, the filament yarn is textured in texturing chamber to give special BCF yarns.
a pneumatic stuffer box, deposited on cooling The high texturing speed attainable with the
drums, and subsequently wound on cylindrical pneumatic stuffer box system allows the spin-
bobbins. As a rule, the textured yarn is also inter- ning of the filament yarn and draw texturing to
laced prior to winding to improve its processing be combined in a highly economical, single-step,
characteristics. One to four yarn ends can be pro- continuous spin-draw texturing process. A spin-
 Fibers, 3. General Production Technology 47

draw texturing machine is shown schematically dimensional crimp. This method of texturing al-
in Figure 62; the draw-texturing unit is located lows the two-step process technology of high-
directly below the conditioner of the spinning speed spinning and subsequent draw texturing
machine. The spun filament yarns are drawn (described in Section 3.3.2) to be developed into
immediately, textured, interlaced, and usually a totally integrated, one-step process.
wound at a rate of 50 – 67 m/s by automatic
winders.

Figure 61. Draw-texturing machine with four ends for

bulked continuous-filament (BCF) yarn
Courtesy of Rieter, Winterthur, Switzerland

3.3.5. Bistructural Texturing

In bistructural texturing, also called spin textur-

ing, the latent crimp present in the spun yarn is
activated by a process known as development
[119], [120] (see also Section 2.3.2.1). Texture
can be developed by means of thermal or hy-
drothermal treatment either during or after sepa-
rate drawing [121]. Alternatively, texture devel-
opment can occur during dyeing or heat-setting
after the smooth yarn has been processed into Figure 62. One-step, spin-draw texturing machine for nylon
textiles [122]. Spinning, drawing, texture devel- 6, bulked continuous-filament (BCF) yarn
a) Extruder; b) Motor and gears ; c) Spin beam; d) Quenching
opment, and winding can also be integrated into system; e) Conditioner; f) Drawing, texturing, and winding
a one-step process [123]. In Section 2.3.2.1 a systems
number of processes are described which can
be used to produce anisotropic filament struc- However, spin texturing is not widely used in
tures that lead to spin-textured yarns. These pro- industry (contrary to earlier expectations) [119],
cesses are all based on the inhomogeneity of [124]. The reason for this could be that bi-
the yarn material in the cross-sectional plane component technology has been predominantly
of the individual filaments. Differences in the used to produce bistructurally textured multi-
shrinkage of the individual filaments, caused filament yarns. This technique involves the si-
by chemical or physical inhomogenity, are pri- multaneous spinning of two polymers and is
marily responsible for the formation of three- much more demanding and also more expen-
48 Fibers, 3. General Production Technology

sive than spinning a single polymer. In addition, To achieve a uniform temperature throughout
bistructurally textured multifilament yarns differ the entire spinning system, it should be heated
in hand (touch) and appearance (crimp) from the with condensing diphyl (a eutectic mixture of
friction-textured yarns that currently dominate diphenyl and diphenyl oxide, boiling range 256 –
the market and have therefore had difficulty in 258 ◦ C at standard pressure) as heat-transfer
being accepted. Especially for polyesters (which medium.
represent about 80 – 90 % of world textured The spin pump conveys a precisely mea-
yarns) the poor crimp stability of bistructural sured volume of melt to the spin pack where it
textured yarns has led only to a few special tex- is distributed and filtered. Pressures may reach
tile applications. 20 MPa. The melt stream finally reaches the
spinneret plate and is extruded through a mul-
tiplicity of holes [126] (Fig. 66). The hole cap-
4. Manufacture of Tow and Staple illary may display various profiles which shape
Fibers the emerging melt stream and the resulting fila-
ment (Fig. 67).
4.1. Fiber Spinning After emerging from the capillary, the melt
stream is cooled by heat exchange with the sur-
Spinning processes used in the production of tow roundings and solidifies to form a filament. Con-
and staple fibers can be divided into three major ditioned air is usually used as a cooling medium
groups which are listed below in order of their and is blown through the bundle of filaments.
commercial importance: The air impinges on the filaments with a lam-
inar flow at a defined velocity [127]. If circu-
1) Melt spinning (conventional, compact, and lar or rectangular spinnerets are used, the neces-
continuous one-step processes) sary amount of air is blown across the filament
2) Wet spinning bundle by means of a quenching shaft. In the
3) Dry spinning case of annularly arranged holes or annular spin-
The spun filaments are combined to form a nerets, central quenching is used, in which air is
tow, which is drawn, washed, heat-set, dried, blown either outward or inward from a tubular
crimped, and packaged. Staple fibers are ob- distributor and thus flows radially past the fila-
tained by cutting the tow into defined lengths. ments (Fig. 68). Central quenching systems can
handle a much larger number of holes than air
shafts and, hence, increase polymer productiv-
4.1.1. Melt Spinning ity per spinneret. They are thus more econom-
ical and, in addition, produce yarn of excellent
4.1.1.1. Conventional Process quality [17]. Spinneret plates with a hole den-
sity of ca. 25 holes per square centimeter and a
The basic principles of melt spinning are de- total of ca. 7000 holes can be used. Throughputs
scribed in Section 2.1.3. Polyesters, polyamides, per spinning position of 240 kg/h and machine
and polyolefins are currently the most important capacities up to 180 t/d can thus be attained. In
melt-spinnable polymers. contrast, the maximum possible number of holes
The molten polymer can be pumped directly in rectangular spinnerets is ca. 3000, and in cir-
from a polycondensation unit to the spinning cular spinnerets with cross-flow quenching sys-
unit (direct spinning). Alternatively, the polymer tems ca. 700.
granulate is dried and/or conditioned, melted in The extruded, solidifying filaments are drawn
a suitable screw extruder, and conveyed to the off by an external force and, depending on the
spinning unit [125]. Since a spinning unit gen- polymer and the fineness, attain their final shape
erally consists of several identical spinning posi- in a zone 3 – 200 cm below the spinneret. The
tions, the polymer is transported to the spin beam bundle of filaments is then gathered together,
along paths of equal length by means of a dis- redirected, and combined with bundles from
tributor. The spin beam (Fig. 63) is connected to other spinning positions to form a tow.
the spin pump (Fig. 64) and also accepts the spin Spin finish is applied to the filaments prior
packs (Fig. 65) by either top or bottom loading. to gathering by means of either a static system
 Fibers, 3. General Production Technology 49

Figure 63. Spin beam for fiber production

Courtesy of Inventa-Fischer AG, Domat/EMS, Switzerland,

(e.g., slot finishing) or a dynamic system (e.g., 4.1.1.2. Compact Process

roller finishing). The spin finish normally con-
sists of a mixture containing demineralized wa- A compact, one-step process has been developed
ter and 0.1 – 5 % of a lubricant. In both cases for the production of polyolefin fibers in which
the spin finish is applied by the finish appli- spinning is followed immediately by drawing
cator to obtain good tow cohesion, satisfactory [131]. In some cases this technology can also be
electrostatic behavior, and the desired degree of applied to polyamides. The reason for this de-
fiber-to-fiber and/or fiber-to-metal friction. The velopment is that polyolefins are best dyed with
tow then reaches the take-off unit which usually pigments in a melt. Since a broad range of colors
comprises four to six electrically driven godets is available, relatively small units are required
(Fig. 69). The tow, which may be as large as 20 – with rapid changeover facilities.
∧ Compact units have been designed which
100 ktex (= 2 × 105 – 1 × 106 dtex) and moves
at a speed of 8 – 33 m/s, finally reaches the deliv- consist of a melt extruder, mixing devices for
ery unit (also shown in Fig. 69). Here, the tow is colored pigments, and a spin beam with 4 –
usually picked up by so-called sunflower wheels, 16 spinning positions. Spinnerets may have up
slightly undulated, and deposited in a container to 80 000 holes. Extruded filaments are cooled
known as a spin can. The spin cans traverse be- by intense air blowing immediately below the
low the delivery unit to ensure a uniform tow spinneret. Throughputs of ca. 100 kg/h per po-
distribution (Fig. 70. They normally hold 500 – sition are attained at take-off speeds of 0.2 –
8000 kg of tow. 0.5 m/s. After being finished, the filament bun-
Attempts have been made to replace this sys- dles are gathered, redirected, and fed immedi-
tem by one in which the relatively high trans- ately into a drawing zone. The speed of drawing
verse tow velocity is reduced by forcing a rotary is ca. 2.5 m/s. After drawing the tow is annealed,
motion on it [129], [130]. However, these at- crimped, and, if necessary, heat-set. It is then cut
tempts failed due to economic reasons or dam- into defined lengths and packed in a baling press.
age to the tow. A 16-position machine operating in a fineness
Melt-spinning plants similar to the one de- range of 1 – 3 dtex produces tow at a rate of ca.
scribed above usually occupy several floors 15 t/d, the rate is higher for coarser fibers. Such
(Fig. 71). a machine has a maximum height of 5.5 m and
occupies a floor area of 35 × 6 m (Fig 72).
50 Fibers, 3. General Production Technology

Figure 65. Spinneret pack

Figure 66. Spinnerets made of high-grade steel used for melt

spinning of staple fibers
Courtesy of Enka tecnica, Heinsberg, Germany

Figure 64. Gear spin pump

A) Cut-away model (courtesy of Feinpruf, Göttingen, Ger- Figure 67. Cross sections of spinneret capillaries
many); B) Mechanism of operation
 Fibers, 3. General Production Technology 51

Figure 68. Central quenching of spun filaments

A) Outward quenching (courtesy of Inventa-Fischer AG, Domat/Ems, Switzerland); B) Schematic of inward quenching [128]

Figure 69. Spinning machine with take-off godets and delivery unit
Courtesy of Fleissner, Egelsbach, Germany
52 Fibers, 3. General Production Technology

Figure 70. Traversing spin can

Courtesy of Fleissner, Egelsbach, Germany

4.1.1.3. Continuous One-Step Process

The continuous one-step process [132], [133]

was developed as a result of the lower speeds
(< 16 m/s) used in conventional spinning and
integrates drawing, annealing, crimping, heat-
setting, and cutting. This process is primarily
used for manufacturing polyolefin fibers but
in special cases can also be applied to other
melt-spinnable polymers such as polyester and
polyamide.
Rectangular spinnerets are used for spinning,
and four spinning positions arecombined into a
draw-texturing unit. The delivery speed of the
drawing and stabilizing step is 33 – 42 m/s at a
fineness of 30 000 – 40 000 dtex. The multifila-
ment tow is then crimped by a hot air-jet textur-
ing system (cf. Section 3.3.3) and subsequently
deposited on a heat-setting conveyor belt. A spe-
cially developed cutter, based on the principle
of rapid cutting (see Section 4.2.5) divides the
textured filament tow into staple fibers of the
desired length.
An installation of this type has a height of ca.
5.4 m and is ca. 4 m wide and 18 – 30 m long, de-
pending on the length of the heat setting oven;
Figure 71. Conventional spinning plant for polyester staple
it can produce staple fibers at a rate of 8 – 10 t/d
fiber production (Fig 73).
 Fibers, 3. General Production Technology 53

Figure 72. Flow diagram of a compact one-step staple fiber spinning process
a) Spinning; b) Drawing; c) Crimping; d) Heat setting e) Cutting

Figure 73. Flow diagram of a high-speed one-step process for continuous staple fiber production
a) Spinning; b) Drawing; c) Crimping; d) Heat setting; e) Cutting

4.1.2. Wet Spinning 4.1.3. Dry Spinning

The basic principles of wet spinning are de- The basic principles of dry spinning are de-
scribed in Section 2.1.4.2, and the production of scribed in Section 2.1.4.1 and the production of
continuous filaments by this method is decribed continuous filaments by this method is described
in Section 3.2.2. If staple fibers are desired, the in Section 3.2.1. In the production of staple
as-spun filaments produced by compact or com- fibers, the tow leaving the spinning shaft is first
bination spinnerets (Figs. 74 and 75) are gath- guided over a finish applicator, then redirected
ered into a tow in, or on leaving, the spin bath. A and combined with the tow from other spinning
typical spinning machine is shown in Figure 76. positions. It is then taken off by driven rollers and
Spinning positions may be arranged on one or deposited in spin cans. A dry-spinning unit for
both sides. Spun filaments are drawn off at rel- the production of staple fibers is illustrated sche-
atively low speed, but this is offset by using a matically in Figure 77. Production rates range
very large number of spinneret holes. from 3 – 8 m/s.
In the continuous processes predominantly
used today, the tow is guided directly to a draw-
ing unit for further processing (cf. Section 4.2). 4.2. Posttreatment of Tow and Staple
Wet-spinning lines produce up to 90 t of poly- Fibers
acrylonitrile (PAC) tow per day (total fineness
= 770 dtex) at a rate of 1.3 m/s. However, PAC The properties of spun fibers do not meet the re-
fibers are also produced by the more economical quirements for their final application. Strength is
melt-spinning process [134]. low, elongation and shrinkage are too high, and
further processibility and blendability with nat-
ural fibers are not assured. As described for the
one-step processes (Sections 4.1.1.2 and 4.1.1.3)
and the wet-spinning process (Section 4.1.2),
54 Fibers, 3. General Production Technology

Figure 74. Spinnerets used in the wet spinning of staple fibers

Courtesy of Enka tecnica, Heinsberg, Germany

Figure 75. Filaments being spun through a spinneret in the Figure 76. Wet-spinning machine for the production of sta-
production of staple fibers by wet spinning ple fibers
Courtesy of Enka, Wuppertal, Germany Courtesy of Enka, Wuppertal, Germany
 Fibers, 3. General Production Technology 55

Figure 77. Dry-spinning unit for production of staple fibers

a) Pump; b) Spin pump; c) Spinneret; d) Spin shaft; e) Finish applicator; f) Redirecting godet, g) Take-off unit; h) Spin can

staple fibers must be converted to useful fibers of demineralized water and a lubricant. Drawing
by a suitable sequence of processing steps which is performed between two or three sets of rollers
include drawing, washing, heat-setting, drying, and is referred to as one- or two-step drawing,
crimping, cutting, and packaging. These pro- respectively [136]. Drawing itself is always di-
cesses are carried out on fiber band production vided into two fields: the first comprising the
lines which can handle a large number of tows range of draw up to the natural draw ratio and
and may be up to 150 m long. The multiple tows the second comprising the region beyond this
are fed into the line and are processed simul- ratio. The most common types of drawing used
taneously. Four widely used examples of such commercially are summarized in Figure 80.
lines are illustrated in Figure 78. Lines produce Temperature control, the position of the draw
200 t of staple fibers per day and have a trac- point, and the type of draw used depend on the
tive power of 18 t, a production speed of 5 m/s polymer and the production process and are pro-
and can handle a total drawn tow of 6×106 dtex prietary know-how of the manufacturer. A suit-
[135]. able draw ratio must also be chosen to obtain
a desired type of fiber from a specific polymer.
Particular care must be taken not to leave any
4.2.1. Drawing of Tow undrawn sections in the filament, which would
result in uneven dyeing. Important factors in this
In the case of fibers produced by melt or dry respect are the density (decitex per centimeter)
spinning, the spin cans containing the as-spun of the tow on the rolls, the uniformity of temper-
fiber tow are placed in a can creel. As shown in ature control in the rollers and baths, modifica-
Figure 79, the tow from these cans is plied and tion of the frictional behavior of fibers by finish
conveyed as a band to the drawing unit of the application, the drawing speed, the position of
production line. the draw point, and last but not least, maintaine-
Prior to being drawn, the fiber band passes nance of constant operating parameters [1], [61],
through an immersion bath filled with fluid to [84]. Today high-capacity polyester fiber lines
adjust its frictional properties and obtain a uni- (100 – 200 t/d) are equiped with a two-step pro-
form temperature (Fig. 80A). The fluid consists
56 Fibers, 3. General Production Technology

Figure 78. Production line for polyester staple fibers

A) Can creel; B) Drawing and heat setting; C) Crimping and drying; D) Cutting and baling

cess with a immersion draw chest as the first 4.2.2. Washing and Finishing
stage.
The draw rollers are water- or vapor-heated Washing. Fibers contain various compo-
and have a diameter up to 45 cm. The draw roller nents which must be removed by washing. Wet-
units are cantilevered and up to 1.8 m long, they spun fibers, for example, contain reaction prod-
can process more than 200 t of fiber per day. ucts, and melt-spun fibers of nylon 6 may con-
Draw ratios range from 1 : 2 to 1 : 6 and draw tain monomeric caprolactam. Washing can take
fineness is up to 600 ktex. The draw fibers leave place at various points along the fiber band pro-
the drawing zone at speeds up to 6 m/s. The duction line: during or after drawing, after heat-
drawing units must be able to withstand draw- setting, crimping (tow), or after cutting (flock).
ing forces up to 210 kN. A typical drawing unit The following devices can be used to wash the
is shown in Figure 81. tow or flock: dip tanks (tow), screen drums
In the case of fibers produced by wet spin- (tow/flock), and screen belts (flock).
ning, the multifilaments extruded from a large Washing fluid (water) is circulated in the bath,
number of spinnerets are gathered to form a par- and its volume, temperature, chemical composi-
tial tow and washed prior to drawing. Multistep tion, and concentration are controlled.
or continuous drawing is usually carried out in
hot water which contains a small amount of sol-
vent. The total draw ratio can be as high as 1 : 10.
 Fibers, 3. General Production Technology 57

Figure 79. Production line showing the fiber band

Courtesy of Fleissner, Egelsbach, Germany

Finishing. The fiber surface must be pro- low temperature (< 90 ◦ C) to prevent changes
vided with an appropriate finish to ensure suit- in fiber structure; this represents pure drying. If
able running properties during production and the drying temperature were increased in this
subsequent processing. In a fiber production case, the fibers would be heat-set and thus lose
line, the finish is applied by immersing the tow in their typical cotton-like properties. Drying and
an immersion bath at the head of the line which heat-setting can be carried out at constant length
is filled with finish consisting of special lubrica- or with free or limited shrinkage.
tion oils (Fig. 82). After being drawn, cotton-like polyester
Alternatively, finish can be applied before the fibers are heat-set at constant length on calen-
crimper using kiss rollers (Fig. 82D), into the ders (Fig. 83).
crimper or after the crimper, or before the cut- Calender rollers are heated with a suitable
ter by using a spraying unit (Fig. 82B and C). heat transfer oil and their surface temperature
Finishes are applied with minimum loss, which is brought up to 230 ◦ C. The tow is run over
means that little or no rinsing is required between the requisite number of rollers, with appropriate
process steps; this eliminates recovery costs and contact times.
minimizes pollution of the environment. Heat-setting with free shrinkage is usually
carried out in a plate belt dryer (Fig. 84A) or a
screen drum dryer (Fig. 84B). Here, the material
4.2.3. Drying and Heat-Setting is deposited in meandering loops or in the form
Fibers are dried primarily to remove water and to of flocks at the entrance to the dryer – setter and
obtain a commercially acceptable weight. How- is transported through the system. The material
ever, heat-setting begins if drying is performed is dried and heat-set by circulating a stream of
at high temperature; this considerably improves heated gas, usually air. In addition to transfer of
the fine structure of fibers (especially that of cel- heat to the fiber material by means of contact or
lulose or wet-spun fibers). On the other hand, convection, radiation may also be used.
polyester fibers with stress-elongation charac-
ter similar to that of cotton are dried at very
58 Fibers, 3. General Production Technology

Figure 80. Principal types of drawing used commercially

A) Two-field, two-step drawing; B) One-field, one-step drawing; C) One-field, two-step drawing; D) Two-field, two-step
drawing; E) Two-field, two-step drawing; F) Two-field, two-step drawing
a) Immersion bath; b) Feed rollers; c) Draw rollers; d) Heat-setting rollers; e) Steam channel; f) Hot-water bath

4.2.4. Crimping of concave rolls or tow plyers. A dancing roll or

a measurement unit is used to obtain uniform,
Texturing in staple fiber production lines is constant tow band tension. Uniform temperature
mainly performed with stuffer box crimpers. throughout the tow is provided by a steam or va-
They are constructed in widths of 20 – 660 mm, por zone which precedes the crimper and also
can process 3 – 10 ktex of tow per centimeter of affects the modulus of elasticity of the fiber and
width, and operate at a speed of up to 7 m/s. The thus crimp formation.
machines must be built with high precision and In the crimper, the material is transported
must be extremely sturdy. A crimping unit used over temperature-controlled rollers, pushed
in staple fiber production lines is shown sche- against the plug of material that is forming, and
matically in Figure 85. thus forced to buckle (cf. Section 2.3.2.2). Crimp
For defect-free processing of tow the material formation is determined by material properties
must be fed into the crimper homogeneously. To (modulus of elasticity, diameter, friction), the
reduce the working widths of the tow bands from geometry of the stuffer box, and the pressure
the preceding stage (drawing/heat setting) to the selected in the box. Steam is often injected into
width of the crimper, they are folded with the aid
 Fibers, 3. General Production Technology 59

Figure 81. Drawing unit

Courtesy of Fleissner, Egelsbach, Germany

Figure 82. Finishing units for staple fibers

A) Immersion bath; B,C) Spraying units; D,E) Finishing units with kiss rollers

the box to set the texture. A crimper is shown in of 6 – 18 mm. Staple lengths of 30 – 45 mm are
Figure 86. suitable for processing in equipment designed
to handle cotton; lengths of 60 – 150 mm can be
processed in equipment designed to handle wool
4.2.5. Cutting or wool blends.
In older, obsolete cutters, the tow moved over
The continuous tow produced on the staple fiber vertically running, slotted wheels and was cut
production line is finally cut by mechanical cut- between the slots by rotating sets of blades. Dif-
ters. For short fibers, the tow is cut into lengths ferent types of cutters are now used, however.
60 Fibers, 3. General Production Technology

Figure 83. Heat-setting calender

Courtesy of Fleissner, Egelsbach, Germany

Figure 84. Dryers used for drying and heat-setting staple fibers
A) Plate belt dryer; B) Screen drum dryer
Cross sections of the dryers are shown on the right.

Figure 85. Crimping unit for staple fibers

a) Tow plyer; b) Dancing roller; c) Steam channel; d) Stuffer box
 Fibers, 3. General Production Technology 61

The Lummus system is capable of cutting tow rial through the blades (Fig. 88). This cutter can
at up to 600 ktex at a rate of 5 m/s. The material operate at high cutting speeds, and 10-ktex tows
is wrapped around a rotating, horizontal ring of can be cut at 83 m/s.
blades and pressed against the cutting edge of In a third type of cutter, a continuous tow is
the blades by a pressure roll (Fig. 87). cut by blades which are arranged in a pattern
similar to the thread of a screw. The parallel ar-
rangement of the fibers is thereby retained and
the cut fibers therefore form a band. In contrast to
the other cutting methods, natural fibers in the
form of slivers can be blended with the staple
fibers in a second step (converter process).

4.2.6. Packaging

Staple fibers are compressed into rectangular

bales weighing up to 500 kg with material densi-
ties of > 0.5 g/cm3 . Usually, the fibers are trans-
ported pneumatically from the cutters to a pre-
press for preliminary compacting and are then
brought to balesize in a main press. In the press,
the material is wrapped in plastic sheeting and
tied with metal or plastic straps.
Continuous tow is folded, deposited in boxes,
and compacted with press rams. It can also be
packed in bales if the tow is first folded and com-
pacted in suitable containers.
Figure 86. Jumbo Crimper
Courtesy of Fleissner, Egelsbach, Germany

5. Manufacture of Monofilaments
Monofilaments with diameters of ca. 0.06 –
2 mm have a wide range of applications, par-
ticularly in industry [137]. Monofilaments can
only be produced from thermoplastic, melt-
spinnable polymers such as polyamides [138],
polyesters [137], polypropylene, polyethylene,
and poly(vinyl chloride). Polymers that can only
be spun by wet spinning (e.g., polyacryloni-
trile) are not suitable for the manufacture of
monofilaments. Strict requirements are placed
on the properties of monofilaments, especially
on the constancy of diameter, shrinkage, and
Figure 87. Cutter operating by the Lummus principle strength. Specially optimized units have been
a) Pressure disk; b) Tow; c) Cut staple fiber; d) Knife blade; developed which provide the required narrow
e) Feed rollers
tolerances and, at the same time, the most eco-
In a high-performance cutting system, the nomical method of monofilament production
tow is drawn between a rotating cutter head [139]. Modern, industrial production of monofil-
and an inclined, free-running pressure disk po- aments is carried out in one step in which spin-
sitioned above it. The narrowing gap between ning, drawing, posttreatment, and winding are
the pressure disk and the cutter head builds up combined into a continuous process. A monofil-
sufficient pressure in the tow to push the mate- ament production plant is shown schematically
62 Fibers, 3. General Production Technology

Figure 88. Tension stand with cutter

Courtesy of Fleissner, Egelsbach, Germany

Figure 89. Monofilament production plant

a) Granulate extrusion; b) Water bath; c) First drawing zone; d) Second drawing zone; e) Heat-setting; f) Winding

in Figure 89. Figure 90 shows a monofilament uously as a yarn warp over guide rolls. They are
winding machine. fed into drawing units equipped with three to
The polymer granulate is melted in an ex- seven draw rolls and hot steam or hot air chan-
truder; the melt is then filtered, fed into the nels.
spin nozzle and pressed through spinnerets. Ad-
ditives such as lubricants or stabilizers can be
added to the granulate or fed as a side stream
into the extruder or into the melt line leaving the
extruder. The additives are then distributed ho-
mogeneously in the melt with the aid of mixing
devices.
Depending on the polymer and the diameter
of the monofilament, up to 200 – 300 monofila-
ments can be spun simultaneously at each spin-
ning position and posttreated in the form of a
yarn warp. The melt pressure and the temper-
ature of the monofilament spin heads must be
kept constant within narrow limits to ensure that
the simultaneously spun monofilaments are of Figure 90. Monofilament winding machine
consistent quality. The fluid melt monofilaments
are spun into a water bath and drawn off contin-
 Fibers, 3. General Production Technology 63

Drawing temperature and draw ratio depend contains several thousand capillary holes. Hole
on the polymer used to produce the monofil- number, size (0.3 – 0.8 mm), and l/d ratio (1 – 6)
aments and on the desired properties of the mainly depend on the polymer properties, fila-
end product. Drawing can be followed by heat- ment fineness, and required capacity.
setting and/or relaxing before the monofilaments The liquid filaments emerge from the spin-
are individually wound on flanged, conical, or neret, are cooled to room temperature with con-
biconical bobbins at a speed of 2 – 3.3 m/s. If ditioned air, and enter into the aerodynamic
necessary, a finish oil can be applied prior draw-off system. To achieve a high tensile
to winding. Computer-controlled winders with strength it is important that the drawing force
loss-free, fully automatic bobbin changers and caused by friction between air and filament sur-
up to 64 winding positions are available. face is applied near the glass transition point.
The drawing forces needed for high filament
speeds are generated by the high velocities of the
6. Process Technologies for air (up to 16000 m/min) that is sucked in through
Spunbonded Nonwovens the drawing slot. Depending on the polymer,
filament speeds of, e.g., up to 6000 m/min for
Nonwovens are classically produced by card- polyester and up to 4000 m/min for polypropyl-
ing staple fibers (→ Nonwoven Fabrics). Spun- ene are reached. The air – filament stream is di-
bonded nonwovens, however, are made from rected downward into the web formation section,
continuous filaments in a one-step procedure; and the filaments are deposited on the moving
investment and production costs are thus lower. screen belt. The filaments are distributed in a
Thermoplastic polymers such as polypropylene, random and entangled manner by controlled tur-
polyethylene, polyamides, or polyesters are melt bulence and turbulent vortices in the air stream.
spun through special spinnerets to form contin- As the web-formation chamber is directly con-
uous filaments which are drawn by means of air nected to the drawing part and this space is fully
streams and directly deposited as a random web protected, no disturbance by ambient air or other
on a moving collection screen belt. Finally, the surrounding effects can take place. This feature
filaments are bonded together by heat, chemi- minimizes edge trimming requirements and re-
cal, or other entangling techniques, e.g., needle sults in economical use of polymer. Underneath
punching or hydroentanglement. the conveyor belt the air is sucked off and re-
Several different process technologies are cycled to the spinning section. Under predeter-
available for the industrial production of spun- mined spinning conditions, the fabric weight can
bonded nonwovens. They differ as to whether be adjusted by varying the speed of the moving
the filament bundles are spun from circular spin- screen belt.
nerets or from rectangular spinnerets like a fila- For boosting the productivity additionally
ment curtain. They also differ with regard to the one or more spinning beams can be added or
production of air streams (over- or underpres- a melt-blown system can be installed between
sure), their guidance and generally in depositing two beams. This permits the production of spun-
the filaments on the collecting belt (web forma- bond/meltblown/spunbond (SMS). The power
tion). consumption of this suction process is relatively
A typical spunbond process [106] is illus- low compared with the process where the dra-
trated in Figure 91. Spinnable thermoplastic woff system operates with compressed air.
polymer chips from a silo are melted in an ex- The process permits the production of webs
truder, into which colored pigments and other with fabric weight of 8 to 300 g/m2 , widths bet-
additives can be injected. The polymer is pre- ween 0.6 and 4.6 m, and filament fineness rang-
filtered through a melt filter (continuous type) ing from 0.6 to 6 dtex.
and fed to the spinning beam. The spinning sys-
tem is vapor-heated with a mixture of diphenyl
and diphenyl oxide and ensures a constant tem- 7. Economic Aspects [145–147]
perature profile across the full width of spin-
neret. A spin pump forces the melt through Since the mid 1970s, excess production capaci-
the melt distribution line to the spinneret which ties have resulted in fierce international compe-
64 Fibers, 3. General Production Technology

Figure 91. Schematic of the production of spunbonded nonwovens

a) Extruder; b) Melt filter; c) Spin pump; d) Spinning beam;e) Quenching chamber; f) Web-formation chamber; g) Suction
blower; h) Conveyor screen; i) Calender; j) Winder

tition among the producers of man-made fibers, duced because granulate no longer has to be pro-
particularly in industrialized Western countries. duced, dried, and remelted. As a result, almost
Later the most strongly growing market for man- all polyester fiber plants built today are continu-
made fiber was in Asian Countries. The eco- ous production lines which employ direct spin-
nomics and thus the competitiveness of a man- ning; production capacities are 100 – 200 t/d in
made fiber enterprise are affected to a high de- one line.
gree by the total capacity of its fiber and filament
plants [2], by the size of the individual produc-
tion lines, and by the technologies used.
Until the early 1970s, for example, the poly-
mer required for the production of polyester
fiber was made primarily in batchwise or con-
tinuous polycondensation plants with capacities
of 30 – 60 t/d; dried granulate, as a rule, was
thus the starting material used for spinning sta-
ple fibers and filament yarns. The profitabil-
ity of a polyester plant increases considerably Figure 92. Dependence of investment costs on number of
with increasing output capacity of a produc- spinning positions and number of holes per spinneret
tion line [17], [85], [142]. A particularly dra- Figures are based on a melt-spinning unit with central
quenching and a production capacity of 45 t/d
matic reduction in manufacturing costs can be
achieved in continuous installations by omitting Investment and manufacturing costs of
the granulate step and employing direct spinning polyester staple fibers are affected to a high
in which the fibers are spun directly from the degree by the output of the spinning positions
melt. Investment costs for buildings and equip- and the capacity of the drawing units. Figure 92
ment are lower, and energy consumption is re- shows that investment costs of a staple fiber
 Fibers, 3. General Production Technology 65

Figure 93. Comparison of investment and production costs for fiber production lines in relation to their capacity

spinning plant can be halved by doubling the four-end machine instead of a two-end machine
1215 spinneret holes per spinning position and [144]. The break-even point is calculated to be
halving the number of spinning positions. Fig- a fineness of 1200 dtex.
ure 93 demonstrates that manufacturing costs in Fierce international competition in the pro-
the drawing unit can be more than halved if the duction of synthetic fibers and the construction
installation has a capacity of 90 t/d instead of of synthetic fiber plants is forcing the man-made
30 t/d. fiber industry and engineering companies to de-
Efforts to improve competitiveness in the area velop new, lower cost, better quality technolo-
of filament yarns have focused on reducing in- gies. Only the replacement of out-of-date, un-
vestment costs by combining multistep, discon- profitable production facilities by new, highpro-
tinuous processes into a single, continuous pro- ductivity technologies can assure the long-term
cess. One-step processing also reduces manufac- profitability and competitiveness of an enter-
turing costs by cutting down personnel require- prise.
ments. However, modern one-step processes not
only provide cost advantages, but generally re-
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87. ICI, DE-OS 2 836 514, 1979 (P. Carr).
68 Fibers, 3. General Production Technology

113. J. Kessler, Chemiefasern Textilind. 36 (1986) 131. A. Schweitzer, Chemiefasern Textilind. 28

295 – 296. (1978) 41 –42.
114. C. Iyer: Dissertationsarbeit, TH Stuttgart 132. BARMAG, DE 3 523 321 A1, 1985 (M.
1974. Bussmann, F. Hensen, W. Runkel).
115. H. Brüttig, DD 17 786, 1957 (H. Bruettig). 133. D. Ahrendt, Textiltechnik (Leipzig) 36 (1986)
116. H. Schellenberg, Chemiefasern Textilind. 34 242 –246.
(1984) 902 – 908. 134. Amer. Cyanamid, US 4 163 770, 1979 (H.
117. D. Ahrendt, H. Dietrichs, Chemiefasern Porosoff).
Textilind. 31 (1981) 207 – 209. 135. F. Schmitt, Melliand Textilber. 63 (1982)
118. H. Vieth, E. Göbel, Textiltechnik (Leipzig) 28 830 – 835.
(1978) 618 – 621; Textiltechnik (Leipzig) 29 136. K. Riggert, Chemiefasern Textilind. 31 (1981)
(1979) 469 – 473. 638 – 648.
119. P. Piller: Bulked Yarns, SNTL-Publishers of 137. G. Beyer, Chemiefasern Textilind. 32 (1982)
Technical Literature, Praque, in coedition with 452.
the Textile Trade Press, 11 Albert Sq., 138. R. Vieweg, A. Müller, Kunststoff-Handbuch,
Manchester M2 5 HD 1973, pp. 430 – 470. vol. VI, Hauser Verlag, München 1966,
120. R. Jeffries: Biocomponent Fibers, Merrow
pp. 336 – 340.
Publishing Co. Ltd., 276 Hemstead Road,
139. Chemiefasern Textilind. 32 (1982) 458.
Watford, Herts, England 1971.
140. L. Hartmann, F. Fourné, Chemiefasern
121. ICI, GB 809 273, 1955 (R. H. Speakman); ICI,
Textilind. 32 (1972) 231 – 236.
US 3 629 386, 1969 (P. E. Knapp).
122. Monsanto, US 4 600 644, 1982 (J. E. Bromley, 141. R. Hoffmeister, Chemiefasern Textilind. 32
J. M. Chamberlin, J. Yu). (1982) 724.
123. Monsanto, US 4 202 854, 1977 (P. T. Howse, 142. L. Riehl, H. Reiter, Chemiefasern Textilind.
A. E. Wilkie). 33 (1983) 22 – 29.
124. F. Fourné, Chemiefasern Textiltechnik 18 143. F. Maag, Chemiefasern Textilind. 31 (1981)
(1968) 353 – 359. 118 –124.
125. L. Riehl, Chemiefasern Textilind. 37 (1987) 144. H. Schellenberg, Chemiefasern Textilind. 34
32 – 42. (1984) 902 – 908.
126. M. E. Schwab, Chemiefasern Textilind. 36 145. World Markets for Textured Yarns, Textile
(1986) 499 – 502. Intelligence Ltd., Romford/UK, 1995.
127. F. Fourné, DE 2 930 553, 1979 (F. Fourné). 146. Chemical Fibers International, Volume 48
128. Du Pont, US 3 050 821, 1962 (J. J. Kilian). (September 1998) 278.
129. Neumag, DE 2 553 866, 1975 (E. Bauch). 147. BARMAG AG, Technical data, FK6 - 1000,
130. IWEKA, DE 2 747 706, 1977 (H. Enneking, G. Tex 100/2 (9/1998).
Schubert, L. Hanger).
 Fibers, 4. Synthetic Organic 1

Fibers, 4. Synthetic Organic

Leland L. Estes, (E. I. Du Pont de Nemours & Co.), Nashville, Tennessee 37215, United States (Chap. 1)
Helmut Sattler, Königstein-Schneidhain, Hoechst Aktiengesellschaft, Federal Republic of Germany
(Chap. 2)
Hans Berg, Königstein-Schneidhain, Hoechst Aktiengesellschaft, Federal Republic of Germany (Chap. 2)
Karl-Heinz Wolf, Bayer AG, Dormagen, Federal Republic of Germany (Chap. 3)
Michael Kausch, Bayer AG, Dormagen, Federal Republic of Germany (Chap. 3)
Hans Schröer, Bayer AG, Dormagen, Federal Republic of Germany (Chap. 3)
Antonio Pellegrini, Moplefan, Milano, Italy (Section 4.1)
Paolo Olivieri, Moplefan, Milano, Italy (Section 4.1)
Werner Schoene, BASF AG, Ludwigshafen, Federal Republic of Germany (Sections 4.2– 4.4)
Alfred Nogaj, Bayer AG, Dormagen, Federal Republic of Germany (Chap. 5)
Carlhans Süling, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 5)
Jacques Menault, (Rhovyl), St-Foy-les-Lyons, France (Chap. 6)
Tetsuro Osugi, Nippon Chemtec Consulting Inc., Osaka, Japan (Chap. 7)
Osamu Morimoto, Nippon Chemtec Consulting Inc., Osaka, Japan (Chap. 7)
Peter E. Frankenburg, E. I. Du Pont de Nemours, Wilmington, Delaware 19898, United States (Chap. 8)

1. Polyamide Fibers . . . . . . . . . . . 4 2.2.2. As-Spun Yarns . . . . . . . . . . . . . 27

1.1. Properties . . . . . . . . . . . . . . . . 4 2.2.3. Drawn Materials . . . . . . . . . . . . 28
1.2. Polyamides for Synthetic Fibers . 5 2.2.4. Dyed Poly(ethylene terephthalate)
1.2.1. Aminocarboxylic Acid Type Material . . . . . . . . . . . . . . . . . 28
Polyamides . . . . . . . . . . . . . . . 6 2.3. Poly(ethylene terephthalate)
1.2.2. Diamine – Dicarboxylic Acid Type Fibers . . . . . . . . . . . . . . . . . . 29
Polyamides . . . . . . . . . . . . . . . 9 2.3.1. Staple Fibers . . . . . . . . . . . . . . 29
1.2.3. Copolyamides . . . . . . . . . . . . . 10 2.3.2. Continuous-Filament Yarns for Ap-
1.3. Special Requirements for parel and Home Furnishings . . . . . 32
Polyamides . . . . . . . . . . . . . . . 11 2.3.3. Continuous-Filament Yarns for In-
1.4. Modifying Additions . . . . . . . . 12 dustrial Applications . . . . . . . . . 35
1.5. Technology of Melt Spinning . . . 13 2.3.4. Spunbonds . . . . . . . . . . . . . . . . 38
1.5.1. Melt Spinning of Nylon . . . . . . . 13 2.3.5. Monofilaments . . . . . . . . . . . . . 39
1.5.2. Special Techniques and Products . . 15 2.4. Other Polyester Fibers . . . . . . . 40
1.6. Uses . . . . . . . . . . . . . . . . . . . 16 2.4.1. Poly(tetramethylene terephthalate) . 40
1.7. Economic Aspects, Manufactur- 2.4.2. Poly(1,4-dimethylenecyclohexane
ers, and Trade Names . . . . . . . . 16 terephthalate) . . . . . . . . . . . . . . 41
2. Polyester Fibers . . . . . . . . . . . . 17 2.5. Uses . . . . . . . . . . . . . . . . . . . 41
2.1. Production . . . . . . . . . . . . . . . 17 2.6. Economic Aspects . . . . . . . . . . 44
2.1.1. Starting Materials and Polymer . . . 17 2.7. Polyester: Summary and Future
2.1.2. Spinning . . . . . . . . . . . . . . . . . 19 Prospects . . . . . . . . . . . . . . . . 45
2.1.3. Drawing . . . . . . . . . . . . . . . . . 21 3. Polyurethane Fibers . . . . . . . . . 48
2.1.4. Aftertreatment . . . . . . . . . . . . . 22 3.1. Physical Properties . . . . . . . . . . 48
2.1.5. Dyeing of Poly(ethylene terephthal- 3.2. Chemical Properties . . . . . . . . . 50
ate) Fiber Products . . . . . . . . . . 23 3.3. Raw Materials . . . . . . . . . . . . . 50
2.2. Structure and Properties . . . . . . 25 3.4. Production of Polymer . . . . . . . 52
2.2.1. Polymer . . . . . . . . . . . . . . . . . 25 3.5. Spinning Processes . . . . . . . . . . 52

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a10 567
2 Fibers, 4. Synthetic Organic

3.6. Uses . . . . . . . . . . . . . . . . . . . 53 5.5. Types of Fibers . . . . . . . . . . . . 80

4. Polyolefin Fibers . . . . . . . . . . . 54 5.6. Economic Aspects . . . . . . . . . . 83
4.1. Polypropylene Fiber . . . . . . . . . 55 6. Poly(vinyl chloride) and
4.1.1. Chemical and Physical Properties . 55 Poly(vinylidene chloride) Fibers . 83
4.1.2. Production . . . . . . . . . . . . . . . . 57 6.1. Fibers from Pure Poly(vinyl chlo-
4.1.2.1. Raw Materials . . . . . . . . . . . . . 57 ride) Homopolymer . . . . . . . . . 84
4.1.2.2. Staple Fiber Production Process . . 57 6.1.1. Fibers from Pure Atactic Homopoly-
4.1.2.3. Continuous Filament Yarn Produc- mer . . . . . . . . . . . . . . . . . . . . 84
tion Process . . . . . . . . . . . . . . . 59 6.1.2. Fibers from Blends of Poly(vinyl
4.1.2.4. Stabilization . . . . . . . . . . . . . . . 59 chloride) Homopolymer . . . . . . . 85
4.1.2.5. Pigmentation . . . . . . . . . . . . . . 60 6.1.3. Products, Properties, and Uses . . . 86
4.1.3. Uses . . . . . . . . . . . . . . . . . . . 61 6.2. Fibers from Postchlorinated
4.1.4. Economic Aspects . . . . . . . . . . . 63 Poly(vinyl chloride) (CPVC) . . . 87
4.2. Polyolefin Film Yarns and Split 6.3. Fibers from Vinyl Chloride
Yarns . . . . . . . . . . . . . . . . . . . 63 Copolymers . . . . . . . . . . . . . . 87
4.2.1. Raw Materials . . . . . . . . . . . . . 63 6.4. Fibers from Poly(vinylidene chlo-
4.2.2. Production of Tapes and Split Yarns 64 ride) and Copolymers . . . . . . . . 88
4.2.3. Uses . . . . . . . . . . . . . . . . . . . 66 7. Poly(vinyl alcohol) Fibers . . . . . 88
4.3. Monofilaments . . . . . . . . . . . . 67 7.1. Physical and Chemical Properties 89
4.3.1. Production . . . . . . . . . . . . . . . . 67
7.2. Production . . . . . . . . . . . . . . . 89
4.3.2. Uses . . . . . . . . . . . . . . . . . . . 68
7.3. Poly(vinyl alcohol) for Fiber . . . 89
4.4. High-Modulus Polyolefin Yarns . 68
7.3.1. Wet Spinning . . . . . . . . . . . . . . 89
4.4.1. Production . . . . . . . . . . . . . . . . 69
7.3.2. Dry Spinning . . . . . . . . . . . . . . 91
4.4.2. Properties and Uses . . . . . . . . . . 69
7.3.3. Mixed Spinning . . . . . . . . . . . . 91
5. Polyacrylonitrile Fibers . . . . . . 69
5.1. Physical Properties . . . . . . . . . . 70 7.4. Uses . . . . . . . . . . . . . . . . . . . 92
5.2. Chemical Properties . . . . . . . . . 70 7.5. Economic Aspects . . . . . . . . . . 92
5.3. Production . . . . . . . . . . . . . . . 71 8. Polytetrafluoroethylene Fibers . . 92
5.3.1. Polymerization . . . . . . . . . . . . . 71 8.1. Physical and Chemical Properties 92
5.3.2. Dissolving . . . . . . . . . . . . . . . . 73 8.2. Production . . . . . . . . . . . . . . . 93
5.3.3. Spinning . . . . . . . . . . . . . . . . . 74 8.3. Uses . . . . . . . . . . . . . . . . . . . 93
5.3.4. Aftertreatment . . . . . . . . . . . . . 75 8.4. Toxicology and Occupational
5.3.5. Special Processes . . . . . . . . . . . 77 Health . . . . . . . . . . . . . . . . . . 94
5.4. Analysis . . . . . . . . . . . . . . . . . 78 9. References . . . . . . . . . . . . . . . 94

The following is a list of specific abbrevia- LOI limiting oxygen index

tions used in this article. LOY low-oriented yarn
MDI methyl diisocyanate
BCF bulked continuous filament
MFI melt flow index
CPVC postchlorinated poly(vinyl
M rD molecular mass distribution
chloride)
PAC polyacrylonitrile
DMA dimethylacetamide
PACM bis(4-aminocyclohexyl)methane
DMF dimethylformamide
PBT poly(butylene terephthalate) =
DMSO dimethyl sulfoxide
poly(tetramethylene terephthalate)
DMT dimethyl terephthalate
PDCT poly(1,4-dimethylenecyclohexane
FOY fully oriented yarn
terephthalate)
HALS hindered amine light stabilizer
PETP poly(ethylene terephthalate)
HDPE high-density polyethylene
POY partially oriented yarn
HE highly elastic
PP polypropylene
HOY highly oriented yarn
PTFE poly(tetrafluoroethylene)
HT high temperature
PUR polyurethane
LDPE low-density polyethylene
PVA poly(vinyl alcohol)
 Fibers, 4. Synthetic Organic 3

PVC poly(vinyl chloride) “outdoor” use because of poor dimensional sta-

PVDC poly(vinylidene chloride) bility.
TDI tolyl, tolylene, or toluene Other general properties of nylon are as fol-
diisocyanate lows:
TMA thermomechanical analysis
TPA terephthalic acid Shrinkage: dependent on conditions; 1 –
UHMM ultrahigh molecular mass 15 % when setting in water or hot air
UHMMPE ultrahigh molecular mass
polyethylene Abrasion resistance: outstanding; espe-
cially suitable for textile floor coverings

Electrostatic charge: high at low relative

humidity; reduced significantly in antistatic
1. Polyamide Fibers fibers (addition of carbon black or polyglycol
ether compounds)
This chapter deals predominantly with lin-
ear polyamide fibers derived from aliphatic
Solubility: at room temperature in concen-
monomers, all of the generic class called ny-
trated inorganic acids, m-cresol, o-chlorophe-
lon. Linear, aliphatic polyamides are conve-
nol, and phenol – alcohol mixtures; at the boil
niently divided into two groups: those made
in benzyl alcohol and phenylethyl alcohol
from aminocarboxylic acids and those made
from diamine – dicarboxylic acids. These are
characterized by the number of carbon atoms Dyeability: with acid, metal-complex, dis-
in the monomeric starting material. For exam- perse, and reactive dyes; special types with basic
ple, nylon 11 is the polycondensate of 11-ami- dyes
noundecanoic acid [H2 N(CH2 )10 COOH]. Ny-
lon 610 is the polycondensate of 1,6-diami- Stability:
nohexane [H2 N(CH2 )6 NH2 ] and sebacic acid Light stability: highly dependent on pigmenta-
[HOOC(CH2 )8 COOH]. Fibers of aromatic tion and presence or absence of stabilizers
polyamides in which the amide linkages attach Thermal oxidation: yellowing and molecular
directly to two aromatic rings are called aramids, degradation reduced by stabilizers (Cu+ or
and are covered under → High-Performance antioxidants)
Fibers. World production of nylon fiber reached Weathering: relatively poor outdoor life, espe-
3.4×106 t/a in 1985 and is expected to grow cially with fine deniers
slowly. The 45-year history of the beginning and Dilute acid: adequate resistance
growth of nylon has been reviewed [7]. Dilute alkali: good resistance
Biological stability: good to very good resis-
tance against decay-producing bacteria, mold
1.1. Properties fungi, and moth larvae
Shape stability: good crease resistance with dry
Nylon fibers are superior to all natural and re- materials. On absorbing water, nylon fibers
generated fibers with respect to high tenacity swell in the direction of the fiber axis. The
and elongation, abrasion resistance, and insen- lengthening must be considered in the manu-
sitivity to rotting and moth attack. By heat treat- facture of clothing, especially with nylon 6
ment, fabrics of nylon fiber can be set into sta- and nylon 66. With felts for floor coverings,
ble shapes through formation of additional hy- dimensional stability is improved by blending
drogen bonds. The highly polar nature of car- with nonswelling fibers such as polypropyl-
bonamide groups also results in swelling of ny- ene.
lon fibers in water or in polar solvents, and
permits simple dyeing processes with disperse, Physical properties of four nylon fibers are
acid, and metallized dyes. Nylon fibers absorb given in Table 1.
moisture and swell longitudinally. This limits
4 Fibers, 4. Synthetic Organic
Table 1. Physical properties of some nylon fibers

Property Nylon 6 Nylon 66 Nylon 11 PACM-12∗

◦
mp, C 214 – 220 255 – 260 190 275

, g/cm3 1.14 1.14 1.04 1.03
Water absorption, %
65 % R.H., 21 ◦ C 3.5 – 4.5 3.5 – 4.5 1.3 1.5 – 2
Water retention 9 – 15 9 – 15 2.9 ca. 3
Tenacity, cN/dtex 3–9 3–9 4–7 2.5 – 3
Elongation at break, % 80 – 15 80 – 15 40 – 15 30 – 25
Wet – dry strength, % 80 – 90 80 – 90 100 NA∗∗
Loop – straight strength, % 70 – 90 70 – 90 NA∗∗ NA∗∗
Elastic modulus, cN/dtex
Textile fibers 5 – 30 5 – 30 45 20 – 30
Industrial fibers 60 – 90 60 – 90 NA∗∗ NA∗∗
Setting temperature, ◦ C 185 – 195 200 – 230 NA∗∗ 190

∗ Nylon from bis(4-aminocyclohexyl)methane and dodecanedicarboxylic acid.

∗∗ Not applicable.

1.2. Polyamides for Synthetic Fibers The effect of C-methyl and N-methyl groups
on the melting temperature of nylons made from
The high molecular mass, linear polyamides that adipic acid and a diamine is as follows:
are useful for synthetic fibers contain mainly
H2 N−(CH2 )4 −NH2 251 ◦ C
methylene groups between the carbonamide H2 N−(CH2 )2 −CH(CH3 )−(CH2 )3 −NH2 180 ◦ C
groups. They comprise those compositions that HN(CH3 )−(CH2 )6 −NH2 145 ◦ C
HN(CH3 )−(CH2 )6 −NH(CH3 ) − 75 ◦ C
can be melted and spun into filaments without
decomposing.
The introduction of cyclic segments into an
aliphatic polyamide chain generally stiffens the Substitution of oxygen or sulfur for a methy-
chain and raises the melting point (Table 2). The lene group in aliphatic polyamides also results
effect is most pronounced when the ring struc- in a lower melting point. In the low molecu-
ture is aromatic and symmetrical, and when the lar mass region, nylon melt temperatures in-
amide group is connected directly to an aro- crease significantly with increasing molecular
matic ring. Connection of two aromatic rings mass. This effect, however, can be neglected at
to the amide group defines the aramid class the high molecular masses necessary for fiber
of polyamides, which usually degrade without production. The strength of nylon fibers also in-
melting and cannot be melt-spun. Melt temper- creases with increased molecular mass, but melt
ature is also strongly affected by ring symmetry, spinning has technological limits because of the
as seen in the 90 ◦ C difference in melting points difficulty of handling very high melt viscosities.
of the meta and para isomers of the two xylene The melting temperature of nylon decreases
diamines. with increased ratio of methylene groups to car-
Introduction of C-alkyl side chains in nylons bonamide groups, and approaches the melting
disrupts molecular order and leads to both a re- temperature of polyethylene (mp 130 – 150 ◦ C,
duction in melt temperature and increased sol- depending on molecular mass). Thus, nylon 22
ubility in organic solvents. The influence of N- melts at 145 ◦ C. However, melting temperatures
alkyl substituents is even greater, because they of the two types of nylon do not decrease uni-
eliminate the possibility of hydrogen bonding formly, because nylons in the homologous series
between polyamide molecules. The polyamide with an even number of methylene groups bet-
of piperazine and adipic acid, which melts at ween carbonamide groups melt at higher tem-
185 ◦ C, is of scientific interest because the ef- peratures than the adjacent nylons with an odd
fect of the missing hydrogen bonds is largely number of methylene groups (Tables 3 and 5).
compensated for by chain stiffening through the This is because the geometrical symmetry of
piperazine radical. the even-numbered configuration permits tighter
chain packing and better hydrogen bonding. Wa-
 Fibers, 4. Synthetic Organic 5
Table 2. Comparison of melting points for various polyamides

Diamine Diacid CAS registry no.∗ mp, ◦ C

m-Xylylene-α,α -diamine adipic [25805-74-7] 243

1,6-Diaminohexane adipic [9011-55-6] 265
p-Xylylene-α,α’-diamine adipic [24938-72-5] 333
1,6-Diaminohexane terephthalic [24938-03-2] 370
p-Xylylene-α,α’-diamine terephthalic [24938-64-5] > 400

∗ For the polyamide from the diamine and diacid.

Table 3. Physical properties of some aminocarboxylic acid type polyamides

Polyamide mp, ◦ C Water absorption, % Wet strength as a
, g/cm3

65 % R. H. 100 % R. H. % of dry strength

4 265 9.1 28.0 70 – 80

6 223 4.3 9.5 85 – 90 1.14
7 233 2.8 5.0 1.10
8 200 1.7 4.0 93 – 97 1.08
9 209 1.5 3.3 1.06
10 188 1.4 3.0 1.04
11 190 1.3 2.8 1.04
12 179 1.3 2.7 100

ter absorption and nylon density also decrease Nylon 2 [25734-27-4]. The polyamide from
with increased number of methylene groups, i.e., aminoacetic acid is really the first member
as the molecule becomes more alkane-like (Ta- of the series defined by the general for-
ble 3). mula H[HN−(CH2 )n −CO]x OH (n = 1). So far,
preparing nylon 2 with sufficiently high molecu-
lar mass for the production of fibers has not been
1.2.1. Aminocarboxylic Acid Type possible. A high order of crystallization would
Polyamides be expected, and spinning would only be possi-
ble by a solvent spinning process. Filaments of
Nylons of the aminocarboxylic type can be pre-
nylon 2 could resemble natural silk very closely
pared by the following methods:
in physical properties.
1) polycondensation of ω-aminocarboxylic High molecular mass nylon 2 derivatives
acids having more than five carbon atoms alkylated on the α-carbon atom may be also
2) hydrolytic polymerization of lactams having viewed as polypeptides of α-aminocarboxylic
more than six ring members, and acids and can be prepared by ionic polymeriza-
3) anionic polymerization of lactams with ex- tion of N-carboxylic acid anhydrides:
clusion of water.
Tables 1 and 3 list the most important physical
properties of this type. Fibers are characterized
by a high tenacity of 6 – 7 g/dtex and a break
elongation of 20 – 30 %. An exception is nylon
4, with a tenacity of ca. 4 g/dtex.

Nylon 1 [32010-01-8]. Nylon 1 falls into this Polymerization can be initiated with a variety
class by virtue of the linear connection of car- of catalysts such as alkali hydroxides and car-
bonamide groups; it is a polyamide based on its bonates, phenols, and amines. Spinnable poly-
chemical structure [8]: mers have been obtained only from pure opti-
−CO−NH−CO−NH−CO−NH−. cal isomers, i.e., l- or d-aminocarboxylic acid
However, derivatives prepared from monoisocy-
anates have no polyamide properties.
6 Fibers, 4. Synthetic Organic

derivatives. The Japanese have produced semi- thoroughly to remove residual monomer, traces
works quantities of polypeptide fibers based on of which accelerate decomposition of the poly-
l-glutamic ω-ester, which are reported to have mer at the melting point. Nylon 4 can be melt-
unusual properties. spun at 279 – 280 ◦ C, but residence time in the
melt must be short to avoid decomposition or
Nylon 3 [25513-34-2]. Nylon 3 would be ex- reversion to γ-butyrolactam. Nylon 4 can also
pected to have good fiber properties, but no eco- be spun from a 45 % formic acid solution, but
nomically attractive route to its preparation has lower tenacity is obtained. Because of its rela-
been found. It melts at 330 ◦ C and should be tively high water absorption (9 % at 65 % R.H.),
spinnable to fibers from superheated aqueous so- nylon 4 can be dyed easily, but it has relatively
lutions [9]. poor crease resistance. The fibers have not been
C-Alkyl derivatives of nylon 3 are of interest significant economically, in part because of their
for fibers because of new syntheses of corre- poor temperature sensitivity in spinning [11].
sponding β-lactams [10].
Chlorocyanogen and sulfur trioxide react to Nylon 6 [25038-54-4]. While not ideal for
form the easily accessible N-carbonylsulfamidic optimum fiber properties, nylon 6 represents
acid chloride. Under mild conditions, this reacts about half of the commercial production of ny-
with olefins to form the β-lactam-N-sulfonyl lon fibers and occupies a transitional position in
chloride, which can be converted to the β-lactam this series. Whereas 4-aminobutyric and 5-ami-
through hydrolysis in a weakly acidic medium: novaleric acid proceed smoothly to the corre-
sponding lactams on heating above melt temper-
ature, 6-aminocaproic acid forms a temperature-
dependent equilibrium condensate. At 250 ◦ C,
this consists of ca. 89 % linear polyamide, 8.5 %
caprolactam, and 2.5 % larger ring amides. This
Because both the β-lactams and the cor- equilibrium condensate is identical with the
responding polyamides generally decompose equilibrium polymer that results from hydrolytic
above 250 ◦ C, these nylons are prepared prefer- polymerization of ε-caprolactam.
ably through anionic polymerization in solution, Problem-free continuous polymerization of
at temperatures of − 15 to 30 ◦ C. For copolymer- caprolactam (→ Caprolactam) can be carried out
ization, the β-lactams must have reasonably sim- in perpendicular flow-through tubes, with small
ilar polymerization rates. Polymerizations are additions of water, at 240 – 270 ◦ C and atmo-
anhydrous with alkaline catalysts, e.g., alkali spheric pressure. Batch polymerization in pres-
lactams or N-alkyl lactams. In contrast to melt- sure autoclaves can also be carried out, which
spun polyamides in which molecular masses of is a preferred technique for small production
15 000 to 25 000 are adequate for good fiber units or for polymer with special additives. An-
properties, molecular masses of > 200 000 are hydrous caprolactam can also be polymerized
required for β-lactams, where fibers are made with alkaline catalysts or cocatalysts, but this
by solution spinning. Fibers with good textile “fast polymerization” is not used in the manu-
properties and remarkedly good oxidative sta- facture of fibers. Excess caprolactam and higher
bility can be prepared from poly(β,β-dimethyl- ring amides must be removed from the equilib-
β-propriolactam), spun from a ca. 15 % solu- rium mixture before further processing to fibers.
tion. Typical solvents are trifluoroethanol, phe- The equilibrium melt is extruded, solidified, cut
nol, and dimethyl sulfoxide. to granules or flake, washed repeatedly with
boiling water, and then vacuum dried. This can
Nylon 4 [24938-56-5]. The polycondensate be done batchwise or continuously. Careful ex-
of 4-aminobutyric acid is prepared by anionic clusion of oxygen is essential in all process-
polymerization of γ-butyrolactam in the pres- ing steps. Nylon 6 can also be polymerized and
ence of alkaline catalysts at < 60 ◦ C. spun directly by passing the equilibrium poly-
The reaction is carried out in an inert hy- mer through a continuous, thin-film evapora-
drocarbon solvent, and conversion is ca. 80 – tor to remove impurities and then pumping it
85 %. Precipitated polymer must be washed
 Fibers, 4. Synthetic Organic 7

directly to the spinning machine [11, pp. 121 – Nylon 11 [25035-04-5]. The synthesis of ny-
134]. lon 11 is based on a five-step process from cas-
Because of its relatively low melting point tor oil to 11-aminoundecanoic acid. A 30 – 40 %
and high water absorption, and the lack of a aqueous dispersion of the acid can be polycon-
technically simple way to convert monomer to a densed in three steps, and the nylon 11 formed
continuously spinnable melt, nylon 6 is not the can be isolated and melt-spun. Addition of phos-
best aminocarboxylic acid type for producing phoric or phosphorus acid facilitates spinning by
synthetic fibers. The reason for its great impor- raising the melt viscosity and limiting side-chain
tance and large production volume is economic. growth. As expected from the longer hydrocar-
The high-purity caprolactam required for fiber bon chain, nylon 11 shows hardly any sensitivity
production is made from favorably priced raw or dimensional change in the presence of mois-
materials (benzene, cyclohexane, or phenol). ture. The fibers are too expensive for general use
and are restricted to a few special applications in
Nylon 7 [25035-01-2]. Nylon 7 is gener- luggage, ropes, transmission belts, and bristles.
ally considered to be the optimum aminocar-
boxylic acid type polyamide for fibers. In both Nylon 12 [24937-16-4]. Nylon 12 is pre-
the condensation of 7-aminoheptanoic acid and pared by hydrolytic polymerization of lauryl lac-
the hydrolytic polymerization of enantholac- tam, made by a four-step process from buta-
tam, yields of linear polymer exceed 99 %. This diene. The reaction to give polymer is essen-
means that nylon 7 can be produced continu- tially complete, so spun products can be pre-
ously in a technically simple polymerization- pared by using a continuous polymerization-
spinning process. Textile properties of nylon 7 spinning process. Because nylon 12 has good
fibers are superior to those of nylon 6 and, to a thermal stability, polymerization temperatures
degree, those of nylon 66. Of particular interest, can be raised to 310 – 340 ◦ C [13]. Except for
compared to nylon 6, are the 10 ◦ C higher melt- a 10 ◦ C lower melting point, fiber properties of
ing temperature and reduced water absorption. nylon 12 closely correspond to those of nylon
These two properties lead to important advan- 11. These fibers are not made in large volume
tages, i.e., a considerably higher wet modulus because of cost, and their use is restricted mainly
and improved crease recovery (Table 4). to industrial specialty areas.
To date, no economically competitive route
for production of the monomer has been re-
ported. Small quantities of nylon 7 are pro- 1.2.2. Diamine – Dicarboxylic Acid Type
duced in the former States of USSR. For this, Polyamides
7-aminoheptanoic acid is reportedly prepared
by telomerization of carbon tetrachloride and Nylons of this group are prepared for fiber
ethylene, via the intermediate 7-chloroheptenoic use primarily by thermal polycondensation of
acid. equimolar amounts of diamines and dicarbox-
ylic acids or their salts. Monomers that can un-
Nylon 8 [25035-02-3]. Nylon 8, which melts dergo intramolecular condensation, like glutaric
at 200 ◦ C, is prepared by hydrolytic polymer- and succinic acids, are not suitable for ther-
ization of caprolactam. The equilibrium poly- mal polycondensation. In commercial practice,
merizate contains only traces of ring amide, so aqueous solutions or suspensions of the salt are
that fibers can be produced by using a contin- processed in batchwise or continuous operation.
uous polymerization-spinning process. Because Polycondensation is induced initially by treat-
of the reduced number of carbonamide groups, ment of the concentrated salt under pressure to
water absorption is low, which provides rela- avoid loss of diamine, and then under vacuum to
tively good wet strength and wet elasticity. How- increase molecular mass to the degree required
ever, raw materials for the synthesis of capro- for fiber production.
lactam are too expensive for this polymer to be This type of nylon can also be prepared
attractive economically. from diamines and dicarboxylic acid dichlorides
through interfacial polymerization. Some ny-
lons, with melting temperatures in a range suit-
8 Fibers, 4. Synthetic Organic
Table 4. Physical and textile properties of high-strength filaments from nylons 6, 7, and 66 [12]

Property Nylon 6 Nylon 7 Nylon 66

Tenacity, cN/dtex 8.0 – 8.5 8.1 – 8.5 8.2 – 8.7

Wet strength, % of dry 81 92 85
Elongation at break, % 24 14 – 16 18
Elastic modulus, cN/dtex∗ 41 46 – 49 54
Wet modulus, % of dry∗∗ 27 62 31
Boil-off shrinkage, % 12 8 – 10 10

, g/cm3 1.14 1.10 1.14
mp, ◦ C 214 – 220 225 – 233 255 – 260
Water absorption, %
65 % R.H. 4.3 2.8 4 – 4.5
100 % R.H. 9 – 10 5 9 – 10

∗ At 1 % elongation.
∗∗ In 25 ◦ C water.

Table 5. Melting temperature of nylons

Diamine Dicarboxylic acid Nylon mp, ◦ C

1,4-Diaminobutane adipic 46 278/295

pimelic 47 233
suberic 48 250
azelaic 49 233
sebacic 410 239
1,5-Diaminopentane glutaric 55 198
adipic 56 223
pimelic 57 183
suberic 58 202
azelaic 59 179
sebacic 510 185 – 195
1,6-Diaminohexane adipic 66 250 – 265
pimelic 67 202 – 228
suberic 68 220 – 232
azelaic 69 185 – 226
sebacic 610 209 – 221
1,7-Diaminoheptane adipic 76 226 – 250
pimelic 77 196 – 214
sebacic 710 187 – 208
1,8-Diaminooctane adipic 86 235 – 250
suberic 88 205 – 225
sebacic 810 197 – 210
1,9-Diaminononane adipic 96 205
azelaic 99 165
sebacic 910 179
1,10 -Diaminodecane adipic 106 230 – 236
suberic 108 208 – 217
sebacic 1010 194 – 203

able for melt spinning, 180 – 280 ◦ C (Table 5), Nylon 66 [32131-17-2]. Because raw ma-
are obtained by combination of aliphatic di- terials are favorably priced for producing
amines and dicarboxylic acids. However, only both adipic acid (cyclohexane) and 1,6-diami-
nylon 66 has any economic significance. nohexane (acrylonitrile, butadiene, and adipic
acid), nylon 66 has outstanding economic im-
Nylon 46 [24936-71-8]. The fiber from 1,4- portance in the production of synthetic fibers
diaminobutane and adipic acid is claimed to have (→ Adipic Acid; → Cyclohexane).
better high-temperature properties than nylon 66 For the production of fiber-grade polymer, a
[14]. Good strength retention and low shrinkage 50 – 60 % aqueous nylon salt solution is heated
suggest industrial applications. in a pressure autoclave, with careful exclusion of
oxygen. The pressure is released slowly, and the
 Fibers, 4. Synthetic Organic 9

resultant low molecular mass polymer is heated 1.2.3. Copolyamides

under vacuum in the same vessel to increase
molecular mass and melt viscosity to the level re- Nylon copolymers are formed easily by poly-
quired for fiber spinning. Polycondensation can condensation of monomer mixtures. Compared
also be carried out continuously [15] and the to the corresponding pure polyamides, they have
resultant melt pumped directly to the spinning lower melt temperatures and higher solubilities.
machine. In the case of copolyamides of 6-aminocaproic
acid and 1,5-hexanediammonium adipate, the
Nylon 610 [9008-66-6]. Nylon 610 is pre- melt temperature minimum is ca. 160 ◦ C at
pared under conditions similar to those for nylon 60 wt % of the amino acid. The melting tempera-
66. Because of low water absorption and high ture of the copolyamides can be reduced still fur-
elasticity, nylon 610 is especially suitable for ther through ternary monomer mixtures. Low-
production of bristles. The cost of sebacic acid, melting copolyamides are suitable, for example,
produced from castor oil, is fairly high and limits for thermal bonding of needle felts and nonwo-
the use of this polymer. ven fabrics. Copolyamides of ε-caprolactam and
11-aminoundecanoic acid are especially suitable
Nylons Containing Aliphatic or Aromatic for fishing lines because of good flexibility and
Rings. There is currently no significant com- increased transparency.
mercial production of linear polyamides con-
taining aliphatic or aromatic ring structures.
Many have been investigated for use in tires for 1.3. Special Requirements for
improved flat spotting, for better carpet aesthet- Polyamides
ics, and for improved wrinkle resistance and tac-
tile aesthetics in nylon apparel fabrics. System- The purity of all nylon starting materials is es-
atic studies have been reported on fibers or films pecially important because reactive impurities
using phenylenediamine, C6 H4 (NH2 )2 , and C4 result in uncontrolled chain growth and can re-
to C12 diacid chlorides [16], and on the relative duce the quality of the spun product, e.g., by
effects of cyclohexylene and phenylene linkages increased yellowing tendency. Mechanical im-
in polyamide fibers prepared from C6 to C12 purities must be removed carefully by filtra-
aliphatic dicarboxylic acids [17]. tion before polymerization. The polymer melt
One ring-containing nylon fiber, T-472 is also filtered to remove mechanical impuri-
[26403-85-0], was marketed commercially in ties and pigment agglomerates, by passing it
the early 1970s by Du Pont. It was based through a bed of sand or powdered metal and
on bis(4-aminocyclohexyl)methane and dode- fine screens, just before it is extruded in filament
canoic acid. form. This is especially important in the pro-
The diamine is obtained by catalytic hy- duction of fine-denier filaments in which coarse
drogenation of 4,4 -diaminodiphenylmethane impurities can reduce quality and yield through
(made from aniline and formaldehyde), result- filament breaks.
ing in a mixture of cis, trans isomers. The mix- Because nylons are particularly sensitive to
ture must be fractionally crystallized to yield the oxidation at elevated temperature, oxygen must
preferred 70 % trans, trans product [18]. This be scrupulously excluded in both the polymer-
isomeric mixture is polycondensed with dode- ization and the spinning steps. The oxygen con-
canoic acid to yield a melt-spinnable polymer tent of the inert gases used, primarily carbon
(mp 275 ◦ C) and fibers with high tenacity and dioxide and nitrogen, should be maintained be-
resilience, and low water sensitivity. low 0.001 %. In both the hydrolytic polymeriza-
The luxury, silklike fabric made from T-472 tion of lactams and the polycondensation of ami-
fiber was marketed under the registered trade nocarboxylic acids, an equilibrium exists whose
name Qiana. The product was withdrawn from position is influenced substantially by the water
the market in the early 1980s for economic rea- content of the polyamide melt:
sons.
H[HN−(CH2 )n −CO]a OH +H[HN−(CH2 )n −CO]b OH

H[HN−(CH2 )n −CO]a + b OH + H2 O
10 Fibers, 4. Synthetic Organic

Water removal leads to an increase in av- concentration in grams per 100 mL, is concen-
erage molecular mass; water addition reduces tration dependent. Plotting viscosity as a func-
average molecular mass. The same is true for tion of decreasing concentration and extrapolat-
nylons of the diamine – dicarboxylic acid type. ing to zero yield the intrinsic viscosity, which is
Viscosity stabilizers are added to the monomeric directly proportional to M m . In the production
starting materials to control the degree of poly- of nylon fibers, sufficient control of the process
merization and prevent an undue increase in vis- can be achieved by routinely measuring and con-
cosity in remelt. Both monofunctional and bi- trolling the viscosity of a standard solution, e.g.,
functional compounds are used to limit chain 1 g/100 mL. The melt viscosity, of practical im-
growth. Especially suitable for this purpose portance for melt spinning, can be determined in
are primary and secondary aliphatic amines rotary, torsional viscometers and capillary vis-
or diamines, aliphatic and aromatic carbox- cometers, or by using the falling ball method.
ylic acids, and dicarboxylic acids. Examples In measuring melt viscosity, oxygen and mois-
are cyclohexylamine, 1,6-diaminohexane, acetic ture must be rigorously excluded and tempera-
acid, benzoic acid, and adipic acid. Trifunctional ture held constant. On melting, polyamides can
compounds are undesirable because they lead to change by amide ring formation, molecular mass
molecular branching. increase, and degradation, so melt viscosity is
Good analytical control of polymer quality likely to vary according to method and mea-
is essential to good spinning continuity and high suring conditions. In general, the melt viscos-
fiber quality for all synthetic polymers. A narrow ity of polyamides for melt spinning is ca. 50 –
molecular mass distribution is desirable. Broad 500 Pa · s.
distributions can result from improper design or The free amino and carboxyl end groups of
improper operation of a continuous polymerizer polyamides are determined by potentiometric or
for nylon, and this frequently leads to inferior conductometric titration with dilute perchloric
fiber properties. acid and alkali hydroxide solution, respectively.
Molecular mass distribution A solvent mixture of phenol, ethanol, and water
can be determined by using the ultracen- is suitable for amino-group titration. A supersat-
trifuge [19], by turbidity titration, by fractional urated polyamide solution, in benzyl alcohol or
precipitation or partition between two liquids, or α-phenylethyl alcohol, is used for carboxyl end-
by chromatography. From the molecular mass group determination. This analytical procedure
distribution, molecular mass can be calculated cannot be used for all polyamides.
as the number average (M n ) or the mass aver- Water analysis is carried out by heating the
age (M m ). The ratio M m /M n is always greater flake or fiber, and released water vapor is car-
than 1 and is a numerical measure of molec- ried with dry nitrogen into Karl Fischer reagent.
ular nonuniformity. The absolute value of M n In this method, both the physically bound water
can be determined cryoscopically, osmotically, and that formed by chemical reaction are deter-
or through end-group analysis; M m can be de- mined.
termined by light scattering [20] or by the hyp- Extractable materials in nylon 6, caprolactam,
sometric distribution of macromolecules in ul- and higher ring amides can be determined by
tracentrifugal sedimentation. extracting the finely divided polymer for sev-
The simplest and most commonly used eral hours in water or lower alcohols. How-
method for obtaining relative values of mass- ever, in this relatively simple method, the high
average molecular mass (M m ) is measurement ring amides are not extracted completely. For
of solution viscosity [19, pp. 49 – 67] in a capil- quantitative determination and separation of ring
lary viscometer at constant temperature, where amides, the polymer is dissolved in formic acid
η relative = flow time of the solution divided by and the linear polyamide molecules are then pre-
flow time of the solvent cipitated by addition of methanol. Ring amides
and can be determined quantitatively in a methanol
η specific = 1/η relative solution by using gel chromatography.
Suitable solvents are concentrated sulfuric acid,
formic acid, and phenol. The specific solution
viscosity, η specfic /c, referred to the polyamide
 Fibers, 4. Synthetic Organic 11

1.4. Modifying Additions pigment addition to the monomer or to the poly-

mer melt, because the particles result in filter
Nylons that absorb water and swell, such as plugging as well as weak sections in the fila-
nylons 6 and 66, can be dyed relatively easily ment. For continuous production of nylon flake
with disperse, acid, or metallized dyes. The dye or fiber, adding a pigment – polymer concentrate
molecules migrate readily into the fiber struc- of 20 – 40 % titanium dioxide to the melt just
ture. The dyeing of nylon fibers with acid dyes before spinning is advantageous. This permits
results from reaction with the amino end groups. quick conversion to different degrees of delus-
The number of such reactive sites is influenced tering, but also imposes strict requirements on
by M n but can be modified by additives such control and mixing.
as viscosity stabilizers. For example, carboxyl- The magnitude of pigment addition can be
ic stabilizers will block amino groups and re- checked by ash determination or photometric ti-
duce affinity for acid dyes. The use of primary tanium analysis. The uniformity of pigment dis-
aliphatic amines or diamines provides additional tribution, as well as the number and size distribu-
basic sites and increases acid dyeability. Intro- tion of pigment agglomerates, can be analyzed
duction of tertiary amine groups into the chain by microscopic examination of thin fiber cross
strongly increases absorption of acid dyes. sections.
Nylons can be modified to accept basic dyes Aging and light protection must be provided
by introduction of strong acidic groups such for some nylons by addition of special additives
as sulfonic acids, e.g., 5-sulfoisophthalic acid, [23]. Manganese(II) compounds, in amounts as
in equimolar mixture with 1,6-diaminohexane low as 5×10−4 %, are especially effective for
[21]. Polycolor effects (graduated color depth, nylons 6 and 66. Titanium dioxide pigments, es-
variable color and shades) can be achieved by pecially of the anatase type, reduce light resis-
dyeing fabrics of mixed nylon fibers with differ- tance, and one variety of anatase TiO2 is coated
ent dyeabilities in a single dye bath containing with manganese to offset this effect. Many man-
acid, basic, and disperse dyes. ganese compounds, such as the acetate, sul-
Delustering is the practice of altering the op- fate, phosphate, polyphosphate, and glycero-
tical properties of a fiber, usually by incorpo- phosphate salts have been proposed. In selecting
ration of a white pigment. This is most often the type and amount of additive, undesirable side
done for textile uses. The most common delus- effects, such as yellowing of the filaments and
terant is titanium dioxide [13463-67-7], added extraction of the manganese(II) during dyeing or
in amounts of 0.03 – 2 %, depending on the ef- wet finishing, must be considered in addition to
fect desired. Of the two forms of titanium diox- the light-protective ability desired. Use of a man-
ide available, the anatase variety is preferred for ganese salt with a reducing anion, such as man-
continuous-filament yarns because the harder ganese(II) hypophosphite, improves the white-
rutile modification causes excessive abrasion ness of fibers. Addition of sodium phenylphos-
and wear on guide surfaces and machine parts phinate, in combination with manganese(II) hy-
over which the yarn runs. The rutile form can pophosphite, substantially improves both white-
be used with staple fibers in which guide wear ness and quality [24].
potential is not so serious. Other pigments, such The heat-aging resistance of nylons must be
as clay, can also be used. Delustering can also improved for uses such as the tire cord. The
be accomplished by surface roughening or by thermal – oxidative degradation of nylon can be
introducing voids into the filament. reduced considerably by adding antioxidants
Size distribution [22] of titantium dioxide (0.1 – 1.0 %), such as substituted aromatic di-
pigments and pigment aggregates is generally amines, and their action can be increased by
0.1 – 1.0 µm, with a frequency maximum in the combining them with trialkyl phenyl phosphites.
region of optimum turbidity at 0.2 – 0.4 µm. Textile nylon, for which yellowing cannot be
However, commercial pigments also contain tolerated, requires special phenolic antioxidants
larger agglomerates, which must be broken substituted with alkyl radicals in the positions
down through wet grinding or separated from ortho to the – OH group. Examples are the
the aqueous dispersion by fractional sedimenta- amine salts of 3,5-dialkyl-4-hydroxyphenylcar-
tion. Pigment agglomeration must be avoided in boxylic acids. Copper(I) salts, in amounts as
12 Fibers, 4. Synthetic Organic

low as 5×10−4 % copper, are also effective. 1.5. Technology of Melt Spinning
Many synergistically acting stabilizer mixtures
are described in the literature, e.g., complex 1.5.1. Melt Spinning of Nylon
compounds of copper(I) iodide and hydrocar-
bon phosphines or phosphites are said to be es- All commercially significant nylons are melt-
pecially effective. spun at temperatures up to ca. 300 ◦ C [27]. Pro-
Spin Dyeing and Optical Brightening. Inor- cesses may be continuous from monomer to
ganic and organic pigments for spin coloration spun fiber, or they can be staged. When a variety
of nylons must be stable under melt process- of small-volume products is required, producing
ing conditions and must give high colorfastness nylon flake and remelting it for the spinning pro-
[25]. Pigment particle size should be less than cess are economically advantageous. This is es-
1 – 2 µm to avoid impairment of fiber strength, pecially true for nylon 6, which must be washed
and agglomerates must be carefully milled or to extract polycondensation byproducts.
separated by sedimentation. Colored pigments In modern plants, flake is usually stored in
are generally added to the starting monomer large hoppers and then transported pneumati-
as aqueous dispersions. They may, however, be cally or in smaller hoppers to the spinning area.
added to the melt as pigment – polymer concen- Prior to spinning, the flake must be conditioned
trates [26]. This technique is desirable for short to proper moisture content because this can have
commercial runs but requires precise metering a strong effect on melt viscosity. Great care is
and good mixing. taken to store and transport flake with exclu-
Suitable additives for spun-dyed nylon are sion of moisture. Also, before being delivered
the yellow to red cadmium pigments, anhydrous to the melt unit, fines and excessively large cuts,
iron oxide pigments, ultramarine, copper ph- as well as contaminating metal particles, are re-
thalocyanine, perylene, and quinacridone pig- moved.
ments. Because nylon melts generally have a Nylon flake is commonly melted by using
strong reducing action, perylene pigments can screw extruders or, in the older process, heated
be reduced on the surface with a significant grids or grates. In either case, oxygen must be
change in color. However, reoxidation often oc- rigorously excluded. Spinning temperature de-
curs in air shortly after extrusion of the filament. pends mainly on the thermal stability and melt
Some azo and anthraquinone dyes are also solu- viscosity of the nylon. With nylon 6 and ny-
ble in nylon melts and are sufficiently stable for lon 66, temperatures are usually kept at 280 –
spin dyeing. 290 ◦ C. After leaving the melt unit, polymer
Dyeing of nylon flake in aqueous baths, be- is delivered to a metering pump and then to a
fore spinning, is an economical way to produce a spin pack. The pack contains filter media, pas-
large range of colors from one flake type. How- sages for distributing polymer within the pack,
ever, the resulting colors do not have the out- and a spinneret. The filter section serves to re-
standing fastness of pigment-spun fibers. move mechanical impurities and to provide high
Black nylon fibers are obtained by using car- shear for the melt. In a typical filter section, the
bon black pigments with an average particle size molten polymer passes through layers of either
of 10 – 30 µm. Carbon black pigment in too high powdered metal or fine sand, then through layers
a concentration can block carboxyl groups, re- of very fine mesh screen, and finally through a
duce the degree of polymerization, and impair photoetched plate before reaching the spinneret.
flow behavior of the melt. The spinneret is a metal plate, usually 6 –
Optical brighteners are frequently used to 10 mm thick, filled with holes, each hole forming
improve aesthetics of textile fibers, especially one filament. Filaments from round spinneret
to hide the effects of soiling. The more stable holes have circular cross sections. The cross sec-
brighteners are added to the monomeric start- tion can be altered to almost any desired filament
ing material, the less stable ones, such as the shape to achieve unusual luster effects, as well as
coumarin type, are injected into the melt. altered physical and tactile properties. Because
the surface tension of the melt leads to a rounded
filament, melt temperature, melt viscosity, and
 Fibers, 4. Synthetic Organic 13

cooling rate must all be adjusted to achieve the heat must be shut off, otherwise molten polymer
desired filament cross section. will rise into the cooler zone and solidify to form
Spinneret holes of 200 – 400 µm can be used a bridge that blocks the flake feed. The melting
to produce nylon filament and staple yarns. The capacity of a grid-spinning unit with a grid diam-
molten polymer extruded from the hole is pulled eter of 160 – 200 mm is ca. 30 – 60 g/min. Higher
away by downstream rolls, reducing the diame- capacity can be achieved with larger grids. One
ter 5- to 50-fold. The diameter, or the mass per melting grid can feed four or more spinnerets.
unit length, of the spun filament is determined by
the rate at which polymer is metered through the Extrusion Spinning. More modern spin-
spinneret hole and the rate at which it is pulled ning equipment uses melt extruders instead of
away. Small particles that pass through the fil- grid units.
ter leave weak spots in the filament, which may Extruders provide a shorter dwell time in the
break in subsequent processing. melt, better mixing, and better viscosity con-
Nylons up to ca. 30 dtex/filament can be spun trol. Their main advantage, however, is the large
into air, but higher diameters require spinning melt capacity, to ca. 1500 kg/d for a 150-mm-
into water or other liquids. Except for a few diameter screw.
specialty uses, such large diameter filaments are Screws with length – diameter ratios of 20 –
generally made for nontextile applications. Tur- 30 are preferred to assure a more uniform melt
bid monofilaments are usually obtained when temperature through the longer compression
spinning into water, because of crystallization zone. An additional mixing zone connected to
and surface corrosion. Clear filaments can be the compression zone improves homogeneity of
prepared by spinning nylon melts into cooled the melt and permits increased throughput [31].
organic liquids such as carbon tetrachloride. The melt is fed at constant pressure from
Unusual and useful filament structures can be the extruder through a jacket-heated transfer
prepared with specially constructed spinnerets line to the spinning machine. One melt extruder
[28]. Two melts are fed simultaneously to a can supply 30 – 40 individual spinning positions,
spinneret hole, which results in a bicomponent each of which might spin eight or more individ-
filament that crimps spontaneously after draw- ual thread lines. Use of a central filter for the
ing and finishing. Suitable melt pairs for this melt, located between the extruder and the spin-
are nylon 66 and a 66 – copolyamide [29] or a ning block, is considered advantageous for some
copolyamide 612 [30]. Spinnerets with two con- processes. This type of filtration is practical for
centric holes yield sheath-core filaments from nylon 6 but not as effective for nylon 66 because
two melts. Injection of an inert gas into the cen- of the tendency of the latter to degrade and form
ter hole causes a void to develop and results in a gels in, and after, the filter.
hollow filament cross section. Melted polymer must be fed to the individ-
ual spinnerets with the same average dwell time.
Grid spinning. Grid spinning was the orig- Distribution piping is designed in cascade form
inal process for melt spinning of nylon. to provide the same melt travel distance to each
Flake is gravity-fed from an overhead hopper spinneret. In addition, dwell time differences
and melted on a spiral coil or grid heated with arising from parabolic velocity distribution of
diphenyl. An atmosphere of superheated steam melt inside the pipe must be balanced with static
is generally provided to control melt equilibra- mixers ahead of each branch. Local or chrono-
tion. In starting up a grid-spinning head, melted logical nonuniformity of the melt can usually be
polymer dropping from the melting grid collects detected first as dyeing differences in filament
in a conical sump, flows into a pressure pump, yarns.
and is fed to a metering pump where it is metered
through the filter pack and spinneret. Because Direct Spinning. Economic and quality ad-
pump demand must always be smaller than the vantages result by feeding continuously poly-
maximum melt capacity, the sump fills until the merized melt directly to the spinning machine.
melt grid is immersed in the melt, thus automat- This is most easily accomplished with nylon
ically regulating melting via the free-grid sur- 66, which produces only small amounts of low
face. When the process is interrupted, the grid molecular mass cyclic amides. Direct spinning
14 Fibers, 4. Synthetic Organic

becomes most attractive when a few products Filaments leaving the quench chimney are
can be made in high volume and such prod- moistened with a spinning finish (oils emulsi-
ucts can be made with little change in overall fied in water) to provide static protection and lu-
throughput. Large transitional changes are to be brication for further processing. Many filaments
avoided. In such systems, introducing additives are combined after finish application to form the
into the melt downstream of the polymerization final, multifilament bundle. If the yarn is to be
unit is also desirable. This requires additional drawn in a separate step, it is normally passed
expenditures for the preparation of melt concen- through a steam tube to promote development
trates, as well as for the melting, metering, and of the proper crystalline structure. For coupled
homogenization equipment required for injec- spinning and drawing, yarn can be forwarded
tion. from the feed roll, which pulls the filaments
As noted earlier, nylon 6 fibers can also away from the spinneret, directly to a set of
be made by direct spinning, but the equilib- faster moving draw rolls and then to a package-
rium mixture, containing substantial amounts of winding unit. Textile yarns are commonly drawn
caprolactam and higher cyclic amides, must be three to four times the original spun length to
dealt with. This is accomplished through thin- develop the required tensile – elongation prop-
film evacuation. erties. Depending on the process and the end
The melt, prepared continuously in a poly- use, packages of ca. 1 – 20 kg are produced.
merization tube, is passed to an evacuating as- Economics of the spinning operation have
sembly at 270 ◦ C [32]. It is distributed through been improved over the years by winding mul-
an annular slit onto a cylindrical wall, as a co- tiple packages on one winding unit, by winding
herent film of melt. As the melt flows down the larger packages for each thread line, and by op-
wall, volatile components (caprolactam and wa- erating the entire process at higher speed. Fila-
ter) evolve at a pressure of ca. 10 Pa. At the ment yarns are now prepared at spinning speeds
bottom of the assembly, the evacuated nylon 6 of 5000 m/min, and useful fiber properties are
melt is homogenized through a mixing stirrer now achieved in some cases without a separate
and conveyed by a compression screw through drawing step [33]. Spinning, drawing, and tex-
the discharge and to the spinning machine. turing may also be combined in one continuous
operation.

1.5.2. Special Techniques and Products Coarse-Denier Nylon Filament Yarns.

Coarse nylon yarns range from 400 to
Fine-Denier Nylon Filament Yarns. Most > 35 000 dtex total and from 6 to ca. 20 dtex
fine-denier filament yarns are used in wearing per filament.
apparel and household upholstery. Products are Rectangular spinnerets are commonly used,
in the region of 10 – 400 dtex total, with fila- spinning several hundred holes per spinneret.
ment counts from 1 to > 100. Single filaments In the production of high-strength nylon yarns
run from 1.5 to ca. 6 dtex (9 – 36 µm). (e.g., tire cord), draw ratios of 5 – 6 are used and
Spinnerets for fine-denier textile filaments drawing is commonly done in two stages, with
are usually made of stainless steel, 40 – 70 mm heating, to develop maximum tenacity and low
in diameter and 10 – 15 mm thick. Because of elongation. Tenacities of 8.0 cN/dtex and 15 –
the high viscosity of the melt, the spinneret hole 17 % elongation are common for nylon 66 tire
initially has a large diameter (2 – 3 mm), called yarns. Package weights of 40 kg are common,
the counterbore, which tapers in a conical sec- and ends from several hundreds of these pack-
tion to a smaller exit hole (200 – 400 µm) from ages are combined and wound on a larger spool
which the melt is extruded. (beam) for shipment to the customer.
With a windup speed of 600 – 1200 m/min, Nylon filament yarns for carpets and other
solidification in the quench (cooling) chimney floor coverings are usually sold in the range of
is completed within ca. 50 cm of the spinneret. 1000 – 3000 dtex total and 15 dtex per filament.
Cool air is blown at right angles across the fil- Nylon for netting and ropes reach 35 000 dtex
ament path, and careful attention must be given total, with 20 dtex per filament. These yarns are
to avoiding pulsation or turbulence in air flow. drawn four to six times their original length with
 Fibers, 4. Synthetic Organic 15

heat assists and are deposited in rope form in a of nylon 6 was only 9 % in 1953, vs. 91 % for ny-
can. Some of these are then stretched further in lon 66, worldwide shipments of the two are now
a hot water bath to develop maximum tenacity. about equal. Installed worldwide capacity, ap-
proaches 4×106 t. In 1985, the geographic dis-
Wires and Bristles of Nylon. Coarser ny- tribution of production was 36 % North Amer-
lon filaments (0.05 – 5 mm) are generally ica, 23 % Western Europe, 17 % Asia (including
made with a higher degree of polymerization. Japan and Taiwan), and 24 % all other; sales by
Copolyamides are often more suitable for fish- end use were 38 % for apparel and home fur-
ing lines. nishings, 34 % for carpets (mostly face fibers),
Several processing steps are frequently cou- and 28 % for industrial uses (truck tires, con-
pled in one continuous operation. Flake is melted veyor belting, etc.); an additional 1.0×106 t of
in a single-screw extruder, and the melt is ex- nylon resin was produced for nonfiber applica-
truded through spinneret holes (1 – 10 mm in di- tions. Major producers of nylon fibers are listed
ameter). The coarse filaments are solidified in a in Table 7 along with types and representative
water bath and drawn between rollers in air or trade names.
hot water at a speed of 200 – 400 m/min. Thicker
wires may be drawn through dies to set the draw
point and round the cross section. To improve Table 6. World production of nylon fibers∗
dimensional stability and stiffness, coarse fila-
Year Production, t Production, %∗∗
ments for bristles are heat-set in boiling water,
either continuously or on reels or bobbins. 1940 5 400 95
1950 62 000 90
1960 410 000 58
1970 1 908 000 38
1980 3 151 000 30
1.6. Uses 1985 3 396 000 27
1988 3 900 000
Fine-denier filament yarns, from 1 to 6 dtex per
∗ Data compiled from Textile Organon.
filament and up to about 400 dtex total, are used ∗∗ Percentage of world production of synthetic fibers.
broadly in wearing apparel, such as ladies un-
derwear, lingerie, stockings, pantyhose, and out-
erwear; in shirting, elastic outer clothing, and Table 7. Major producers and trade names of nylon fibers∗
recreational clothing; and in home upholstery
Manufacturer Nylon Trade names
and automotive decorative coverings. Heavy-
denier filament yarns, 6 – 20 dtex per filament Du Pont (United States) 66 Antron, Cordura, Cantrece
BASF (FRG) 6 Zeftron
and up to 3000 dtex total, are used in carpets Rhône-Poulenc (France) 66 Nylon
and other floor coverings, belt fabrics, tire cord, Allied Signal (United States) 6 Caprolan, Anso, Captiva
netting, and ropes. Nylon staple fibers, ranging Monsanto (United States) 66 Nailon R, Cadon, Cumuloft
6 Helion, Polycord
from 1.0 to 15 dtex per filament, are used directly ICI (United Kingdom) 66 Bri-Nylon
or blended with cotton, felt, and other synthetics BASF 6 Zeftron
Bayer (FRG) 6 Bayer-Perlon, Dorix
for apparel, floor covering, and industrial uses. Courtaulds (France) 6 Celon
Monofilament nylons, 20 to > 1000 dtex per fil- Enka-Glanstoff (FRG) 6 Enka-Perlon, Enkalon,
ament, are used in items such as fishing lines, Enkatron
Hoechst (FRG) 6 Perlon Hoechst
luggage, paintbrush bristles, and cordage. Snia Viscosa (Italy) 6 Lilion
Teijin (Japan) 66 Teijin-Nylon
Toray (Japan) 6 Amilan
66 Toray-Nylon
1.7. Economic Aspects, Manufacturers, Visco-Suisse (Switzerland) 6 Flixor
66 Edlon
and Trade Names
∗ The first six are listed in order of sales volume; the remainder
Some 3.9×106 t of nylon fiber was produced are alphabetical.

worldwide in 1988 (see Table 6), with a value of

over $ 11×109 [302]. Over 98 % of the total is
either nylon 6 or nylon 66. Whereas the fraction
16 Fibers, 4. Synthetic Organic

2. Polyester Fibers For a detailed description of the chemistry,

raw materials, production, and analysis of poly-
History. The first spinnable high molecu- esters, see → Polyesters. The following discus-
lar mass polyesters were prepared by W. H. sion contains information pertinent to an un-
Carothers and co-workers in the laboratories derstanding of the production and properties of
of E. I. du Pont de Nemours & Co. around 1930 these fibers. Section 2.1 covers aspects of pro-
[34]. Dicarboxylic acids in use then were se- duction common to all types of PETP fibers; spe-
bacic acid, hexadecanedicarboxylic acid, and cific information can be found under the individ-
others; some diols used were ethylene glycol ual fibers (Sections 2.2 and 2.3).
and propylene glycol. The discovery that hard-
ened spun strands could be drawn to several
times their original length and, thereby strength- 2.1. Production
ened, was made with these polyesters [35]. How-
ever, their melting points were ca. 75 ◦ C, too 2.1.1. Starting Materials and Polymer
low for practical application. For this reason,
Carothers turned his attention to the more Ethylene Glycol [107-21-1]. Ethylene gly-
promising polyamides [36]. col is produced commercially by the reaction of
In the late 1930s, investigations showed that ethylene oxide with water, which in turn is ob-
terephthalic acid and other aromatic acids could tained by the oxidation of ethylene (→ Ethylene
yield useful polyamides. Therefore, polyesters Glycol; → Ethylene). Prerequisites for smooth
containing terephthalic acid as the dicarboxyl- polycondensation to poly (ethylene terephthal-
ic acid were studied at several locations [37]. ate) and for the desired polymer properties are
Poly(ethylene terephthalate) was discovered in extreme purity of ethylene glycol and other raw
the laboratories of Calico Printers Association. materials and the absence of water.
Beginning in 1940, Whinfield and Dickson
devoted themselves mainly to poly(ethylene Dimethyl Terephthalate [120-61-6]
terephthalate) [38], [39], while Schlack was (DMT). Until the end of the 1960s, econom-
working on poly(tetramethylene terephthalate) ical production of terephthalic acid in the purity
[40]. required for fibers was difficult. For that rea-
In 1947, ICI and Du Pont acquired patent son, the more easily available dimethyl ester of
rights for Great Britain and the United States, terephthalic acid was generally chosen as the
respectively, and initiated the commercial de- starting component for PETP (→ Terephthalic
velopment of polyester fibers [37]. In the early Acid, Dimethyl Terephthalate, and Isophthalic
1960s, ICI licensed its technology worldwide to Acid).
some large fiber producers whose own devel- This material is produced commercially pri-
opments led to today’s mass production. Thus, marily by the Witten process (identical to the
poly(ethylene terephthalate) has gradually be- Imhausen or Katzschmann process [42]).
come the most important fiber polymer [41]. p-Xylene [106-42-3] is subjected to a two-
According to DIN definition 60 001, fibers step, liquid-phase oxidation in air. The p-toluic
are designated polyester if the polymer chain acid so produced is esterified with methanol to
contains at least 85 % of an ester of a diol the methyl ester of p-toluic acid, which is then
and terephthalic acid. Poly(ethylene tere- esterified with methanol to DMT.
phthalate) [25038-59-9] (PETP), poly(oxy-
1,2-ethanediyloxycarbonyl-1,4-phenylene- Terephthalic Acid [100-21-0] (TPA)
carbonyl), is a polyester with terephthalic acid (→ Terephthalic Acid, Dimethyl Terephthalate,
[100-21-0] as the dicarboxylic acid and ethylene and Isophthalic Acid).
glycol as the diol (n = 80 – 150): Since the early 1970s, extra pure terephthalic
acid of fiber quality has been produced commer-
cially primarily by the Amoco process [43].
Inhibition of the oxidation of the second
methyl group of p-xylene is suppressed with the
aid of added bromine-containing promoters as
 Fibers, 4. Synthetic Organic 17

cocatalysts. As with DMT, the oxidation takes In this step, the catalysts are primarily antimony
place in air and produces raw terephthalic acid, trioxide or oxides of similar amphoteric metals.
which is dissolved at high temperature under Phosphorus compounds are added as stabilizers
pressure in water, hydrated, and thus purified. to inactivate the transesterification catalyst.
Other additives, e.g., titanium dioxide for
Polymer. The polymer is prepared in two delustering or carbon black for black coloration,
steps: can be added to the melt prior to polyconden-
1) Transesterification of dimethyl terephthalate sation. Once polycondensation is complete, the
(1) with ethylene glycol to bisglycol tere- condensate is forced out of the vessel with ni-
phthalate (2) (continuous or batchwise) or trogen and quenched in water. The melt, which
direct esterification of terephthalic acid. is thus solidified largely in the amorphous state,
2) Polycondensation (continuous or batchwise) can then be formed into chips.
to give poly(ethylene terephthalate) (3). Continuous Process. Continuous transesteri-
fication and polycondensation occur in several,
mostly horizontal, reactors in a manner similar
to the batchwise process.
As the polyester melt is formed during con-
densation, care is taken to keep its layer thick-
ness small and its surface correspondingly large.
This is necessary because diffusion of excess
glycol determines the rate of polycondensation.
Discharge from the last reactor occurs by means
of an extruder or a pump. The polyester melt
is then either passed to the spinning units and
spun immediately or chilled in water and cut into
chips. Continuous processing units are generally
quite large, with throughputs of up to 100 t/d and
average holdup times of the material in the unit
of 5 – 10 h.
The batch process is preferred for special poly-
mer types, particularly for small amounts of Poly(ethylene terephthalate) from Tere-
polymer. The continuous process is used for phthalic Acid. Since highly purified, fiber-
standard polymer types in large volume, espe- grade terephthalic acid has become available at
cially if spinning immediately follows polycon- low cost, it is increasingly being esterified di-
densation. rectly with ethylene glycol (molar ratio of tere-
phthalic acid to ethylene glycol 1 : 1.1 to 1 : 1.5).
Poly(ethylene terephthalate) from Di- The reaction occurs at about 260 ◦ C un-
methyl Terephthalate. Commercial transester- der pressure and generally requires no catalyst.
ification of dimethyl terephthalate with subse- Lower linear oligomers are formed. After the
quent polycondensation was initially carried out glycol has been distilled, polycondensation fol-
batchwise. lows. Its course is similar to that with DMT as
Batchwise Process. First, DMT is esterified as the starting product. A polycondensation cata-
quantitatively as sible with an excess of ethyl- lyst is also required.
ene glycol (molar ratio range of DMT to eth- The economic advantages of this route are
ylene glycol 1 : 2.5 to 1 : 4.5) between 150 and that circulation of methanol is eliminated, sub-
180 ◦ C. Catalysts are primarily zinc, calcium, stantially less excess glycol is necessary, and
and manganese acetates. Bisglycol terephthal- above all, the amount (in grams) of starting ma-
ate, as well as higher homologues, are formed. terial required is less by ca. 14 % because of the
Excess glycol is distilled at temperatures up to lower molecular mass of TPA vs. DMT. How-
250 ◦ C. ever, direct esterification results in somewhat
Polycondensation is carried out at higher more diethylene glycol byproduct. This process
temperatures, up to ca. 285 ◦ C, under vacuum. is used in continuously operating modern plants.
18 Fibers, 4. Synthetic Organic

Poly(ethylene terephthalate) with Very exhibits a special characteristic which distin-

High Molecular Mass. Industrial end uses re- guishes it from other commercial melt-spinnable
quire very high molecular masses (correspond- polymers: because of its relatively high glass
ing to very high average lengths of molecules) to transition temperature (70 ◦ C), the spun mate-
attain the necessary tenacity and modulus. Be- rial solidifies completely in the spinning shaft
cause removal of excess glycol in polyconden- to form a stable, supercooled melt with molec-
sation is rate determining, reducing the thick- ular orientation more or less in the yarn direc-
ness of the melt layer as the reaction progresses tion [37]. This orientation, measured by birefrin-
would be appropriate. However, due to the melt gence, is proportional to the tensile stress along
viscosity increase during polycondensation, this the path of the yarn at the time and place of so-
becomes more and more difficult. Holdup time at lidification, [44], [45].
high melt temperature is thus increased, which As filaments solidify, they also attain their fi-
produces thermal degradation in parallel with nal speed (winding speed) and thus their final lin-
polymerization. Polymer whiteness thus deteri- ear density (as-spun fineness). Where the solid-
orates, and COOH end groups are formed in un- ification point lies along the path of the as-spun
desirable concentrations in addition to the OH yarn, depends on spinning conditions; distances
end groups. To get around these problems, PETP between 20 and 150 cm from the spinneret have
of very high molecular mass is now generally been reported [45].
produced by postcondensation in the solid phase Because of the relatively low tendency of
(solid condensation). PETP to crystallize at room temperature, the as-
Granulate PETP, produced by melt conden- spun yarn is amorphous as long as drawdown
sation, is dried and exposed to heat either batch- tensions are not too great. Stress-induced crys-
wise in vacuum or continuously under an anhy- tallization occurs only at higher tensile stress
drous gaseous protective blanket free of oxygen as a result of spinning speeds above ca. 3000 –
(generally nitrogen) at temperatures up to ca. 4000 m/min or of very intense air quench; this
250 ◦ C (i.e., somewhat below the melting point). crystallinity also is frozen into the yarn. Under
A lamellar structure with noncrystalline regions these processing conditions, the as-spun yarn is
and voids forms (→ Fibers, 2. Structure). Poly- partially crystalline [46], [47].
condensation occurs in parallel with recrystal- At very high spinning speeds (at about
lization and additional crystallization. The gly- 8000 m/min), the crystallinity of the as-spun
col – water mixture produced diffuses through yarn can be as high as 50 % [48], [49], and
the noncrystalline regions and mainly through the distribution of directions of the crystallites
the interlamellar voids that are being formed. becomes even more narrow. At the same time,
The result, in addition to acceptable polymer the layered structure of crystalline order, which
color, is primarily the desired low concentration resembles that of PETP spun slowly and then
of COOH end groups. Once the desired average drawn, is slowly transformed into a more fibril-
molecular mass has been attained, the granulate lar structure of larger ordered regions. Despite
is chilled and packaged. Alternatively, it can be the high orientation of the crystalline fractions,
melted directly with the exclusion of water and the total orientation again decreases somewhat;
sent to the spinning units. therefore, orientation of the amorphous material
between the fibrils is assumed to decrease [50].
At spinning speeds > 4000 m/min, an addi-
2.1.2. Spinning tional sheath-core orientation occurs in the fil-
aments [48]. This effect can cause the orienta-
The melting point of poly(ethylene terephthal- tion in the sheath, measured by birefringence, to
ate) (265 ◦ C) is clearly below the decomposi- be almost twice as great as in the filament core
tion temperature of the melt; therefore, PETP [51], [52]. Correspondingly, the sheath of the
can be melt-spun (see also → Fibers, 3. Gen- filaments is also more highly crystalline. These
eral Production Technology, Chap. 3.1.). During differences remain during further processing of
melt spinning, a molecular orientation is created the as-spun yarn and can lead to nonuniformities
in the filaments by the drawdown tension; this in dyeing if they are not controlled in the process
orientation is frozen during cooling. Here, PETP [53].
 Fibers, 4. Synthetic Organic 19

As mentioned, the orientation and even the PETP granulate in a vacuum is better, for ex-
crystallinity of filaments depend on spinning ample, in batches in large tumble dryers.
conditions and increase with increasing spinning From the dryer, the granulate reaches the
speed, stronger air quench, and higher molecu- melt extruder, which transports the melt to one
lar mass. Both characteristics decrease with in- or more spinning machines. Because of ther-
creasing spinning temperature, with higher mass mal degradation of the melt, maintaining equal
transport, and thus with greater as-spun linear holdup times in the hot lines between the ex-
density. If the spinning speed is increased and truder and the attached spinning units is impor-
the fineness is held constant by a proportional tant; the temperature of these lines must also be
increase in mass transport, the effect of spin- the same. Only then can the uniformity of the
ning speed predominates. The orientation and as-spun yarn and the end products be assured.
even the crystallinity increase [45][46][47]. The Spinning units differ considerably in con-
diameter of the spinneret holes, hence the spin – struction and processing data, depending on the
draw ratio, has relatively little effect on the final end product. The same is true for the method
spin orientation and crystallinity except when of cooling, finishing, drawing down, and col-
spinning speeds are ≥5000 m/min [50]. lecting the as-spun yarn [37]. Common opera-
Orientation and crystallinity of the filaments tional winding speed ranges from ca. 500 m/min
are characteristics of the as-spun yarn that must for industrial yarns to 6500 m/min for filament
be considered in further processing because of yarns spun at the highest speed. Thick filaments,
their effect on the properties of the end product. e.g., monofilaments, are spun at a much lower
Both factors are held as constant as possible with speed. Common to all is the spinning tempera-
respect to time and between the spinning units. ture, which is 270 – 310 ◦ C. For details, see Sec-
tion 2.3.
Spinning Process. As described in Sec-
tion 2.1, PETP is produced either continuously
or batchwise. In the continuous process, the 2.1.3. Drawing
spinning and polymerization units can be con-
nected. Thus, freshly condensed melt flows di- The glass transition temperature of PETP is ca.
rectly to the spinning units. Because the eco- 70 ◦ C, which is somewhat above room temper-
nomic advantages of direct spinning are obvious, ature. Therefore, when PETP yarn spun at rela-
its use for high-volume end products, e.g., for tively low speed is elongated slowly, cold draw-
staple fibers and standard filament yarns, which ing occurs with a draw point [54]. From the lin-
are always made by the same process, is increas- ear densities on both sides of the draw point or
ing constantly [84]. from the length of the plateau of the stress –
The PETP granulate that is delivered to a strain diagram (see Section 2.2.2), a “natural
spinning plant is first stored in silos. The gran- draw ratio” can be specified. This ratio depends
ulate must be dried immediately before melting on the orientation of the as-spun yarn, which al-
because even the smallest amount of water in ready represents a part of the total orientation
the polymer causes hydrolytic degradation of the [56]. The product of the orienting spin – draw
melt. Residual water content < 0.01 % is desir- and the natural draw ratio is constant to a first
able. approximation and is equal to ca. 6 – 7 [57].
Drying is carried out mostly in continuous In commercial practice, as-spun PETP yarn
shaft dryers. The granulate moves slowly down- is always drawn at a temperature ≥ 80 ◦ C. Be-
ward, while a hot, often predried, countercurrent cause of the added work of drawing, the real
air stream blows over it. Since amorphous PETP yarn temperature in the draw zone is frequently
granulate tends to become sticky during heat- higher than the external temperature, depending
ing, a crystallizer in which the chips are slightly on the drawing arrangement.
crystallized, at least on the surface, often pre- During drawing [44], the molecular network
cedes the dryer [55]. Many dryer designs are of the as-spun yarn is oriented further. The in-
known, with throughputs amounting to several creasing parallelism of the molecular chains ini-
tons per hour. For some products, drying the tiates PETP crystallization. With further draw-
ing, the crystalline regions and the amorphous
20 Fibers, 4. Synthetic Organic

areas between them become more and more stresses and would break. As with other poly-
oriented [58]. Orientation, crystallinity, and mers, two-stage drawing is necessary; the pre-
strength of the drawn yarn increase with in- drawn yarn enters a second draw zone where it
creasing draw ratio, whereas break elonga- is then capable of withstanding the drawing ten-
tion decreases [59]. This is illustrated by the sion.
stress –strain diagrams of yarns drawn differ- Drawing Process. In industrial practice, PETP
ently (Fig. 1). as-spun yarn is almost always drawn continu-
ously between two godets or sets of rolls, whose
speeds determine the draw ratio [54]. In so do-
ing, the required draw temperature is imparted
to the yarn by heaters or heated rolls [37]. Keep-
ing the draw point stationary is important; oth-
erwise the drawn product will contain differen-
tially drawn areas, which produce defects, par-
ticularly nonuniform dye uptake. Details of each
drawing arrangement are dictated by the prod-
uct to be drawn (see also → Fibers, 3. General
Figure 1. Stress – strain curves of two drawn PETP yarns Production Technology, Chap. 2.2.).
—— Draw ratio 1 : 1.52; – – – – Draw ratio 1 : 1.83

In addition, the product of orienting spin-

2.1.4. Aftertreatment
draw and draw ratio is approximately constant
for the maximum possible draw ratio and for Thermal Aftertreatment. At room temper-
drawing to a given break elongation [57]. Thus, ature, oriented and noncrystallized segments of
PETP yarn spun at higher speeds needs to be the PETP molecular chains in a drawn thread-
drawn less to attain a given break elongation. like structure are frozen and immobile; the entire
However, this affects the structure of the drawn structure is not in equilibrium. When the yarn is
material [53], [57], [60]. Because less energy is heated beyond the glass transition temperature,
added during drawing, the crystallinity is some- the amorphous chain segments begin to move
what lower, and both the total orientation, as so as to achieve an entropically more favorable,
measured by birefringence, and the tenacity of less oriented position, to the extent permitted by
the yarn are reduced [61]. These relations begin their restraints in the crystalline regions. These
to change at spinning speeds of ca. 5000 m/min. regions also lose orientation and, as an overall
Then the as-spun yarn is so highly crystalline result, the yarn shrinks. The extent of shrinkage
that the ordered regions are no longer loosened depends on the orientation and crystallinity of
during drawing but orient themselves as far as the drawn structure; it increases with increasing
possible as a whole along the fiber axis. The temperature and, initially, also with the duration
crystallinity again increases [48]. of heat treatment [44], [59], [62]. Any plasticiz-
The more the drawing temperature exceeds ers, e.g., water, that have diffused into the struc-
the glass transition temperature the more easily ture favor shrinkage.
can PETP be drawn [44]. Drawing tension drops The thermal instability of drawn PETP yarn
if drawing temperature is increased and also if structures would be quite troublesome during
the glass transition temperature is decreased, ei- further processing and in textile end products.
ther by water absorption by the as-spun yarn [37] Therefore, it is often reduced during fiber and
or by modifications of the polymer. However, yarn manufacture by a thermal aftertreatment
drawing temperature must not be set too high, for called heat-setting (see also → Fibers, 3. Gen-
then the purely plastic and nonorienting elonga- eral Production Technology, Chap. 2.4.) [37],
tion becomes too large a percentage of the total [63].
draw. Structures that are allowed to shrink without
The draw ratio would have to be set very high restraint between 110 and 180 ◦ C are thermally
to achieve high strength. The yarn in the draw stable below the setting temperature. In this
zone would then no longer be able to absorb process, orientation decreases markedly, which
 Fibers, 4. Synthetic Organic 21

manifests itself on the stress – strain curve as and the initial slope of the stress – strain curve of
a saddle with a yield stress of ca. 1 cN/dtex the yarn and the tenacity increase. The extent of
(Fig. 2). If the product, which has been heat- changes in shrinkability depends on processing
set without restraint, is loaded to this yield conditions.
stress saddle, it is permanently deformed. In gen- In practice, a middle course is often adopted,
eral, normal textile applications rarely reach this i.e., heat-setting while constant shrinkage is
amount of loading. allowed [63]. This increases crystallinity and
somewhat reduces orientation. The increase in
extensibility of the material approximately cor-
responds to the shrinkage permitted; at the same
time, a slight saddle is formed on the stress –
strain curve. The residual shrinkage of mate-
rial heat-set in this way is smaller by about the
amount of shrinkage permitted during setting.
The many processing parameters, such as draw
ratio, heat-setting temperature, and shrinkage al-
lowed during setting, permit matching the prop-
Figure 2. Stress – strain curves of drawn PETP yarn, subse-
erties of the PETP product quite closely to the
quently allowed to shrink freely requirements of each end use.
– – – – Drawn yarn; —— Drawn and allowed to shrink freely Heat-setting does more than prevent thermal
for 5 min in steam instability. The structural rearrangements it in-
During unrestrained heat-setting, crys- duces make prior changes in shape impressed
tallinity increases considerably, primarily favor- on the yarn permanent [37]. This feature is used
ing the ordered regions already present. Degrees widely in producing and processing fiber prod-
of crystallinity up to 50 % have been reported. ucts, e.g., in ironing or pleating when creases
The amorphous fraction is correspondingly re- are to be set hot. However, in producing the fi-
duced, but the chain segments are disoriented brous structure and in further heat-setting, care
in response to shrinkage. With increasing crys- must be taken to chose conditions which will as-
tallinity, maximum dye uptake (i.e., the satu- sure that any subsequent heat-setting will still be
ration concentration) decreases but dye diffu- effective. “Deadening” a fiber (or a textile struc-
sion becomes much easier as the amorphous ture formed from it), so that it can no longer be
chain segments disorient. In this way, dyeability heat-set, should not be done.
reaches a minimum at heat-setting temperatures During setting, primarily the orientation of
of 150 – 180 ◦ C [59], [62], [64]. the amorphous parts changes; however, growing
If heat-setting takes place at constant length crystalline regions also disorient if any shrink-
without any shrinkage, the effects are intensified age has been permitted. This leads to a corre-
with temperature and duration of heat-setting. sponding change in the superstructure of the
Crystallinity also increases but less so than dur- PETP fiber. In general, the layered structure be-
ing unrestrained heat-setting. The PETP prod- comes more pronounced. The orientation angle
ucts are not completely stable thermally but will of the crystalline layers with respect to the fiber
retain some residual shrinkage [59], [63]. There- axis increases [59].
fore, the temperature at which this type of heat- Structural rearrangements during heat-
setting is carried out is frequently very high, e.g., setting and the resultant changes in textile prop-
220 ◦ C. Cooling the material under tension af- erties depend in a complicated way on the struc-
ter it leaves the heat-setting zone is important ture and prior history of the PETP yarn and
to prevent any shrinkage. Heat-setting at con- on the conditions of the heat-setting process.
stant length decreases extensibility and increases Therefore, formulating general, quantitative re-
strength. lationships is impossible. These depend on the
Hot postdrawing of a previously drawn yarn given heat-setting process, which differs from
represents heat-setting with negative shrinkage. product to product. All setting processes are
Crystallinity and orientation increase markedly, included in the manufacturing process immedi-
ately after drawing or deformation.
22 Fibers, 4. Synthetic Organic

Deformation. Melt-spun fibers including The diffusion constant is also affected by the
PETP are generally flat and, in this condition, ordering of the molecules, though to a much
unsuitable for many applications [37]. Hence, lesser degree. This becomes evident if the tem-
all staple fibers and tows must be matched to perature of heat treatment prior to dyeing ex-
natural fibers by crimping.(→ Fibers, 3. General ceeds 180 ◦ C. Above this temperature, the non-
Production Technology, Chap. 2.3.) PETP fila- crystalline regions (layers between crystalline
ment yarns for apparel are textured (→ Fibers, layers) are loosened, which restores the mobil-
3. General Production Technology, Chap. 3.3.) ity of the molecular segments in these regions;
on a large scale. The processes and installations parts of molecules that up to then had been ex-
used in both cases are quite similar for all man- tended can coil up or even refold, which leads to
made fibers. The deformations produced are fre- a growth in crystalline regions transverse to the
quently heat-set, either without tension (staple molecular axis and to an “emptying” of the non-
fibers heat-set without restraint) or with tension crystalline regions. Material that has been spun
(texturing), depending on the product. The fea- at high speed and then drawn behaves similarly
tures specific to PETP are product-related and, (see Section 2.3.2) [53]. However, such ordered
where necessary, are described in Chapter 3. states in the noncrystalline regions of the fiber
are first of all key to controlling the saturation
concentration c∞ .
2.1.5. Dyeing of Poly(ethylene terephthalate) The fiber can take up dye to any significant
Fiber Products degree only at temperatures above T g . At these
temperatures, the polymer is present as a highly
Dyeing of textiles and dyeing technology in gen- viscous liquid in which the mobility of molecu-
eral are discussed under → Textile Dyeing. lar segments in the noncrystalline regions is re-
As a result of polycondensation and sub- stricted. The saturation concentration evidently
sequent degradation, PETP contains OH and depends on the accessible free volume in the
COOH end groups. Neither is suitable for bond- noncrystalline regions and in voids. It is also cer-
ing ionic dyes. Therefore, PETP is dyed with dis- tainly affected by the structure of the interfaces
perse dyes unless it has been modified to contain of these volumes. A quantitative description is
ionic end groups (→ Disperse Dyes). These dyes not yet possible.
are available in powder or liquid form. They are Thus, with reference to fiber structure, the
only slightly soluble in water and are, therefore, diffusion constant D is the most important
used as aqueous dispersions in the dye bath or orientation-dependent kinetic parameter of dye
even as foam. Dye preparations necessarily con- migration through the “liquid” polymer regions.
tain dispersants. The saturation concentration is determined by
Migration of dyes into the fiber is controlled the states of order of the supercrystalline struc-
by the laws of diffusion [65]. The parameter de- ture (small-angle X-ray structure). However,
termining the rate of migration is thus the dif- practical dyeing behavior is essentially deter-
fusion constant D, which depends on the size mined by the diffusion constant.
and structure of the dye molecule. The saturation Poly(ethylene terephthalate) fibers can be
concentration c∞ , reached at very long dyeing dyed to deep shades without using auxiliary
times, is the second parameter required to de- chemicals only at temperatures ca. 50 ◦ C above
scribe the kinetics of dyeing. the glass transition temperature. Such dyeing is
Investigations have shown that D is affected carried out in aqueous media under pressure in
substantially by the orientation of the molec- a closed vessel and is called high-temperature
ular segments in the noncrystalline region of (HT) dyeing. High-temperature dyeing of tex-
the fiber. With increasing orientation, molecular tiles made of 100 % PETP or blends of PETP
mobility decreases, and the glass transition tem- with cotton or other cellulosic fibers presents no
perature T g , a measure of mobility, increases. problems. Any wool in the blend, however, is
Beginning at ca. 68 ◦ C in an isotropic, amor- damaged.
phous PETP, T g can reach 100 ◦ C in a highly Carriers are used for open dyeing in boil-
oriented, partially crystalline fiber [66], [67]. ing water, especially of blends of PETP and
wool. These chemicals are swelling agents, i.e.,
 Fibers, 4. Synthetic Organic 23

poor solvents, for the polyester fiber. They tem- 90 s holdup time at 180 – 220 ◦ C), high through-
porarily loosen intermolecular bonds in the fiber puts, which improve the economics of dyeing,
and thus increase the mobility of molecular seg- can be achieved. Blends of PETP with cotton
ments. In other words, they lower the glass and other cellulosic fibers are preferably dyed
transition temperature. The problems connected by these processes.
with cleanup of wastewater are a disadvantage. Aftertreatment of dyed goods is essential for
Therefore, PETP fibers have been developed the quality of the dyeing. This is especially true
that can be dyed to deep shades in boiling wa- with regard to their fastness, but also holds for
ter without carrier (see Polymer, Section 2.2.1) other properties of dyed goods (fibers, yarns,
[68]. These fibers contain block comonomers, and textile fabrics) such as processibility, ap-
generally polyglycols, and meet all requirements pearance, hand, and mechanical properties. In
of the apparel and home furnishings trades. deep dyeing, particularly, residual dye remains
However, minor losses in light- and washfast- on the fiber surface after drying and heat-setting
ness of the dyeings compared to unmodified with deleterious effects, particularly on fast-
PETP are unavoidable. ness. A reducing, alkaline, postdyeing, clean-
Ionic dyeing for differential dyeing requires ing treatment removes these dyes, as well as
appropriate ionic end groups in the molecule. any oligomers that are diffused from the inte-
Sodium salts of 5-sulfoisophthalic acid dimethyl rior to the surface of the fibers. Temperature and
ester [138-25-0] and 5-sulfoisophthalic acid pH of the postcleaning bath must be carefully
[22326-31-4] have been used; they can be added controlled because of the danger of hydrolytic
during transesterification of DMT or during di- degradation.
rect esterification of TPA [69]. Fibers can be
dyed with cationic dyes without difficulty, but
the dyeings are much less lightfast. 2.2. Structure and Properties
Dyeing with acid dyes requires basic end
groups. Thus far, building such end groups into 2.2.1. Polymer
PETP, e.g., via amines, has not been possible
without yellowing or high aminolytic degrada- Chemical Structure.
tion, resulting from the high polycondensation Homopolymer. In addition to the OH end
and spinning temperatures. groups of the macromolecules, PETP fibers
contain 10 – 40 milliequivalents of carboxyl
Dyeing Processes. The most important dye- (COOH) end groups per kilogram of fiber. These
ing processes are the exhaust process and the are produced in the melt at elevated temperature
continuous process; aftertreatment of PETP dye- (especially beginning at 280 ◦ C) by breaking of
ings is very important for the quality of the dye- the ester bonds. Because COOH end groups cat-
ing. alyze hydrolytic degradation of the polyester,
The dyeing process most widely used with they are occasionally protected (e.g., with ep-
PETP fiber products is the exhaust process. oxide compounds or carbodiimides), especially
Depending on the situation in each dye plant in products destined for industrial use [70].
(wastewater) and the chemical composition of Diethylene glycol, which is present in the
the dyed goods (presence of wool), dyeing can PETP chain in concentrations up to ca. 1 mol %,
be carried out under pressure at HT conditions affects softening behavior of the polyester, dye-
(60 – 90 min at 125 – 140 ◦ C), or it may be car- ability of the fibers, and to a certain extent, light-
ried out open or under low pressure, respectively, fastness. For this reason, diglycol formation is
with carrier (60 – 90 min at 95 – 110 ◦ C). Com- suppressed as much as possible by adjusting the
bining both processes is rare and used only if conditions of the reaction.
highly oriented PETP products are to be dyed to In addition to macromolecules, the polymer
deep shades. contains ca. 2 % oligomers, primarily cyclic
Continuous processes are also used. With the trimers, but also linear oligomers. The former
aid of saturated steam, superheated steam (pad can adversely affect washing and dyeing.
steam process, 2 – 8 min holdup time at 160 – Additional impurities in the polyester are
180 ◦ C), or hot air (pad thermosol process, 15 – acetaldehyde and degradation products. At
24 Fibers, 4. Synthetic Organic

higher thermal loading of the melt during fur- transparent and brilliant white appearance of
ther processing, these can lead to formation of fiber products.
gel particles and discoloration. The most frequently used additive is titanium
In the solid state, PETP absorbs ca. 0.4 % of dioxide [13463-67-7], mostly anatase but occa-
water from the atmosphere at 20 ◦ C and 65 % sionally the harder rutile, which serve to dull the
relative humidity. Because even minute amounts fiber. Particles with average grain sizes between
of water can cause, or at least substantially fa- 0.3 and 0.4 µm are added to the transesterifica-
vor, hydrolytic degradation, the polyester must tion product in concentrations of 0.1 – 3 %.
be carefully dried to a moisture content below Dyed fiber products are made by adding solu-
0.01 % prior to spinning. ble dyes or pigments, if extreme lightfastness of
Copolymer. The principle of copolymeriza- dyed goods is required, to the melt. To produce
tion of PETP with suitable monomers is used to black fibers, carbon black is usually added.
improve certain fiber properties. Many attempts have been made to achieve
The relatively high glass transition temper- permanently antistatic polyester fibers by ad-
ature of the fibers limits dyeability in boiling mixture of suitable compounds. Surface resis-
water to light and medium shades (see Sec- tances of 1010 Ω have been attained [74]. How-
tion 2.1.5). Deep shades can be obtained by us- ever, not much practical use has as yet been
ing higher dyeing temperature (HT dyeing at ca. made of these possibilities. In general, the de-
135 ◦ C under pressure) or carriers. When these sired electrical surface conductivity is obtained
procedures are impractical, e.g., because of the by finishes applied to the fiber.
presence of wool or the contamination of waste-
water, fibers of block copolymers (PETP with Physical – Chemical Structure. The most
polyglycols) can be used [68], [69]. By loosen- important structural variable of fiber-forming
ing the noncrystalline regions, the glass transi- polymers is the average molecular mass. This
tion temperature of these fibers is lowered far describes the mass of the average macro-
enough to attain both the required diffusion and molecule and is the product of the molecular
the desired saturation concentration of disperse mass of the monomer and the average degree of
dyes in the fiber. polymerization (→ Polymerization Processes).
In differential dyeing (single bath dyeing A measure of the molecular mass and, hence,
of textile fabrics to various shades), fibers are the length of molecules is the specific viscosity,
needed that can be dyed with both cationic η spec , measured in dilute solution:
and disperse dyes. The sodium salt of 5-
sulfoisophthalic acid [51876-65-4] is almost ex- ηspec = (η−η0 ) /η0
clusively built into the PETP molecule for this
purpose [69]. where η is the viscosity of the solution and η 0
The low pilling property of textile fabrics, the viscosity of solvent. For poly(ethylene tere-
necessary for practical use, requires low-pilling phthalate), η cspe is between 0.5 and 1.5, depend-
PETP staple fibers (see Section 2.3.1). Low ing on the application of the fiber products.
molecular mass PETP is used for these fibers. Generally, molecular mass is described by the
In addition, cross-links sensitive to hydrolysis intrinsic viscosity [η], often designated as IV
are also built into the polyester with the aid of,
for example, organosilicon compounds [71]. [η] = limc→0 ηspec /c
A particular requirement for home furnish- where c is the concentration of polymer in the
ings is low flammability. For years PETP fibers solution being measured. Again, depending on
have been used in which flame retardants in the area of application, [η] for PETP ranges from
the form of suitable phosphorus compounds are 0.45 dL/g for low-pilling fibers to 1.05 dL/g for
co-condensed with PETP (→ Flame Retardants) tire cord, which corresponds to a span of 50 to
[72], [73]. In this way, flame protection becomes over 200 for the average degree of polymeriza-
permanent; it cannot be lost in washing or dry tion.
cleaning. The distribution of molecular mass corre-
Additives. In many cases, the polymer in- sponds to that given by Flory for condensation
cludes additives intended to change the normally
 Fibers, 4. Synthetic Organic 25

polymers [75]. Changes in this distribution func- only during crystallization but also during ori-
tion by degradation can be reversed by melting. entation and disorientation. This ratio correlates
The distribution function of molecular mass is to the mechanical properties of shaped PETP ar-
rarely measured and is not used for product test- ticles [77].
ing. When PETP granulate is melted and the
Melt viscosity is measured with capillary or melt is forced through spinneret holes, as-spun
rotary viscometers. In polymers intended for filaments are formed. The orientation of the
standard fibers, it is ca. 250 Pa · s at 285 ◦ C. Melt macromolecules in these filaments, character-
viscosity increases rapidly with increasing [η] ized by the birefringence ∆n of the filaments,
and decreasing temperature. It is one of the ba- depends to a large extent on windup speed. Thus,
sic variables of spinnability. The orientation of ∆n at a windup speed of 1500 m/min is only
the macromolecules during filament formation, ca. 0.010, but at 3500 m/min it is as much as
is particularly dependent on melt viscosity. 0.055. Density, too, is subject to this depen-
The transition temperatures, generally mea- dence. At 1500 m/min it is ca. 1.34 g/cm3 , and
sured by differential thermal analysis, are the at 3500 m/min it is 1.35 g/cm3 . The degrees of
final determinants of the orientation, crystalliza- crystallinity behave similarly [78].
tion, and melting behavior of PETP. The glass During drawing of as-spun filaments, the
transition temperature is measured as ca. 68 ◦ C macromolecules are oriented further, and the
on the isotropic and amorphous polymer. It de- birefringence of filament yarns for industrial
pends on the orientation and crystallinity of the uses increases to ca. 0.240. The ability of PETP
polymer and thus can be as high as 100 ◦ C to crystallize is exploited in many ways during
in highly oriented, semicrystalline, industrial, drawing and also in subsequent aftertreatment.
continuous-filament yarns. In the isotropic and Thus, the fiber density ranges from 1.36 g/cm3
amorphous polymer, the crystallization temper- for drawn high-shrinkage staple fibers up to
ature is ca. 100 ◦ C; the maximum rate of crys- 1.41 g/cm3 for highly drawn low-shrinkage fila-
tallization is observed between 140 and 180 ◦ C. ment yarns.
The melting point of PETP, which depends on
crystallinity and crystal size, lies between 255
and 265 ◦ C. 2.2.2. As-Spun Yarns

Physical Structure. Poly(ethylene tere- Nonuniformities of as-spun yarn along a fila-

phthalate) quenched from the melt is isotropic ment or filament bundle, but also from filament
and almost amorphous. The density of amor- to filament, from bundle to bundle, or even from
phous PETP is 1.335 g/cm3 . The polymer can plant to plant, are reflected in the structure of
be crystallized primarily by the action of heat the final product. There, they appear as differ-
but also by the presence of agents such as di- ences in textile properties, primarily in dye up-
chloromethane or dioxane. The crystal structure take. For this reason, yarn is carefully monitored
is triclinic; the density of the crystalline regions during spinning. The glass transition tempera-
is 1.515 g/cm3 [76]. ture of PETP (70 ◦ C) causes the as-spun yarn to
The configuration and conformation of be quite stable at room temperature and makes
monomeric terephthalic acid and ethylene gly- measurement of orientation and even of crys-
col in the macromolecule are also known. In- tallinity relatively easy. Intervening in the man-
frared spectroscopy shows that the terephthal- ufacturing process in case of deviation is then
ic acid component is present in the trans con- possible.
figuration in the crystalline part, but in the cis Many physical measurement techniques are
configuration in the noncrystalline part. The IR available to investigate the structure of PETP
method shows that the glycol component ex- as-spun yarn. The total orientation of a fila-
ists in the trans conformation in the undisturbed ment is measured by optical birefringence. Ex-
crystalline region and in both the gauche and cept for highly crystalline as-spun yarn, the bire-
the trans conformation in the noncrystalline re- fringence is proportional to the orientation fac-
gion. The mass ratio of the glycol components in tor [44]. If suitably measured, it provides in-
the gauche and trans conformations changes not dications of any possible sheath-core structure.
26 Fibers, 4. Synthetic Organic

Another measure of orientation is the velocity shrinkage is again recommended as a measure

of sound and with it the sonic modulus [79], of crystallinity, even of dyeability of the final
[80]. They change little at lower orientation product [53], [61].
and increase noticeably only at spinning speeds Differential Thermal Analysis (DTA). The
≥ 2500 m/min [47]. glass transition temperature, the temperature of
The degree of crystallinity of as-spun yarn the maximum rate of crystallization, the melting
can be calculated easily from its density ; care is point of crystallites, and the final melting point
required, however, because the densities of com- can all be determined from DTA curves [47].
pletely amorphous and completely crystalline Mechanical Tests. If a PETP as-spun yarn is
PETP, required in these calculations, are not en- elongated at room temperature and its tensile
tirely independent of orientation [47]. In addi- stress is measured at the same time, the stress –
tion, true separation of the amorphous and crys- strain curves shown in Figure 3 are obtained. For
talline phases is presumed, which is sometimes as-spun yarn of lower orientation, a saddle ap-
questionable. pears after the initial rise in stress, while a draw
Much information can be gained from X-ray point crawls along the clamped yarn [54]. The
investigations. Wide-angle patters or goniome- percentage of elongation reached at the end of
try provide data on the size, quantity, and ori- this saddle is called the natural draw ratio Rn of
entation of the crystallites, and the approximate the as-spun yarn. With increasing spinning ori-
degree of crystallization. With their aid, total ori- entation, shown in the figure by higher spinning
entation can be divided into orientation of the speeds, Rn decreases; this is because a greater
amorphous and of the crystalline fractions of the amount of extensibility has been anticipated dur-
filament. Small angle X-ray scattering permits ing spinning [57]. If spinning orientation be-
conclusions to be drawn concerning the super- comes too large, Rn can no longer be specified
structure, i.e., the mutual arrangement of crys- [53], [60]. Then either the elongation of the as-
talline and amorphous regions and also the state spun yarn at a given load or the force necessary to
of order of the latter. produce a given elongation is used [57]. In prac-
Thermal Measurements. If as-spun yarn or tice, determining the operational draw ratio that
tow is heated at constant length beyond the soft- imparts a definite property, such as break elon-
ening point to ca. 100 ◦ C, a shrinkage stress that gation or dye uptake to the final product might be
corresponds to the orienting stress during spin- useful. This, however, assumes that no changes
ning is created [57]. This stress is, therefore, a occur in further processing.
measure of orientation and is largely propor-
tional to the optical birefringence. These two
quantities diverge only at high spinning speeds.
If as-spun yarn is heated without restraint, it
shrinks, sometimes very much. In so doing, the
orienting elongation D, frozen in during spin-
ning, is recovered; hence, D can be calculated
from the spun yarn shrinkage [81]. As expected
from theory, the quantity D2 – 1/D is approxi-
mately proportional to birefringence and shrink-
age stress at constant length, which are measures
of orientation [81], [82]. However, this is true
Figure 3. Stress – strain curves of PETP as-spun yarns spun
only for spinning speeds up to 1500 m/min with at four spinning speeds
normal quench. Beyond that, shrinkage is im- Spinning speeds:
peded by crystalline regions developed in the ——– 1200 m/min
sample during spinning or by the regions created · · · · · · 2000 m/min
− · − · 3000 m/min
during measurement. Thus, spun yarn shrink- – – – – 4000 m/min
age goes through a maximum of 60 – 70 % at
spinning speeds between 2000 and 4000 m/min To monitor the spinning process and possibly
and then drops rapidly with increasing speed pinpoint defects in commercial practice, tests
[46], [53], [57]. In this spinning range, spun yarn should be limited to those that can be most read-
 Fibers, 4. Synthetic Organic 27

ily and accurately carried out and that provide fibers is mentioned (see Section 2.1.5, Dyeing
averages over a sufficient quantity of as-spun Processes). This damage consists of molecular
yarn. Each kind of test, taken separately, is use- degradation, which can extend to different de-
ful only for monitoring, not for control. If a test grees from the fiber skin to the core. The con-
quantity exceeds the tolerance range, use of an- sequence, in general, is a reduction in tensile
other kind of test is recommended to readjust the strength and breaking elongation of the fibers
process conditions. caused by the embrittlement connected with
degradation. At the same time, the hand of the
textile fabric can occasionally be changed. How-
2.2.3. Drawn Materials ever, sometimes such changes of the hand are
desired (e.g., by alkalization).
During drawing, PETP crystallizes in the tri- Another change in the properties of PETP
clinic configuration mentioned in Section 2.2.1, fibers or textiles is sometimes produced by
“Poly(ethylene terephthalate) with Very High shrinkage during dyeing, which may be accom-
Molecular Mass.” The supermolecular structure panied by crystallization processes. Carefully
is assumed to consist of somewhat parallel lay- controlling the dimensions of, and stresses in,
ers, inclined to the fiber axis. With increasing textile fabrics as well as the drying and setting
draw, the distance between the layers, measured temperatures is required.
in a direction normal to the layer surface, de-
creases, and the layers rotate more in the direc-
tion of the fiber axis [59], [83]. 2.3. Poly(ethylene terephthalate) Fibers
In practice, material that has been drawn but
not processed further is almost never available 2.3.1. Staple Fibers
as an intermediate product. A posttreatment al-
most always follows immediately, as described Special Features of the Manufacturing
in Section 2.1.4. Process. In the manufacture of PETP staple
fibers, polymers with intrinsic viscosities [η] of
0.65 – 0.75 are generally used; for special types,
2.2.4. Dyed Poly(ethylene terephthalate) polymers of much lower viscosity with [η] ca.
Material 0.5 are occasionally used. The equipment on
which PETP staple fibers are produced is usu-
Fastness Properties. The lightfastness of ally large, with daily production up to 50 t and
dyed textiles for apparel and home furnishings is more. Therefore, feeding the spinning units di-
important in preserving their coloration. A light- rectly from a condensation unit makes economic
fastness rating of 6 can be achieved readily in sense (see also → Fibers, 3. General Production
articles of unmodified PETP fibers with most Technology) [84].
commercially available disperse dyes. The light- A spinning unit for PETP staple fibers con-
fastness of PETP fibers, modified to be dyeable sists of 8 – 32 spinning positions including their
to deep shades at the boil without carrier, may accompanying spinning shafts, aligned side by
be half a rating lower. Dyeings of PETP fibers, side. Each position is supplied with melt, either
modified to be cationic dyeable, generally do not simultaneously or in groups, by an extruder or
rate higher than 4 – 5 in lightfastness. directly from a condensation unit [37].
Heat-setting fastness, rubbing fastness, and Depending on the type of air quench, spin-
washfastness of dyeings of PETP fibers meet all nerets may be circular with uniformly arranged
practical requirements. The only exception is the spinneret holes, they may be plates in which the
slightly lower washfastness of modified PETP holes are arranged rectangularly, and finally they
fiber, dyeable without carrier. A wash tempera- may be circular with an annular arrangement of
ture of 40 ◦ C should not be exceeded. holes [84]. The number of holes is based on the
as-spun fineness and the feed of the spinning
Degradation and Mechanical Properties. position. The spinneret hole shape is not always
In discussing alkaline postdyeing cleaning treat- round. For profiled fibers with nonround cross
ment, the danger of hydrolytic damage to PETP sections, such as triangles, five-pointed stars, or
28 Fibers, 4. Synthetic Organic

even hollow fibers, the holes must have profiles spinning can [89]. A sheath-core effect in the
that exaggerate those of the final product because filaments also presents difficulties.
the profile impressed by the hole tends to blur As customary in the production of staple
somewhat during spinning. fibers and tows from melt- or dry-spun synthetic
The output of a spinning position has been in- polymers, the as-spun tows are combined and
creased from 500 g/min to 1500 g/min and more further processed continuously as a tow band.
by increasing the number of spinneret holes, by The tow band (up to ca. 1.20 m wide) is first
forceful quenching, and by increasing the spin- immersed in a warm bath where the stresses in
ning speed. the individual strands are equalized; the tow is
For example, a filament bundle with a linear thoroughly wetted, and if necessary, additional
density of 8 dtex per filament is spun from an finish is added. From the immersion bath, the
1125-hole spinneret at a speed of 1500 m/min. tow enters the draw zone between two sets of
The output per spinning position is 1350 g/min. rolls [85].
A 16-position spinning machine then provides During drawing, the draw points or draw
about 31 t/d of as-spun yarn in the form of a tow zones of all filaments in the band must be as
with total length of 2160 km and a linear density close together as possible and must not wander
of 144 000 dtex, consisting of 18 000 individual [85]. A number of drawing processes are avail-
filaments. able for this [90]. If the tow is cold when it enters
The length of the spinning shafts is deter- the draw zone, the yield stress must be lowered
mined by the need not only to ensure that the by sudden heating, e.g., via a steam jet, so that
filaments are cooled below 70 ◦ C but also to pre- drawing can occur. In this process, the draw ra-
vent the moving individual filaments from stick- tio is limited, and if necessary, a second drawing
ing together. The shafts are generally 5 m long step must be provided.
but, with a suitable quench, they may be shorter If the tow is heated on hot feed rolls, drawing
[84]. begins on the last or next-to-last feed roll and
Finish is applied to the filament bundle at can even be facilitated, if necessary, by an im-
the lower end of the shaft to ensure trouble-free mersion bath under the third roll from the end.
packaging of the as-spun material. The spin fin- It is also usual to pass the tow through an ad-
ish is also used to impart surface characteristics ditional hot zone in the draw stand. With this
to the fibers needed downstream during manu- process, reaching higher draws with one draw-
facturing and textile processing [85], [86], [87]. ing is possible.
This is more economical and protects the envi- Drawing in water is a compromise in which
ronment better, but some compromises with re- only the last feed roll is heated and dipped into
spect to processibility during tow drawing and the hot water draw bath. Drawing begins at that
textile processing are unavoidable. point.
After the finish application, strands coming If postdrawing is to be accomplished in a sep-
down from the spinning units are turned horizon- arate draw zone, the draw rolls of the first stage
tally and combined into a tow, which is drawn are heated because they represent the feed rolls
off and deposited in a spinning can. Depending of the second draw, which is then carried out in
on the installation, these cans hold 0.5 – 2 t of a heating device.
tow, all of which should have the same length. The stress – strain behavior of the end product
The fibrous as-spun product is preoriented; in can be preselected by the draw ratio but is more
newer spinning units with very effective quench, critically affected by the type and place of heat-
for example, it is characterized by a birefrin- setting. Thus, fibers that are to exhibit a steep
gence of (8 – 14)×10−3 or by a natural draw ra- stress – strain curve with high initial modulus,
tio of ca. 1 : 2.5. similar to cotton, are relatively highly drawn,
High-speed spinning at ca. 3000 m/min, e.g., 1 : 4.5 to 1 : 6, depending on the as-spun
which is advantageous for textile filament yarns, yarn. After drawing, the tow is heat-set under
has been attempted for production of PETP sta- tension, usually at constant length. The heat-
ple fibers [88]. Problems still exist in developing setting temperature is between 160 and 230 ◦ C,
a reliable process for depositing the tow in the depending on the shrinkage desired. After set-
ting, the tow traverses a cooling zone under
 Fibers, 4. Synthetic Organic 29

tension and then enters the crimper. To facil- they range from drapery and curtain fabrics,
itate crimping, it is first slightly moistened or through furniture coverings, pillows and pillow
steamed. The tow must not become too hot in the stuffing, table and bed linen, to wall and floor
crimper; otherwise it relaxes and textile proper- coverings. They have a whole host of industrial
ties deteriorate. After crimping, finish can again end uses along with filament yarns, spunbonded
be applied if necessary, in which case the tow products, and monofilaments. A few examples
must again be carefully dried [90]. of applications are in filtration, automobile in-
Fibers that are to have a flat stress – strain teriors, geotextiles, and material for the sewing
curve similar to wool do not need to be so highly trade.
drawn; a draw ratio range of ca. 1 : 2.5 to 1 : 3 Yarns made from PETP fibers can be pro-
will suffice. After drawing, the tow is sent im- cessed without reservation in weaving and knit-
mediately to the crimper via a short steam zone. ting as well as in tufting. The fibers are com-
The crimp is then heat-set without tension, of- pletely suitable for processing as unblended
ten on traveling grate machines. The heat-setting yarns (100 % PETP), as well as in blends with
temperature, ca. 120 – 180 ◦ C, is selected ac- cotton, wool, silk, cellulosic man-made fibers,
cording to the amount of shrinkage desired in acrylic fibers, and many more.
the end product. The flat stress – strain curve is Of all polyester fibers, cotton types have the
formed by the tensionless setting, and the crimp largest market share. These are processed into
becomes highly stable. blended yarns, and these in turn into blended ar-
Finally, the crimped and, if necessary, ticles. These contain cotton, viscose, or modal
shrinkage-stabilized tow is packaged. Either it fibers in what are today considered the “clas-
is compressed into a bale and sold as endless sical” blend ratios of 65 : 35 or 1 : 1 (PETP to
tow, or it passes through a cutter and is cut into cotton) and in other ratios.
staple fibers, which are then baled. The usual The stress – strain curve of cotton types is
mass of a bale can range up to 500 kg. shown in Figure 4. Its initial slope corresponds
Staple fiber draw lines are up to 80 m long approximately to that of cotton. Their finenesses
and produce from 20 to 250 t/d, the latter, of of 0.4, 0.9, 1.3, and 2.4 dtex, and the major one
course only for high-volume products. Delivery of 1.7 dtex, at cut lengths of 30 mm and 38 mm
speeds range from 150 to 300 m/min, with tow are matched to cotton.
sizes up to 600 ktex and more [91]. Investment
and manufacturing costs per ton per day are re-
duced considerably with increasing productivity
of these draw lines [89].
Completely continuous installations with ca-
pacities of 12 – 15 t/d produce smaller lots. They
are supposed to be superior to the usual tow band
installations in terms of investment and man-
ufacturing costs, but they produce fibers with
three-dimensional crimp. Whether such fibers
can be spun in blends with natural fibers and
whether fabrics produced from such yarns will
be acceptable in the marketplace remain open
questions [89]. Figure 4. Stress – strain curves of PETP cotton type staple
fibers
Types of Fibers, Properties, and Uses. ———— Cotton
– – – – – PETP cotton type (normal shrinkage)
Polyester staple fibers encompass the broadest − · − · − PETP cotton type (low shrinkage)
product spectrum of any fiber. They can be found · · · · · · · · PETP sewing thread type
in all areas of application [37, 92–94]. They are
used in apparel for overcoats, jackets, leisure- Fibers with normal high shrinkage and others
and sportswear, ladies’ outerwear, men’s suiting, with reduced shrinkage are available and used
work and protective clothing, children’s wear, to vary the hand and appearance of textile fab-
underwear, and sleepwear. In home furnishings, rics over a wide range. With the additional pos-
30 Fibers, 4. Synthetic Organic

sibilities offered by the choice of fineness and choring the pill to break. In this manner, the pill
weave construction, the textile processor can ex- disappears soon after it is formed.
ert a major influence on the permeability of, for A third group consists of the fiberfill types
example, tent, overcoat, shirt, and blouse fab- commercially available as staple fibers but also
rics. In comparison to wool types of polyester as continuous tow. These fibers are used both
fiber, dyeing of highly oriented cotton types is in apparel (primarily for heat insulation) and in
somewhat slower but, like the former, presents home furnishings (primarily in pillows, cush-
no problems. ions, and bedding). Their crimp is two- or three-
Special cotton-type fibers, which are also dimensional. To improve the hand of fiberfill,
offered as continuous tow for processing on such fibers are often provided with a special fin-
stretch – breaking converters, are intended for ish, based primarily on silicone. The range of
sewing. These fibers are especially highly drawn linear densities of these fibers is between 1.5
and, therefore, have the highest moduli (resis- and 14 dtex at a cut length of 30 – 80 mm (most
tance to elongation) and tenacities. common length, 60 mm). This group also con-
Wool types are intended primarily for pro- tains high-shrinkage fibers with a shrinkage at
cessing in blends with wool. The major blend the boil of 50 %.
ratio is 55 : 45 (PETP to wool). The stress – In home furnishings and automobile inte-
strain curves of these fibers are matched to that riors, polyester carpet types are used. These
of wool (see Fig. 5) by tensionless heat-setting also include poly(tetramethylene terephthalate)
during fiber manufacture, as described in Sec- fibers, see Section 2.4.1 (→ Polyesters, → Floor
tion 2.1.4. Shrinkage, therefore, is low, and dye- Coverings). Carpet fibers based on PETP are
ability is optimum. The spectrum of fineness used as both normal and high-shrinkage types
and cut length ranges from 1.7 dtex (38 mm) to in home furnishings and in needle-punched felt.
6.7 dtex (120 mm). Wool types are also avail- Such fibers are also made with various cross sec-
able as continuous tow for processing on cut- tions; their finenesses and cut lengths range from
ter – converters. 6.7 dtex (135 mm) to 20 dtex (150 mm). An es-
sential characteristic of polyester floor coverings
is that their mechanical properties are unaffected
by moisture.
Special types of PETP staple fibers have se-
cured a place in the market. Some can be dyed
in an open vessel without carrier to deep shades
[68]. Such staple fibers and tows meet special
requirements of environmental protection where
wool blends have to be used (carriers) and HT
dyeing is, therefore, excluded. These fibers ex-
ist as standard types and as pill-resistant tows.
Cationic dyeable staple fibers are used in rel-
atively small amounts in the wool area and in
polyester carpets.
Figure 5. Stress – strain curves of PETP wool types Since the mid 1970s,flame-retardant PETP
—— Wool fibers have rounded out the product spectrum
– – – – PETP wool type (normal) [73]. These fibers are used in apparel and, es-
· · · · · PETP wool type (low pilling)
pecially, in home furnishings. They meet legal
The so-called pilling phenomenon, which oc- requirements and even exceed them in some
curs in blends with wool, has been responsible cases. For these, PETP copolymers with phos-
for considerable developmental cost. Small balls phorus compounds have proved particularly use-
or pills are formed on the surface of textile fab- ful. Fibers of this type combine the comfort ex-
rics during use. Suitable fibers have been de- pected of unmodified PETP fibers with mod-
veloped to solve this problem [59], [93]. Their ern safety requirements. They are distinguished
special structure eventually causes the fibers an- by deep dyeability with disperse dyes. Because
of their diverse applications, these fiber types
 Fibers, 4. Synthetic Organic 31

are available in finenesses and cut lengths from is drawn down at ca. 700 m/min and finally
1.7 dtex (38 mm) to 13 dtex (150 mm). wound at ca. 3000 m/min. Winders developed
for high-speed spinning in 1983 permit drawing
down at speeds up to ca. 4000 m/min with final
2.3.2. Continuous-Filament Yarns for windup speeds up to 6000 m/min [87]. This pro-
Apparel and Home Furnishings cess is highly cost-effective, and product quality
is good.
Special Features of the Manufacturing In a variant of the spin-drawing process, the
Process. Poly(ethylene terephthalate) that is to draw rolls are mounted near the spinneret at the
be spun into continuous-filament yarn for ap- point where the filaments have just attained their
parel generally exhibits an intrinsic viscosity [η] final fineness and are still warm [96]. This pro-
of 0.70 – 0.75 [37]. It must be highly purified, cess, too, is rated highly for cost and quality of
especially when used in high-speed spinning, product.
which is often the case. The polymer must also Spinning speeds have gradually been raised
be dried carefully to < 0.01 % H2 O. to 2800 – 4500 m/min to increase productivity of
As in staple fiber units, the spinning posi- the spinning units. The result has been produc-
tions of a spinning machine are aligned in a row. tion of partially oriented yarn (POY) [53], [95].
Quenching is mostly done by a transverse air These yarns are less sensitive because of their in-
flow with several spinnerets in a single shaft so herent slight crystallinity and require less draw-
that all filament bundles are affected uniformly. ing. Drawing can now be combined with tex-
At the lower end of the spinning shafts, the fil- turing into a single process, with considerable
ament bundles are individually combined into savings in investment and operating costs [97].
yarns while finish is applied to them. Finishing Drawoff rolls or godets are not required in
with a perforated yarn guide has been generally high-speed spinning, and drawing-off can be left
adopted. Below the spinning shafts, the yarns are to the winder; however, special measures must
usually drawn off by godets, the circumference be taken to match the spinning tension to the
and revolutions of which determine the spinning optimum (mostly lower) windup tension [87].
speed; the yarns are then wound individually on Yarn spun at higher speed and then drawn
bobbins [37]. takes up dye more readily; because it is more
Originally, spinning speeds were 500 – highly oriented, postdrawing is lower and en-
1500 m/min. The as-spun yarn was amorphous tails less additional crystallinity. Material spun
and characterized by an orientation birefrin- at very high speed is, moreover, said to have an
gence ∆n of (3 – 10)×10−3 , a so-called low especially loose structure, with fewer large crys-
orientation yarn (LOY ) [53], [95]. The as-spun talline regions, even after drawing [53].
yarn was drawn by passing it, with friction, over Commercial high-speed spinning has be-
heated pins in the draw zone and then addition- come possible only through the development
ally, with surface contact, over a hot plate. This of suitable winders, which can also be used
process was replaced by drawing on heated rolls for as-spun yarn. They can go as high as
with several wraps [37]. For heat-setting, the 6000 m/min and, for experimental purposes, up
delivery roll of the set of draw rolls was also to 10 000 m/min [98].
heated but at considerably higher temperature. In the speed range of 3000 – 4000 m/min,
Final drawoff was by a third pair of rolls. The productivity no longer increases substantially
drawn yarn was wound on a twister (draw twist- with spinning speed. Hence, yarn spun at 2800 –
ing) or on a winder (draw winding); frequently 4000 m/min has been adopted as the starting ma-
it was then twisted, heat-set, and rewound. Such terial for draw texturing [95]. Therefore, addi-
units, which involve slow spinning and separate tional investment in increased spinning speed
drawing, are still operating but are probably no is probably not worthwhile [99]. Efforts have
longer being built. been directed at reducing spin orientation and
Improvements in winding frames for drawn thus increasing draw ratio and productivity. For
yarn led to the next development, spin drawing . example, a heating tube below the spinneret re-
In this process, a set of draw rolls is mounted duces spin orientation [100], as do minor addi-
below each spinning shaft. The as-spun yarn tions to the polymer of low-viscosity polymers
32 Fibers, 4. Synthetic Organic

[101] or components with slight cross-linking fibers, in a relatively expensive process, fila-
action [102]. ment yarn is available immediately.
The drawing process is combined with textur- Filament yarn is offered flat, i.e., with silk-
ing in draw texturing to produce textured yarns like, or variously crimped textures; thus, it pro-
from material spun at high speed. In this process, vides opportunities to change the hand, bulk, and
the yarn is drawn in the texturing zone on the first optical appearance of downstream goods and to
heater of the texturing unit, i.e., between the de- accomodate styling requirements in apparel and
livery rolls and the twister. This places stringent home furnishings, which far exceed the range
requirements on the as-spun yarn. Its structural attainable with natural fibers [37], [92][93][94].
properties, such as orientation and crystallinity, Partially oriented yarns (POY) have, since the
must be uniform to ensure uniform dyeability of introduction of high-speed spinning technology
the end product. In addition, the as-spun yarn (see Section 2.1.2), led to successful intermedi-
must not have any defects such as broken fil- ates for internal fiber production as well as to sal-
aments. In most cases, the yarn is additionally able products. These filament yarns are spun and
heat-set on a second heater in the texturing unit wound at speeds of ca. 3000 – 4500 m/min. They
with a 7 – 14 % contraction in length. This set- are precursors for pirn drawing (cops drawing),
ting process reduces the crimp elasticity of the warp drawing (→ Fibers, 3. General Production
yarn, which is then dimensionally stable. Technology), as well as warp drawing – sizing or
The major problem in the manufacture of draw texturing. Most POY products with a fine-
textured PETP yarns is uniform dyeability. The ness of 300 dtex and 32, 34, or 36 filaments per
many process steps and, hence, variables require yarn (dtex 300 f 32, etc.) are produced for draw
special attention during manufacture. Total test- texturing, which is the largest end use.
ing costs are high.
A smaller fraction of PETP filament yarns Flat Yarns. For direct textile processing in
for apparel is processed without texturing. Flat weaving and knitting, suitable flat fully oriented
yarns are obtained by the old process of separate yarns (FOY) are available on pirns, bobbins,
spinning and drawing mentioned previously, as or as warp beams. They are sold with round,
well as by spin drawing. More recently, flat yarns trilobal, triangular, or even octalobal cross sec-
have also been spun at high speed [48], [53]. Sev- tions with an individual filament fineness of 2 –
eral processes, such as high-speed spin drawing 5 dtex and a yarn fineness of 22 – 167 dtex.
and warp drawing [103], [104], can accomplish
this economically and with high product quality.
Because PETP yarns spun at 6000 m/min still
have flat stress – strain curves, they cannot be
used as is [95]. Thermal treatment in the spin-
ning shaft, e.g., a heating zone in the shaft,
helps increase their orientation and crystallinity
[105], [106]. The stress – strain behavior of this
highly oriented yarn (HOY) then suffices for sev-
eral special applications. At still higher spinning
speed, the sheath – core effect of orientation and
crystallinity can exert a negative influence [53],
[107]. Figure 6. Stress – strain curve of highly oriented filament
yarns (HOY)
Types of Continuous-Filament Yarn,
Pirn (cops) material intended for weaving
Properties, and Uses. Continuous-filament
and warp knitting is produced “classically” with
yarns are products of the man-made fiber in-
twist from LOY or from POY. Material in bob-
dustry that can be converted directly to textile
bins, on the other hand, is used exclusively in
fabrics, i.e., without intermediate processing.
weaving and comes primarily from one-step pro-
Whereas staple fibers are produced by first cut-
cesses such as spin drawing or high-speed spin-
ting crimped filaments which then must be spun
ning (4000 – 6000 m/min) (see Section 2.1.2).
into a yarn, possibly in mixtures with other
 Fibers, 4. Synthetic Organic 33

The fineness of individual filaments made by this of such yarns, however, are closer to flat yarns.
latter process ranges from 0.6 to 3 dtex. These Other yarns are formed by cotexturing different
HOY yarns are distinguished by uniform dye- types of individual filaments. These approach
ability. A stress – strain curve, which, in contrast staple yarns, even with regard to the comfort of
to standard yarn, exhibits higher tensile elonga- clothing made from them.
tion, is shown in Figure 6. Warp beams, finally, Extremely low fineness filaments with indi-
are produced by the warp-drawing process from vidual counts down to 0.1 dtex (produced by
POY exclusively for warp knitting. For weaving, splitting thicker filaments) or 0.6 dtex (spun di-
the warp draw – sizing process is used. rectly) are used in textiles with the appearance
Textured Yarns. The major application for and feel of buckskin.
textured yarn, primarily false-twist textured, is In differential dyeing cationic dyeable yarns
in knitting and weaving for apparel. Air-textured are used in addition to normal disperse dye-
yarn, on the other hand, is used predominantly in able filament yarns. When yarns are made from
home furnishings and is processed by weaving. blends of disperse dyable individual filaments
False-twist textured yarns are draw-textured, and cationic dyeable ones, they may be dyed in
starting with POY, mostly by the friction pro- different colors.
cess, but in some cases by the spindle pro- Flame retardancy in home furnishings, espe-
cess. Their linear density is 50 – 200 dtex (sin- cially in drapes and curtain fabrics, is achieved
gles yarn), with an individual filament fineness with filament yarns that consist of modified
of 1.25 – 5 dtex. The round cross section of POY PETP. By inserting a phosphorus compound into
filaments is distorted by draw texturing. How- the fiber molecule, the flame retardancy of such
ever, special yarn types are produced with a tri- yarns is permanent and cannot be removed in
angular profile, which is preserved during draw washing or dry cleaning.
texturing. This type of individual filament cross Finally, filament yarns with permanent anti-
section imparts a special luster, almost a glit- static properties are available. In general, how-
ter, to textile fabrics. The linear density of most ever, the surface conductivity required for pro-
false-twist textured yarns now used in knitting cessing and for some end uses is achieved by
and weaving is ca. 167 dtex. Fine yarn down to applying finishes.
50 dtex/40 filaments is used in ladies’ blouses,
for example.
Air-textured yarn can be made from either 2.3.3. Continuous-Filament Yarns for
POY or FOY. With POY, a drawing step pre- Industrial Applications
cedes air texturing on the texturing machine,
whereas FOY is textured directly. In this pro- Special Features of the Manufacturing
cess the filament cross section, usually round, Process. Filament yarns for industrial use are
is preserved. The linear density of such yarn is generally spun from higher molecular mass
200 – 3000 dtex for single yarn, which is appro- PETP, which is the only way to achieve high
priate for its primary use in home furnishings. strength. For low-fineness, high-tenacity yarn
The fineness of individual filaments is 2 – 3 dtex. (final fineness < 1000 dtex) PETP with an intrin-
Special Types. The extensive product line of sic viscosity [η] of 0.75 – 0.80 is used; for coarse,
continuous-filament yarns includes many spe- high-tenacity yarns (final fineness ≥ 1000 dtex),
cial types. Examples of interesting new develop- the intrinsic viscosity [η] of PETP is 0.95 – 1.05.
ments are filament yarns with staple yarn char- Such molecular masses are achieved either by
acter, i.e., filament yarns with the less regular continuous polycondensation with direct spin-
and bulkier structure of staple yarns, which is ning or, preferably, by postcondensation in the
achieved by the type and arrangement of indi- solid state [37].
vidual filaments. In some cases, free fiber ends During condensation in the melt, COOH end
even protrude from the yarn. groups, which catalyze hydrolytic degradation
A large variety of properties is possible today. of PETP in the melt, are formed in the poly-
Among the most important are yarns with high mer and can disarrange the structure in the fi-
bulk character, which is achieved by differential nal product. These end groups can be protected
shrinkage of individual filaments. The properties with carbodiimides [70] or similarly acting sub-
34 Fibers, 4. Synthetic Organic

stances, which are added to the polymer in small steps by spinning and further treatment as a
amounts prior to spinning. No COOH groups warp. During spin drawing, the spinning speed is
are formed if solid-state condensation is carried ca. 700 m/min; when spun on bobbins for warp
out in a vacuum or under a protective gas and processing, it is ca. 700 – 1000 m/min. Yarn has
at temperatures below the melting point. Care been spun at much higher speed, in which case
must be taken, however, that the polymer does the disturbing influences mentioned previously
not absorb water during storage or during trans- are compensated in other ways [111].
portation from the condensation to the melting The spin-draw machines for coarse high-
equipment. tenacity yarn resemble those for fine high-
Polymer with a high viscosity requires a tenacity yarn except that some parts are even
rather high spinning temperature, e.g., ca. more massive [94]. Because of the high operat-
290 ◦ C for fine yarn and ca. 310 ◦ C for coarse ing speed (up to 4000 m/min) the residence time
yarn [37]. To minimize thermal degradation of on heat setting rolls and beyond is short. There-
the melt, the lines carrying melt from extruder to fore, preparing low-shrinkage material by spin
spinneret must be as short as possible. Also, the drawing is difficult; however, the strength that
melt in the distribution lines after the extruder is can be achieved is considerable.
kept relatively “cold” and warmed to the higher In the draw-line process, a warp of yarn is
spinning temperature only in the spinning pack drawn in two steps and then heat-set. After the
[108]. last set of rolls, which determines the setting
Fine, high-tenacity yarn has a linear density shrinkage, the yarn is wound on individual bob-
similar to that of textile yarn. For this reason, it bins. The delivery speed of such draw lines
is spun on a similar machine. The yarn is either is 120 – 300 m/min, with a productivity of 4 –
spun and drawn in separate process steps or spin- 10 t/d.
drawn continuously. The spinning speed for fine The ability of the end product to shrink and
high-tenacity yarn in the two-step process is its shrinkage force can be reduced, both in spin
approximately 1000 m/min and 500 m/min and drawing and in warp processing, by permitting
higher during spin drawing. The draw ratio is shrinkage in the heat-setting step. This increases
ca. 5; the yarn is usually allowed to shrink ca. elongation of the yarn at loads important in prac-
10 % during heat-setting at a hot roll temperature tical applications. The much higher residence
of ca. 240 ◦ C. The delivery speed of the draw- time of the yarn in postdrawing and setting in
ing machines is ca. 700 m/min, but during spin the warp process leads to lower residual shrink-
drawing, it is substantially higher (ca. 2500 – age at equal relative elongation of the end prod-
3000 m/min). uct (relative elongation being the elongation at a
A special, high-volume variant of fine, high- given load). Inversely, at equal residual shrink-
tenacity yarn is sewing yarn. By plying, twisting, age, the relative elongation of the product from
and renewed heat-setting, throwsters turn this the warp process is lower. These relationships
yarn into sewing thread, whose most important are influenced further by the polymer used, the
characteristic is the sewing length achievable. spinning process, and the drawing conditions.
The goal is sewing yarn that needs no further In certain end uses, coarse industrial PETP
plying and twisting to make it comparable in yarn must exhibit good adhesion to rubber. For
processability to sewing thread of staple fiber. this purpose, an appropriate adhesive finish is
During spinning of particularly viscous poly- applied during spinning or in warp processing
mers for coarse industrial yarn, very high draw- prior to heat-setting. This finish may contain
ing forces develop in the filaments. These forces epoxy compounds (Epikote) or similarly acting
can be relieved by delaying filament cooling material.
with the aid of a heating tube directly be-
low the spinneret, which reduces spin orienta- Industrial Yarns, Properties, and Uses. Of
tion and equalizes the structure of the filaments the three product forms used industrially, i.e.,
[100], [109]. In this way, noticeably higher final high-tenacity filament yarns, spunbonded prod-
strength can be attained [110]. ucts, and monofilaments, the filament yarns
Coarse high-tenacity PETP yarn is produced have by far the broadest application [37],
either in one step by spin drawing or in two [92][93][94]. This ranges from the building in-
 Fibers, 4. Synthetic Organic 35
Table 8. Filament yarns for industrial end uses

Types Shrinkage Fineness, Number of Filament Tenacity, Elongation, %

in hot air at dtex filaments fineness, cN/tex
200 ◦ C, % dtex

Yarns for sewing 17 – 18 74 – 455 24 – 96 3.1 – 4.7 68 – 70 12 – 13

threads, normal
shrinkage
Yarns for sewing 7 49 – 940 16 – 200 2.5 – 4.7 68 – 70 16 – 17
threads, low
shrinkage
Fine yarns, normal 18 – 19 280 – 940 48 – 200 3.3 – 5.8 65 – 70 12 – 14.5
shrinkage
Fine yarns, normal 19 – 22 550 – 940 50 – 100 9.4 – 11 66 – 69 19 – 22
shrinkage
(spun-dyed black)
Fine yarns, low 4 – 14 140 – 550 24 – 96 5.8 60 21
shrinkage
Coarse yarns, normal 15.5 – 22 1100 – 1670 100 – 200 5.5 – 11 72 – 73 13 – 15.5
shrinkage
Coarse yarns, normal 15.5 – 22 1100 – 1670 100 – 200 8.4 – 11 66 – 72 12.5 – 13.5
shrinkage
(spun-dyed black)
Coarse yarns, low 3.5 – 5.0 1100 – 1670 200 5.5 – 8.4 72 16.5 – 17.5
shrinkage (7.5 – 8.5)∗ (73 – 75)∗ (11.5 – 12.5)∗
Coarse yarns for 10 – 18 1100 – 1400 200 5.5 – 7 75 12
tire cord
Coarse yarns 22 2200 – 11 000 400 – 2000 5.5 other values depend on
(plied fineness) single yarn

∗ With adhesive finish.

dustry through machine and motor vehicle con- yarn breakage. All these requirements are met
struction, chemistry, mining, agriculture and or exceeded by fine denier, high-tenacity PETP
forestry, transportation, sporting goods, protec- filament yarns. They have performed well along-
tion of the workplace and the environment, to side PETP staple yarns and PETP stretch-broken
apparel and home furnishings. Such yarns are yarns in 100 % PETP sewing yarns as well as in
offered on the market in three major categories: core-spun yarns.
sewing yarn, fine yarn, and coarse yarn. Depend- Sewing Yarns with Normal Shrinkage. Fila-
ing on end use, these yarns are employed either ment yarns with normal shrinkage are suitable
as normal-shrinkage or low-shrinkage types. In for 100 % PETP sewing yarns, which must be
addition to fine and coarse white yarns, spun- heatset (Table 8). Sewing threads prepared from
dyed black types are also available. The extraor- them are used especially in high-performance
dinarily broad product line is rounded out by areas, e.g., safety belts, cushions, leather shoes,
plied fineness of coarse filament yarns. For an luggage, and handbags.
overview see Table 8. Sewing Yarns with Low Shrinkage. Low-
Sewing Yarns. The value of sewn textiles, shrinkage filament yarns are offered in a broad
particularly their appearance and durability, de- range of finenesses (Table 8). The largest end
pends to a large extent on seam performance. use is in core-spun yarns. By spinning a sheath
To best complement textile design and construc- of cotton, viscose, or other polymeric staple
tion, the seam must meet many requirements, fiber around a PETP filament core, the prop-
the most important of which are neat appear- erties of both fiber types are combined. The
ance, high tenacity and abrasion resistance, high sheath assures sewability; the core, mechanical
lightfastness (especially to ultraviolet radiation), efficiency. Such yarns meet high requirements
resistance to chemicals, and washfastness. In of aesthetics, dyeability, and temperature resis-
addition, good sewability is significant for the tance.
sewing yarns; this is defined as achieving a high Fine Filament Yarns. Both normal- and low-
sewing length at high sewing speeds without shrinkage fine filament yarns are available for
36 Fibers, 4. Synthetic Organic

general use. Filament yarns with normal shrink- heat during mechanical loading. They, there-
age are offered as white or spun-dyed black fore, have all the prerequisites to utilize fully
types. Both types are preferred in lashing straps, the high chemical stability (resistance to hydro-
tapes, belts, ropes, nets, and fire hoses. lysis) provided by extremely low concentrations
Low-shrinkage fine filament yarns are of- of COOH groups. Solid-phase polycondensa-
fered only in white (Table 8). They have a wide tion combined with chemical capping of the ma-
range of applications, extending from base fab- jority of any still-existing COOH groups (see
rics for PVC or rubber coating for tarpaulins, Section 2.2.1) makes possible the high stability
membranes, containers, awnings, and tent roofs, of the tire cord.
through conveyor belts, V-belts, hoses, filter fab- The high-tenacity, coarse-filament single
rics, and drying screens for paper making to sail- yarns discussed so far are complemented for
cloth. Its use in sailcloth demonstrates the ability many end uses by a series of plied yarns. These
of PETP to meet the requirements of low mass, include some that are adhesively finished for
high tenacity, and uniformity, as well as resis- use with rubber, others that have low-shrinkage
tance to UV light, chemicals, water, and mildew. like the single yarns, and still others that have
Coarse Filament Yarns. Coarse yarns, like normal shrinkage. Their finenesses extend up to
fine yarns, are offered with either normal or low 11 000 dtex. These yarns are intended for use
shrinkage (Table 8). Yarns with normal shrink- in the coating sector as well as in straps, belts,
age are available in white or spun-dyed black ropes, nets, and hoses.
versions. White yarns, analogous to the corre-
sponding fine yarns, are intended for lashing
straps, belts, ropes, nets, hoses (especially pres- 2.3.4. Spunbonds
sure hoses), and safety belts. The situation is
quite similar with respect to the black types, Special Features of the Manufacturing
which are used primarily in safety belts and lash- Process. Spunbonded products are consolidated
ing straps. random layers of 2- to 10-dtex continuous fil-
Low-shrinkage coarse filament yarns, which aments [112]. They are produced as continu-
are offered exclusively in white, have equally ous sheets up to 5 m wide in a continuous pro-
wide-ranging applications, such as base fab- cess from polymers of average intrinsic viscosity
rics for PVC or rubber coating for tarpaulins, ([η] ca. 0.7). Their unit weights range from 20
membranes, containers, awnings and tent roofs, to 500 g/cm2 (→ Fibers, 3. General Production
hoses, filter fabrics, belts, conveyor belts, V- Technology).
belts, and drying. A spunbond production line usually consists
An especially interesting end use for low- of several rows of spinnerets with mutually dis-
shrinkage, high-tenacity, adhesively finished fil- placed spinning packs. Each filament bundle is
ament yarns is in automobile tires. The proper- accelerated by a draw tube under the spinneret to
ties of such yarns make them highly suitable for a final speed of ≥ 5000 m/min and thus is drawn
the carcass of radial tires. Tires with these yarns [113]. Spreading devices open the filament bun-
no longer exhibit the disturbing phenomenon of dle and lay the filaments down on a moving
flat spotting, observed in nylon-reinforced tires. belt in overlapping random patterns. Various de-
(Flat spotting is the formation of an elliptical signs are known for these spreading devices; i.e.,
footprint in the tire during standing, resulting mechanical, pneumatic, and electrostatic [112].
from molecular deformation of nylon because Properties of the filaments are the same as
of its low glass transition temperature. It causes those of filament yarns spun at high speed: tenac-
a bumpy ride until the tire warms up.) Since ity ca. 3.5 cN/dtex, break elongation ca. 70 %,
the early 1960s, much effort has been expended and shrinkage at 200 ◦ C ca. 3 %. The orienta-
to solve the problems of PETP tire-cord mate- tion is characterized by a birefringence ∆n of
rial. In addition to rubber adhesion, these in- ca. 100×10−3 , and the degree of crystallinity is
cluded the hydrolytic stability of PETP. High- ca. 40 %.
tenacity filament yarns for tires are rather low The loose filament web, laid down as uni-
in shrinkage. They have high moduli, exhibit formly as possible, is then consolidated by using
high flexural strength, and thus produce little various processes singly or in combination, such
 Fibers, 4. Synthetic Organic 37

as needle punching, calendering, and bonding. throughout (measured on strips 5 cm wide).

For certain applications, the web must be made Break elongations are 60 – 100 % for needle-
thermally stable by additional heat-setting. punched webs, 20 – 60 % for bonded and nee-
dled webs, and generally < 30 % for thermally
Spunbonded Products, Properties, and bonded webs.
Uses. Polyester spunbonds are available in unit
weights of 20 – 500 g/m2 and in widths of 1 –
5 m. The consolidation discussed in the preced- 2.3.5. Monofilaments
ing section via needle punching, bonding, or cal-
endering requires, in addition to PETP and suit- Special Features of the Manufacturing
able binders, the use of polyesters of lower melt- Process. In the production of PETP monofila-
ing point or even of PETP fibers with a sheath of ments, polymers with intrinsic viscosities [η] of
a different polymer. Polyester spunbonds are of- 0.7 – 0.9 are used. Polymers of higher viscosity
fered commercially under various trade names: are often brought to their required value by solid-
phase condensation. Because these polymers
Asahi Asahi Kasei then have a lower content of COOH groups, they
Colbond BV Coltron
EniChemFibre SpA Terbond-Spun have advantages for use in hydrolysis-resistant
Hoechst Trevira-spunbond monofilaments with increased hot – wet durabil-
Lutravil Lutradur
Reemay, Inc. Reemay
ity. Occasionally, the COOH end groups of the
Rhône-Poulenc Bidim polymers are also protected chemically.
Teijin Unisel Monofilaments with final thicknesses of
Toray Axter
Toyobo Toyobo Volans 0.03 – 2 mm are spun in air, cooled immediately
Unitika Marix in water, then drawn, heat-set, and packaged on
a directly connected draw line [114]. Each ex-
truder usually has its own spinning head and,
Lightweight webs (20 – 50 g/m2 ) are avail- accordingly, its own draw line. Various designs
able with individual filament counts of 2 – are recommended for spinning heads and spin-
3 dtex. They are used as cover webs in sanitary nerets, such as circular spinnerets and spinnerets
products and in horticulture. with straight rows of holes [115]. Feed for each
Nonwoven products (50 – 130 g/m2 ) have fil- spinneret hole should be the same. A few cen-
aments with individual finenesses of 4 – 5 dtex. timeters below the spinneret, the filaments enter
Their end uses are in construction and in shoe a water bath, whose temperature is above the
caps. glass transition temperature of PETP (70 ◦ C).
Materials with unit weights of 130 – The filaments are cooled but remain soft. In the
500 g/m2 and individual filament finenesses up bath, they change direction, are brought out of
to 10 dtex are intended especially for use in con- the bath as a warp sheet, and are drawn off by a
struction (e.g., carriers for asphalt sheets for set of rolls at a rate of less than 100 m/min. The
roofing), needle felts, embossed PVC coatings, filaments have no spin orientation.
underground construction, hydraulic engineer- The first draw almost always takes place in
ing, and road building. water at 90 – 95 ◦ C; the second draw, also takes
In addition to their large use in construction, place in a water bath, a higher boiling liquid, or
polyester spunbonds are already being used suc- a heater tunnel. Die plates are sometimes used
cessfully in automobiles (e.g., trunk linings) as for more accurate adjustment of the thickness.
well as in protective clothing and for environ- Heat-setting occurs in a heater tunnel, usually
mental protection (covering of storage basins). at 130 – 180 ◦ C. Depending on the type desired,
Web properties depend predominantly on the more or less shrinkage is permitted and the total
often different technologies for web production draw ratio (ca. 1 : 4 to 1 : 6) is selected. At the
(laydown and bonding). No systematic data ex- end of the roll train, the monofilaments are taken
ist up to now that relate web structure to various up on individual bobbins on a creel.
end uses. However, in general, needle-punched In almost all applications of PETP monofil-
webs are bulky, whereas thermally bonded webs aments a uniform diameter is the most impor-
are thin. Web strengths are ca. 2 – 4 N g−1 m−2 tant mark of quality. Tolerance of ± 3 % is re-
38 Fibers, 4. Synthetic Organic

quired; if the process is carefully controlled, it Fig. 7) and, at the same time, high shrinkage.
will often be less. Additional quality require- Coarser wires range from 0.080 – 2.00. In addi-
ments are smooth surface and, if necessary, uni- tion, some wires have a rectangular cross section
form cross section. Textile properties of a given with diameters from 0.25 and 0.50 mm to 0.57
type must always remain constant, especially and 0.88 mm.
shrinkage tension and shrinkage. In monofila- Monofilaments for weaving, especially for
ments with improved resistance to hydrolysis, paper machine sieves are available as normal,
the residual strength after prolonged use should hydrolysis-resistant, and chemically stabilized
be preserved uniformly. types. The most important representatives have
high elongation (wires for the weft) or low elon-
Types of Monofilaments, Properties, and gation (wires for the warp) but low shrinkage.
Uses. Monofilaments are produced with diame- Another important group comprises zip-
ters of 0.034 – 2.00 mm These are thick filaments per monofilaments, with a diameter of 0.40 –
(the finenesses corresponding to these diameters 1.16 mm. This competes with polyamide wire.
are 12.5 – 43 000 dtex) and are, therefore, often A major advantage with PETP monofilaments is
called wires. A broad spectrum of types of PETP that their stress – strain properties and shrink-
monofilaments is found commercially in wo- age behavior can be varied to a great extent.
ven fabrics and zippers. These end uses place Thus, zipper wires are available over a whole
strict requirements on uniformity of diameter gamut of combinations from low, elastic exten-
and properties, and especially on stress – strain sibility with high shrinkage to high, plastic ex-
behavior and shrinkage. The mechanical proper- tensibility with low shrinkage. The majority of
ties of typical PETP monofilaments are evident these types exhibit low, elastic extensibility and
from the stress – strain curves in Figure 7. medium shrinkage at the boil.
In general, the combination of modulus and
shrinkage properties of zipper wire and wires
for weaving is determined by the special manu-
facturing process. It is chosen according to the
load – time program and the thermal exposure of
monofilaments during use. The ability to vary
their properties so widely makes possible the
adaptation of PETP monofilaments to any kind
of processing and to any end use.

2.4. Other Polyester Fibers

2.4.1. Poly(tetramethylene terephthalate)

Figure 7. Stress – strain curves of typical PETP monofila-
ments
——– Finest monofilament (0.055 mm diameter) The polyester of terephthalic acid and 1,4-
− − − Monofilament for weaving (weft type) butanediol [110-63-4] is a comparatively old
· · · · · · Monofilament for zippers fiber polymer [40].
Monofilaments for weaving are used in the
building industry in interior construction and in-
terior installation. Other, often large, areas of ap-
plication are paper machine sieves, safety belts,
filter and screening fabrics, as well as conveyor
Because 1,4-butanediol has always been
belts. Fish nets, cordage, fishing lines, and medi-
more expensive than ethylene gly-
cal applications all require the special properties
col, poly(tetramethylene terephthalate)
of monofilaments for weaving.
[30965-26-5], also called poly(butylene tere-
The finest monofilaments, with diameters
phthalate) or PBT, remained more or less on
of 0.034 – 0.055 mm, have high elongation (see
the sidelines. Not until the middle of the 1960s
 Fibers, 4. Synthetic Organic 39

were special PBT products developed by sev- the boil without carrier because of its lower glass
eral producers; the advantages of these products transition temperature.
compared to PETP permitted use of the more In addition to its elastic behavior and easy
expensive 1,4-butanediol [116]. Today, these dyeability, PBT has other favorable properties.
PBT products have become well-entrenched in For example, it tends to swell less than PETP.
the marketplace. All these factors, taken together, make PBT
Production of PBT is similar to that of an interesting raw material for textile zippers.
PETP. Dimethyl terephthalate is transesterified Finally, because of their resistance to alkali,
and subsequently polycondensed, either batch- good abrasion resistance, and elastic behavior,
wise or continuously. However, the catalysts PBT monofilaments are advantageously used in
used with PETP promote ring closure of 1,4- screen fabrics, which are constantly exposed to
butanediol, leading to the potentially explo- hot water or slightly alkaline media. In this way,
sive tetrahydrofuran. Therefore, tetraisopropyl fibers for carpets and monofilaments for zippers
titanate [546-68-9], for example, is used as cat- and screens have become products in which the
alyst in both process steps. more expensive polymer (PBT) pays for itself.
Because the aliphatic sections of the molec-
ular chains are longer and thus more mobile, the
transition temperatures of PBT, mp ca. 230 ◦ C 2.4.2. Poly(1,4-dimethylenecyclohexane
and glass transition temperature ca. 25 ◦ C, are terephthalate)
lower than those of PETP. In addition, PBT crys-
tallizes more readily than PETP. The PBT unit Fibers of poly(1,4-dimethylenecyclohexane
cell exists in two modifications. Of these, one is terephthalate) [25135-20-0], PDCT, have been
more extended, ca. 11 % longer, and reverts to on the market since the late 1950s under the trade
the shorter one when unloaded. This is responsi- name Kodel II (Tennessee Eastman Company,
ble for the better recovery of PBT products from United States) (see below).
stretching and bending. The intermediates are dimethyl terephthal-
Like PETP, PBT is spun on standard ma- ate (DMT) (Section 2.1.1) and 1,4-bis(hydro-
chines from the melt. Because of the lower glass xymethyl)cyclohexane [105-08-8] commonly
transition temperature, formation of spin orien- known as 1,4-cyclohexanedimethanol. This diol
tation not only occurs along the spinning path is produced by the two-step hydrogenation of
but continues into the drawoff and the windup. DMT at 160 – 180 ◦ C and high pressure in the
In addition, clearly recognizable crystallization presence of catalysts (→ Alcohols, Polyhydric,
of PBT occurs during spinning, which in turn Chap. 2.7.). The diol can exist as either the trans
also affects orientation. Properties of the as-spun or the cis isomer. By appropriate choice of re-
yarn thus depend in a complicated manner on action conditions, the trans – cis ratio can be ad-
spinning conditions. justed to 7 : 3. To prepare the polymer, DMT
After the usual drawing and heat-setting, PBT is transesterified with the diol and after excess
has a flatter stress – strain behavior than PETP diol is distilled, polycondensation takes place in
(Fig. 8). The permanent extension of a PBT a manner analogous to PETP.
product after straining, however, is much less The polymer is transparent and amorphous.
(Fig. 9) [116]. For example, after a strain of It crystallizes in the triclinic system. The crys-
15 %, the permanent extension of PETP is 8.5 %; talline density is 1.265 g/cm3 for polymer with
that of PBT, only 2.5 %. For this reason, PBT trans isomer and 1.303 g/cm3 for polymer with
is particularly suited for carpet fibers, which cis isomer [117], [118]. Wide-angle X-ray di-
must exhibit good recovery after loading. Unlike agrams of crystalline samples show a continu-
PETP, PBT can be dyed easily to deep shades at ous transition of the trans crystal lattice to the
cis crystal lattice with increasing cis – trans ra-
40 Fibers, 4. Synthetic Organic

Figure 8. Stress – strain curves of drawn and heat-set PETP and PBT yarns [116]
A) Drawn; B) Drawn and heat-set without clamping; C) Drawn and heat-set with clamping; D) Drawn, heat-set with clamping,
plus heat-set without clamping
– – – – PETP; —— PBT

tio. The fiber density is 1.22 – 1.23 g/cm3 . Small- of the polymer [118]. The result is greater crimp
angle X-ray investigations show a fibrillar struc- stability of PDCT fibers and, hence, greater bulk
ture with lattice layers at an angle to the fiber of nonwovens and textile fabrics. Because of
axis. the higher glass transition temperature, how-
The glass transition temperature of the poly- ever, PDCT fibers are more difficult to dye than
mer is 76 ◦ C; in drawn and crystalline fibers, it PETP fibers. Therefore, the dyeing temperature
can be as high as 100 ◦ C. The melting point is for PDCT fibers must be increased or suitable
285 – 295 ◦ C [92]. carriers and dyes chosen.
Compared to PETP, the tenacity of PDCT sta- Applications of PDCT fibers are in areas such
ple fibers is ca. 30 % less, with the same elon- as fiberfill and carpets that require especially
gation at break. The abrasion resistance behaves high crimp stability and generally high recovery
similarly. The tensile or bending recovery of the forces following deformation at room tempera-
fibers from equal deformation at room tempera- ture. These fibers are also used in blankets and
ture, on the other hand, is greater for PDCT be- synthetic furs [118].
cause of the higher glass transition temperature
 Fibers, 4. Synthetic Organic 41

Figure 9. Permanent extension of PETP and PBT yarns after strain [116]
A) Drawn; B) Drawn and heat-set without clamping; C) Drawn and heat-set with clamping; D) Drawn, heat-set with clamping,
plus heat-set without clamping
– – – – PETP; —— PBT

2.5. Uses pers, woven screens, geotextiles, roofing sheets,

or book covers.
Staple fibers, continuous-filament yarns, The extremely high performance of PETP is
monofilaments, and spunbonds of polyester are reflected in the breadth of end uses [37], [59],
found in all major textile markets. Among the [69], [92, 93], [119], [121]. This performance is
polyesters, poly(ethylene terephthalate) is the based primarily on two properties of the fiber
most important polymer. Apparel, such as out- products: the dimensional stability of the textiles
erwear or sportswear, as well as work clothing made from PETP under mechanical and thermal
and protective clothing, could not be imagined stress, and their ease of care. Both properties
without PETP fibers, either 100 % or in blends are primarily determined by the glass transition
with other man-made or natural fibers. Sim- temperature which, depending on the chemical
ilarly, PETP fibers are widely used in home structure of the polymer and the degree of orien-
furnishings, such as drapes and curtains, fur- tation and order, lies between ca. 70 and 100 ◦ C
niture covers, table and bed linens, cushions, (see Section 2.2.1, → Fibers, 2. Structure). The
pillows, and carpets. fibers can be crystallized at any stage of their
Polyester products have been particularly manufacture and during further processing. This
successful in industrial markets. Here, they are permits production of any desired shape.
encountered everywhere fibers can be used. Polyester fibers are available in all possible
In many cases, because of their properties, forms in which natural and man-made fibers ex-
especially their relatively low density (ca. ist and can be processed on equipment used to
1.38 g/cm3 ), they have provided elegant and, at manufacture yarns, woven fabrics, knit goods,
the same time, economical solutions to prob- and even nonwovens. Grouped broadly, the
lems. Examples are sewing thread, tarpaulins forms of PETP are the following:
and awnings, safety belts, V-belts, tire cord, zip-
42 Fibers, 4. Synthetic Organic

1) Staple fibers with a fineness of 0.4 – 20 dtex; World production of fibers increased from ca.
short cut fibers, 6 mm length, fibers of 30 – 14.9×106 t/a in 1960 to 34.8×106 t/a in 1985.
60 mm up to 150 mm; round or modified Natural fibers, essentially cotton and wool, con-
cross sections; crimped (except for flat cut tributed ca. 7.6×106 t/a of this increase, whereas
fibers). man-made fibers contributed ca. 12.2×106 t/a
2) Textile continuous-filament yarns with a [41], [120]. Production of man-made fibers has
fineness of 20 – 200 dtex; individual filament increased fivefold from 1960 to 1985. Because
fineness of 0.5 dtex (special types 0.1 dtex) to the fraction contributed by cellulosic fibers de-
5 dtex; flat, textured, or with staple yarn char- creased, the increase in production of man-made
acter; round or modified cross sections. The fibers can be ascribed solely to synthetic fibers
fineness of air-textured, continuous-filament (Fig. 10).
yarns is 200 – 3000 dtex. From small beginnings prior to 1960,
3) Fine high-tenacity continuous-filament polyester fibers, essentially poly(ethylene tere-
yarns and yarns for sewing threads with a phthalate), attained a volume of 6.5×106 t/a by
fineness of 50 – 940 dtex, with individual fil- 1985. Their percentage of the production and
aments of 3 – 10 dtex; flat with round cross consumption of all synthetic fibers tripled bet-
sections. ween 1960 and 1985 (Fig. 11) and is now almost
4) Coarse high-tenacity continuous-filament 50 %.
yarns with a fineness of 1100 – 1670 dtex
(plied fineness up to 11 000 dtex); individual
filaments of 5 – 11 dtex; flat with round cross
sections.
5) Spunbonds in widths of 1 – 5 m; unit weights
of 20 – 500 g/m2 , with an individual filament
fineness of 2 – 10 dtex.
6) Monofilaments with a diameter of 0.034 – ca.
2 mm; flat with round or modified cross sec-
tions.

Figure 11. Production of polyester fiber compared to all

2.6. Economic Aspects chemical fibers and to synthetic fibers
Plain area = PETP proportion of all chemical fiber produc-
tion; Vertically hatched area = PETP proportion of synthetic
fiber production
∗ Estimated.

The two most important fiber forms are sta-

ple fibers and filament yarns. For staple fibers,
including tow and nonwovens (Fig. 12), the pro-
duction of cellulosic fibers remained approxi-
mately constant between 1965 and 1985. During
this time, production of polyamide and poly-
acrylonitrile fibers, the latter predominating,
increased sixfold. The increase in poly(ethyl-
ene terephthalate) is about twice as great, i.e.,
twelvefold. As far as end uses are concerned,
PETP fibers compete with other synthetic fibers
only in a few limited areas. They are used mainly
in areas previously reserved for natural and cel-
Figure 10. World production of man-made fibers lulosic fibers.
Vertically hatched area = polyester fibers; Plain area = other
synthetic fibers; Horizontally hatched area = cellulosic fibers
In continuous-filament yarns, including in-
∗ Estimated. dustrial yarns and monofilaments (Fig. 13), pro-
 Fibers, 4. Synthetic Organic 43

duction of cellulosic fibers has decreased. Even during occasional wide swings in the market.
before the rise of PETP, polyamide yarns had a For this reason, only large chemical companies
secure niche in the market; between 1960 and were and are in a position to operate PETP fiber
1985, their production increased approximately plants. A selection of trade names and producers
threefold. The production of polyester yarns in- follows [119]:
creased twentyfold to equal that of polyamide
yarns. Little competition exists between the two; Allied Polyester (Allied, United States)
if any, it is in the industrial area. Here, too, Dacron (Du Pont, United States)
polyester continuous-filament yarns have pri- Diolen (Enka, Federal Republic of Germany)
marily penetrated areas previously dominated by Fortrel (Celanese, United States)
cellulosic continuous-filament yarns or by spun Grilene (Emser Werke, Switzerland)
yarns of natural fibers. Grisuten (German Democratic Republic)
Kodel (Tennesee Eastman Co., United States)
Tergal (Rhône-Poulenc, France)
Terital (Montefibre, Italy)
Terlenka (Enka, The Netherlands)
Tersuisse (Viscosuisse, Switzerland)
Terylene (ICI, United Kingdom)
Teteron (Teijin, Toray, Japan)
Trevira (Hoechst, Federal Republic of Germany,
United States)
Wistel (Snia Viscosa, Italy)

Figure 12. World production of staple fibers (key fiber ma-

terials) 2.7. Polyester: Summary and Future
Vertically hatched area = polyester; Diagonally hatched, in-
clined to the left = polyamides; Diagonally hatched, inclined
Prospects
to the right = polyacrylonitrile; Horizontally hatched area =
cellulose Properties. The following properties are re-
∗ Estimated. sponsible for polyester fibers being used in all
areas where fibers are applied:
1) the extremely broad range of mechanical
properties of staple fibers and filament yarns,
2) their variable and easily adjustable shrinkage
properties,
3) their ease of dyeing combined with high fast-
ness properties,
4) their high chemical, solvent, and UV resis-
tance,
5) the low flammability of even the standard
Figure 13. World production of continuous-filament yarns
polymer, which can be further improved by
(key fiber materials) modification without significantly impairing
Vertically hatched area = polyester; Diagonally hatched, in- other valuable fiber properties,
clined to the right = polyamides; Horizontally hatched area 6) the deformability of the fibers and the fabrics
= cellulose
∗ Estimated.
made from them,
7) the ability to make these deformations (e.g.,
Understandably, a vast amount of industrial crimp, creases, and pleats) permanent,
development work and capital was required to 8) the low moisture uptake and, hence, rapid
build such enormous PETP fiber production. drying,
Sample figures are available for the early years 9) the fact that most soil remains on the surface
of the PETP fiber, Terylene [38]. Large capi- where it is easily removed with water or sol-
tal reserves were needed to maintain production vents.
44 Fibers, 4. Synthetic Organic

These properties are largely insensitive to the spunbonds, or monofilaments will continue to
presence of water at moderate temperature. To- be made by condensation. It will, likewise, con-
gether, they are responsible for the dimensional tinue to be melt-spun through spinnerets; the
stability and easy care of textiles made from as-spun material will be drawn in some man-
polyester fibers. ner; and the drawn material will be posttreated
according to end use. Processes, that differ in
Comparison with Other Man-made principle from this scheme have not shown up.
Fibers. Polyester fiber products, especially However, individual efforts are underway in
those from PETP, are used commercially in many locations to further improve the qual-
large amounts in all common fiber forms: sta- ity of intermediate and end products, to make
ple fibers, filament yarns for textile and indus- processes more economical, and to adapt the
trial applications, spunbonded products, and products to the frequently changing and some-
monofilaments. The plethora of products and times even entirely new needs of downstream
broad spectrum of applications are not nearly processors and end users [94].
the rule for other major synthetic fibers, e.g., For example, attempts are underway to im-
nylon 6 and 66 polyamides or polyacrylonitrile. prove polymer uniformity from plant to plant
Both nylon 6 and nylon 66 filament yarns are and over long periods of time by careful process
used worldwide, especially in textured yarns and control, e.g., via automation and self-regulation.
as tire cord, as are nylon spunbonds and monofil- Equipment changes and variations in the catalyst
aments. The same is true for staple fibers in car- system as well as in the temperature – vacuum
pets. However, polyamide fibers are not easy to program should improve the economics of poly-
heat-set, which limits their application in apparel mer production. The key to this is increasingly
mainly to woven and knit goods. combining continuous polycondensation with
With polyacrylonitrile, the product with the spinning, i.e., direct spinning. This combination
highest volume is staple fiber. They are used in of process steps, not only here but in the entire
apparel, especially in knitting, and in home fur- production of polyester products, will do much
nishings in weaving, as well as in carpets. The to improve the quality and manufacturing cost
strong dependence of mechanical properties on of the end product. Finally, various polymer ad-
the presence of moisture at elevated temperature ditives will impart novel properties to the end
(poor dimensional stability) makes these fibers products.
unattractive for woven fabrics in apparel. Fil- The uniformity and purity of staple fibers are
ament yarns and fibers for industrial uses are being improved by changes in plants, e.g., in
still specialty products. To some extent, how- the manner of quenching during spinning and in
ever, they are very successful, for example, as as- the machinery of the draw line. This work will
bestos replacement in fiber-reinforced concrete. also improve the economics of the entire pro-
Polyacrylonitrile monofilaments or spunbonds cess. Additionally, staple fibers and tows must be
are not produced because of the problems pre- adapted to the constantly evolving processes and
sented by solution spinning (coagulation and plants of downstream processors. These adap-
residual solvent). tations involve mainly crimp and finish. The
Polypropylene, like polyester, is available in changing market, which often differs from coun-
all types of fiber and nonwoven forms. How- try to country, requires manufacturers to alter the
ever, the relatively low temperature resistance balance of properties of their products accord-
and lightfastness, as well as shortcomings in di- ingly. This will necessitate variations in machine
mensional stability under permanent load, limit settings and in the equipment of the draw lines.
the use of this polymer to special areas of ap- A distant goal of staple fiber process develop-
parel, home furnishings, and industrial applica- ment is to spin at high speed and to draw and
tions. Dyeability problems are forcing the use of posttreat in one step.
spin dyeing in the apparel and home furnishings Purity and especially uniformity of dyeing
sectors. also head the list of quality requirements for
filament yarns for apparel and home furnish-
Future Process Development. Polyester ings. They are being improved constantly by
fiber polymer for staple fibers, filament yarns, careful process control and automation. Pro-
 Fibers, 4. Synthetic Organic 45

ductivity should be increased by even higher binders will be replaced more and more by ther-
spinning speeds, although considerable physical mal bonding. The use of polyester carpet fibers
fiber problems and equipment problems remain is expected to broaden constantly because of the
to be solved. Work is underway in several loca- development of new fiber types and carpet con-
tions. structions.
With filament yarns for industrial use, the Development work will focus on new types
question is to adapt strength and shrinkage be- of filament yarns for apparel and home furnish-
havior permanently to the requirements of each ings, particularly further improvement in aes-
downstream processor and end user, and to ex- thetics and wear comfort. In silklike textiles, the
plore additional end uses. This work involves trend to ever finer yarns and individual filaments,
the polymer as well as the plants and processing combined with variation in filament cross sec-
conditions. It entails improving the economics tion, will continue. In heavier fabrics, however,
of polymer production, spinning, and process- filament yarns with the character of staple yarns
ing of as-spun yarn. will continue to find new markets.
In spunbonded products, uniformity of textile High-tenacity polyester filament yarns for in-
properties and uniformity of thickness are im- dustrial end uses with optimum all-around bal-
portant. They can be improved by careful moni- ance of properties and relatively low cost will
toring and automation of the process. Construc- continue to be available between standard tex-
tional work on spinning, drawing, and laydown tile yarns and special high-modulus fibers for
equipment should result in both better and lower constantly growing, as well as new, areas of ap-
cost nonwovens. The greatest effort, however, is plication.
to open even broader and different end use areas Spunbonded products based on polyester will
to spunbonds by varying such web properties as probably be used in the future in composite sys-
filament fineness, web thickness, unit mass, and tems, to an even greater extent than now. Con-
type of bonding. Because spunbonds represent a tributing to this will be further exploration of the
relatively new type of product, this work is likely possibility of widely varying their structure and
to be successful. their properties.
Monofilaments require as much uniformity A considerable expansion of end use areas
as possible with respect to textile properties and for monofilaments, especially into the industrial
thickness in all applications. Work is, therefore, sector, is expected, based on the further replace-
underway continuously to improve the process ment of other fiber and natural products, espe-
by equipment changes and monitoring. Further- cially metals.
more, much work is being done on varying the
textile properties and the monofilament polymer Future Economic Aspects. Figures 10, 11,
to open up new end uses. 12, 13 present estimates of world production of
man-made fibers in 1990. Overall, an increase
Future Applications. Based on the success is expected, which, in absolute terms, is only
of polyester staple fibers as a component of slightly less than that between 1980 and 1985
blends with wool, cotton, and other cellulosic (Fig. 10). The fraction of polyester fibers as a
and man-made fibers, their use especially in percentage of synthetic fibers and of all man-
blends and also in 100 % articles is expected made fibers will continue to grow, but no longer
to increase. This expectation is supported by as rapidly (Fig. 11). Nevertheless, the fraction of
the outstanding wear comfort of clothing made polyester fibers is expected to reach 50 % of all
from these mixtures [121]. Polyester fibers cause synthetic fibers.
moisture given up by the skin to be transported Among the staple fibers, polyester will in-
away, through the clothing to the outside. New crease somewhat more than products of other
types of fibers with voids will reinforce this polymers (Fig. 12), while filament yarns of
transport mechanism in the clothing and fiberfill polyester will remain about even with those of
sector and will permit further improvements in polyamides (Fig. 13).
comfort. New developments, especially in dry- Table 9 shows the average yearly increases in
laid nonwovens, will open up further end uses consumption of all polyester fibers from 1985 to
for polyester fibers. In so doing, consolidation by 1990 and beyond, as a whole and divided into in-
46 Fibers, 4. Synthetic Organic

dividual fiber types. Staple fibers and monofila- sector. They will also be subject to fluctuations
ments are expected to develop like the average of in world economy, especially to those affecting
all polyester fibers, while filament yarns for ap- the cost of polymer intermediates and the price
parel seem to be approaching saturation. In con- of cotton. The effects of unpredictable changes
trast, well above-average increases are expected in consumer preferences and, hence, in fashions
for industrial filament yarns and especially for also contribute to the uncertainties of these esti-
spunbonds. Whereas these two products repre- mates.
sent only 5.4 and 1.7 %, respectively, of the vol- Overall, however, estimates of the average
ume of all polyester fibers, they are, neverthe- yearly growth in consumption of various fiber
less, highly interesting from an economic point types suggest that the producers of polyester
of view. fibers will have to continue to improve the qual-
Table 9. Estimated average annual growth in the consumption of
ity of their existing products and to open up new
polyester fiber and other types of fiber areas of application by developing new products.
Growth, % per year

Fiber 1985 – 1990 1990 – 1993 3. Polyurethane Fibers

Staple fibers and tow 3.2 2.7
Textile filament yarns 2.2 1.5
Following the discovery in 1937 of the diiso-
Industrial filament yarns 4.4 3.4 cyanate addition polymerization process by O.
Spunbonds 8.4 5.3 Bayer and co-workers [122], this principle was
Monofilaments 3.3 2.4
All polyester fibers 3.0 2.4 applied to the production of polyurethane (PUR)
Other synthetic fibers 1.6 0.8 fibers. Hard PUR fibers, first developed to com-
All synthetic fibers 2.3 1.6
Cellulosic fibers 0.2 −3.8
pete with nylon 66, are no longer important. On
All man-made fibers 1.9 0.7 the other hand, the same principle of synthesis
Natural fibers 1.3 1.1 was successfully applied to the manufacture of
All fibers 1.6 0.9
highly elastic yarns [123], [124].
Synthetic high-polymer fibers containing at
For comparison, Table 9 also shows the av- least 85 wt % of segmented polyurethane are
erage yearly growth rates of other fiber groups. called elasthane [125]; the term spandex is used
At least until 1990, the consumption of man- in the United States and in this chapter.
made fibers will increase somewhat more than Spandex fibers are characterized by high
world consumption of all fibers. Cellulosic fibers elongation and elasticity. Like rubber yarns
are initially expected to remain about the same (elastodiene fibers), they belong to the class
and then to decrease markedly, possibly because of elastomeric fibers. Spandex, produced as
of displacement by competing polyester fibers. continuous-filament yarn, is used almost ex-
Synthetic fibers as a whole will grow much more clusively to manufacture elastic textiles and is
than all fibers. Natural fibers cannot grow ap- always employed in combination with other
preciably because little room can be found for fibers. Although spandex has gained consider-
expansion of land under cultivation. The increas- able technical and economic importance, world-
ing worldwide demand for fibers will have to be wide production, which amounted to 23 000 t in
met to a greater extent by synthetic fibers [119]. 1985, is relatively small compared to other tex-
Because the remaining synthetic fibers are tile fibers. Commercial products (see Table 10)
expected to grow no more than all fibers, the have distinctive raw materials bases, chemi-
most significant growth compared to other types cal structures, and manufacturing and spinning
of fibers will be in polyester fibers. The rea- processes, which, in the final analysis, are re-
son for this is their extreme versatility. By vary- sponsible for the specific balance of properties
ing the polymer and the processing conditions, [126][127][128][129][130].
polyester fibers can be adapted to the manifold
requirements of the marketplace.
Understandably, these estimates are uncer- 3.1. Physical Properties
tain. The global growth rates will undoubtedly Spandex is highly extensible by application of
vary from country to country and from sector to an external force. When the load is removed,
 Fibers, 4. Synthetic Organic 47
Table 10. Commercial spandex products as of 1985

Trade name Producer Country Composition∗ Spinning

process

Acelan Tae Kwang Korea polyether/MDI/diamine

Cleerspan (Glospan) Globe Manufacturing United States polyester/TDI/diamine reaction
polyether/MDI/diamine dry
Dorlastan Bayer AG Federal Republic polyester/MDI/diamine dry
of Germany
Elaston Chemitex Poland
Cellviskoza
Espa Toyobo Japan polyether/MDI/diamine dry
Fujibo Fuji Japan polyester/polyether/MDI/diamine wet
Spandex Spinning
Loobell Kanebo Japan polyether/MDI/diol from the melt
Lycra Du Pont United States polyether/MDI/diamine dry
Brazil polyester/MDI/diamine dry
The Netherlands
Canada
Great Britain
Mexico
Argentina
Lynel Fillatice Italy polyester/MDI/diamine reaction
Mobilon Nisshinbo Japan from the
melt
Spinning
Opelon Toyo Products Co. Japan polyether/MDI/diamine dry
Roica Asahi Japan polyether/MDI/diamine dry
Chem. Ind polyester/MDI/diamine
Spandaven Gomelast Venezuela polyether/MDI/diamine wet
Vispan Elastofibre Italy polyesterurethane reaction
Pirelli

∗ TDI, toluene diisocyanate; MDI, 4,4 -methylenebis(phenyl isocyanate).

the material rapidly and completely reverts to its Table 11. Mechanical properties of continuous filament spandex
original state. This is a result of the two-phase yarns
structure of the hard and soft segments. The soft Property Range of values
segments, which are highly mobile at the use
temperature, are coiled in the unloaded state and Fineness 20 – 5000 dtex
Elongation at maximum tensile load
stretched in the loaded state. The restoring force Standard-elongation types 420 – 570 %
results from the increase in entropy during rever- High-elongation types 600 – 800 %
Tenacity
sion to the coiled state (entropy elasticity). The Referred to original fineness 0.45 – 1.2 cN/dtex
crystalline hard segments of symmetrical aro- Referred to fineness at break a 3 – 7 cN/dtex
matic urea groups form a network structure via Cyclic loading to 300 % elongation
Modulus, 150 % b 0.04c – 0.1 d cN/dtex
hydrogen bonds and thus provide form stability Modulus, 300 % b 0.1c – 0.25 d cN/dtex
[131–144]. Residual elongation 10 – 30 %
Characteristic stress – strain curves of a com- a
Fineness at maximum textile elongation.
mercial spandex are shown in Figure 14 b
Referred to original fineness.
c
in a cyclical loading – unloading experiment High-elongation types.
d
(stress – strain cycle). The mechanical properties Standard-elongation types.

of spandex filament yarns for the usual range of

types and finenesses are listed in Table 11 (see
→ Fibers, 1. Survey, Chap. 5.).
48 Fibers, 4. Synthetic Organic

3.3. Raw Materials

Segmented polyurethane, the raw material for
spandex fibers, consists of long-chain dihydroxy
compounds (macrodiols), aromatic diisocyanate
compounds, and short-chain diamino or di-
hydroxy compounds (chain extenders). Because
of their chain mobility, the long-chain diols (soft
segments) are responsible for the extensibility.
The urethane and urea groups, formed by aro-
matic diisocyanates and short-chain diols (hard
segments), function as physical cross-links and
are the source of yarn strength.

Macrodiols. Macrodiols suitable for

the manufacture of spandex have molar
Figure 14. Stress – strain cycle of a 480-dtex spandex yarn masses of 1 – 3 kg/mol and melting points
(Dorlastan type V 400) ∗ < 50 ◦ C. Only polyether and polyester
∗ 1 is first curve; 5 is fifth curve; –
– is elongation; –– is diol are important. The most frequently
recovery. used polyether diols is poly(tetramethy-
Below the glass transition temperature of the lene ether glycol) [25190-06-1], polymer-
soft segments, spandex loses its elasticity. In ized from tetrahydrofuran via ring opening
commercial products, this temperature of 210 – (→ Polyoxyalkylenes, → Polyoxymethylenes).
250 K is far below normal environmental tem- Spandex fibers with polyether soft segments
perature range. Critically important for textile are highly resistant to hydrolysis and alkali,
processors is the behavior at high temperature and have excellent low-temperature properties.
(160 – 170 ◦ C, which is the temperature during They are, however, sensitive to light, atmo-
textile treatment and shaping processes). spheric oxygen, and the chlorinated water of
swimming pools and must be specially pro-
tected from them.
Among the polyester diols used, adipic
3.2. Chemical Properties
acid polyesters have gained great impor-
tance, whereas polycaprolactone diols have not.
Compared to rubber yarns, spandex is substan-
For polyadipates, mixtures of C2 – C6 diols,
tially more stable to chemical influences during
e.g., 1,2-ethanediol – 2,4-butanediol and 1,6-
textile processing and subsequent use. Any pos-
hexanediol – 2,2-dimethyl-1,3-propanediol are
sible damage manifests itself primarily in a loss
used most frequently. Polyester spandex is more
of strength and an onset of yellowing. As ex-
resistant to chlorinated water than polyether
pected, polyether spandex is more affected by
types and is insensitive to oxidative damage. Its
oxidative processes and polyester spandex by
sensitivity to hydrolysis can be reduced by the
hydrolysis. The stability of spandex subjected to
use of diols with a greater number of carbon
various chemical treatments is given in Table 12.
atoms. Polyesters of mixed diols give spandex
Spandex-containing textiles can be cleaned
with a low tendency to crystallize during exten-
chemically without problem. Sensitivity to
sion and with improved elastic properties.
photo oxidative damage is increased by unsat-
Trade names. Polyethers: Terathane (Du Pont),
urated fatty acids and cosmetic oils [146]. Ni-
Polymeg (Quaker Oats), Poly-THF (BASF),
trogen oxides lead to yellowing and, hence, are
PTMG (Mitsubishi).
detrimental to white textiles that contain span-
Polyesters: Niax (Union Carbide,
dex. Compared to rubber yarns, spandex has a
Desmophen (Bayer).
greater affinity for textile dyes.
Diisocyanates. Commercial spandex is al-
most exclusively produced from 4,4 -methy-
 Fibers, 4. Synthetic Organic 49
Table 12. Chemical resistance of spandex

Chemical treatment Polyether spandexa Polyester spandexa Remarks

◦
HCl 10 %, 20 C, 24 h low high
H2 SO4 10 %, 20 ◦ C, 24 h low high
CH3 COOH 10 %, 20 ◦ C, 24 h none none
Cl2 – H2 O 20 mg/L, 20 ◦ C, 24 h high b low some yellowing
NaOH, followed by rinsing, suctioning, rinsing none none
Cleaning in gasoline low low
Xeno-test c , 50 h low low some yellowing
Xeno-test c , 100 h medium low little to moderate
yellowing
a
In the classification used, the following strength loss is to be expected: none, 0 – 5 %; low, 5 – 20 %; medium, 20 – 40 %; high, 40 – 90 %;
total, 90 – 100 %.
b
Can largely be prevented by use of ZnO as spinning additive [145].
c
Light source: Hanau 450 (UV-emitting xenon gas lamp).

lenebis(phenyl isocyanate) [101-68-8] (MDI; methylacetamide and dimethylformamide, can

→ Isocyanates, Organic). Toluene diisocyanate be used.
[26471-62-5] (TDI), which was used in the early
years of spandex production, is rarely employed Stabiliziers and Adjuvants. Because of the
today. Although aliphatic diisocyanates lead to use of aromatic diisocyanates, light tends to
polyurethanes with increased light durability, discolor spandex [153]. Spandex in which
they are of little use because of increased dif- polyethers are used as soft segment is, in addi-
ficulties in processing the spinning solutions. tion, attacked photooxidatively. The following
However, 1,6-diisocyanatohexane can be em- are used as stabilizers for these processes: phe-
ployed as a modifier [147]. nolic antioxidants, sterically hindered amines,
light-protective agents (e.g., benzotriazoles),
Chain Extenders. Most spandex producers and phosphites. They must meet special require-
use short-chain aliphatic diamines, such as 1,2- ments such as low thermal volatility and good
diaminoethane or 1,2-diaminopropane, as chain laundering resistance.
extenders because they give fibers with the best Spandex yellows under the influence of ni-
thermal and hydrothermal properties. Hydrazine trogen oxides, which are contained primarily in
hydrate, carbonic acid, dicarboxylic acid dihy- combustion gases. Tertiary amine compounds
drazides, aminocarboxylic acid hydrazides, and have proved to be effective protectors against
semicarbazidocarboxylic acid hydrazides [148], these; in addition, the patent literature describes
[149] were used earlier as chain extenders, but a whole series of protective agents, e.g., carbox-
are no longer of any significance. Occasion- ylic acid hydrazides [154], esters [155], [156],
ally, small amounts of codiamines, such as 1,3- and phosphites [157], [158].
diaminocyclohexane [150] or N-methylbis (3- Polyether spandex, which is sensitive to
aminopropyl)amine [151], are used in combi- chlorinated water, can be protected by tertiary
nation with ethylenediamine. This favorably af- amine compounds; polymers or polyurethanes
fects certain properties, e.g., solubility and stor- with basic groups are used, such as poly(N,N-
age behavior. 1,4-Butanediol, frequently used dialkylamino)ethyl acrylates and methacrylates
in thermoplastic polyurethanes, results in span- [150], [159]. Protective action is also obtained
dex with unsatisfactory properties. 1,4-Bis(2- by inclusion of zinc oxide during spinning [145].
hydroxyethoxy)benzene, on the other hand, pro- The dyeability of mixed articles (fabrics
duces a melt-spun spandex with improved prop- containing a mixture of yarns of polyamide
erties [152]. and spandex) with acid dyes can be im-
proved by adding basic compounds to the
Solvents. Spandex fibers based on
spandex. Alternatively, basic substituents,
polyurethane – polyurea decompose during
e.g., N-alkyldialkanolamines or N-alkyldiami-
melting; therefore, they are spun from solu-
noalkylamines, can be built into the polymer
tion. Only dipolar aprotic solvents, usually di-
50 Fibers, 4. Synthetic Organic

molecule [160]. Previously, spandex was pro- rapid and intense mixing is, therefore, required
duced mainly as delustered yarns. Titanium during chain extension. Reactivity can be re-
dioxide was used as a delusterant, usually in duced by formation of a carbamate from the
concentrations of 2 – 5 %, to obtain as good a diamine and carbon dioxide prior to chain ex-
degree of whiteness as possible. Additional im- tension [164].
provement in whiteness was obtained by adding Both batchwise and continuous processes are
nuancing dyes or pigments. However, nondelus- used during chain extension. Spandex solutions
tered spandex types have gained greater promi- with solids contents of ca. 20 – 35 % and viscosi-
nence because they make possible more bril- ties of ca. 50 – 300 Pa · s (25 ◦ C) are obtained.
liant colors in dyed polyamide – spandex fabrics Molecular mass is controlled during chain exten-
[161]. sion by using monoamines, e.g., diethylamine,
Freshly spun spandex yarn is slightly tacky. as chain terminators. The polyurethane – ureas
After being wound on the bobbin, cohesion bet- produced from diamines are linear polymers
ween yarn layers develops with storage time. and, hence, soluble in the reaction media used.
To counteract this and to improve the un- With trifunctional starting components, cova-
winding and processing behavior, separating lently cross-linked polyurethanes are obtained,
and lubricating agents are used, e.g., polydi- which are simultaneously chain extended and
methylsiloxane and metal soaps [162]. formed into a yarn [149] in the reaction-spinning
process (see Section 3.5).

3.4. Production of Polymer

3.5. Spinning Processes
The fiber raw material is produced by the two-
stage prepolymer – chain extender process, fre- In contrast to elastic yarns based on rubber, span-
quently used in polyurethane chemistry. dex can be spun by using technologies generally
known in the synthetic fiber industry. Because
Production of Isocyanate Prepolymer. In spandex based on polyurethane cannot be pro-
this process step, an α, ω-OH functional poly- cessed thermoplastically, solution-spinning pro-
mer (macrodiol) is reacted with an aromatic cesses are used to produce yarns.
diisocyanate (called a polymer-analogous reac-
tion) to yield an α, ω-NCO functional polymer Solution Spinning. Of the solution-spinning
(macrodiisocyanate). The reaction is carried out processes (dry, wet, and reaction spinning), dry
in the melt or in a highly polar solvent (e.g., di- spinning has become the most important because
methylacetamide) at 50 – 80 ◦ C in a batchwise it lends itself more readily than the others to pro-
or a continuous process. The molecular mass duction of the fine spandex yarns that are in-
of the prepolymer, which subsequently plays an creasingly in demand today.
important role in determining the elastic prop- Dry-Spinning Process (see Fig. 15). The high-
erties of the spandex, can be adjusted via the viscosity elastomer solution is spun through
molecular mass of the macrodiol and the molar multihole spinnerets (d) into heated spinning
ratio of NCO : OH [163]. The prepolymers have cells (e). During the process, the solvent evapo-
number-average molar masses of 4 – 8 kg/mol, rates, is absorbed by the entrained hot spin gases
as well as NCO contents of 2 – 4 wt %, and are (air or inert gas), and is carried away. The solvent
generally processed immediately without inter- is separated by condensation and possibly scrub-
mediate storage. bing of the off-gas, distilled, and recycled. The
individual filaments are cemented with the aid
Chain Extension (Polymerization). In of a false-twisting device (j) to form a multifila-
chain extension, the macrodiisocyanate is re- ment [165], [166]. Finish is applied to the yarn,
acted with a diamine in a highly polar solvent which is wound up at a rate of 200 – 800 m/min.
(e.g., dimethyl acetamide) to give a high molecu- The drawoff speed is greater than the spinning
lar mass polyurethane – polyurea. The most fre- speed (spin draw). The orientation thus produced
quently used short-chain aliphatic diamines re- affects yarn properties. To improve productiv-
act rapidly. To obtain a good polymer structure, ity, several multifilaments are spun from a single
 Fibers, 4. Synthetic Organic 51

spinning cell at the same time. Figure 16 shows than in dry spinning, but equipment and energy
a cross section of a dry-spun spandex yarn. costs are lower.

Figure 17. Schematic of a spandex wet- or reaction-spinning

machine [126]
a) Spinning solution or prepolymer; b) Spinning pump;
c) Filter; d) Precipitating or reaction spin bath; e) Spinneret;
f) Wash or subsequent reaction bath; g) Finish; h) Windup

Reaction-Spinning Process. In this process,

chain extension of the isocyanate prepolymer by
the amine and formation of the yarn occur simul-
taneously in the precipitation bath [167]. During
spinning of the prepolymer into the reaction spin
bath, a solid polymer skin forms immediately on
the yarn surface and provides the stability neces-
Figure 15. Dry-spinning process for spandex filament yarns sary to draw off the yarn. Complete solidification
[149] is achieved in a second step. With this process,
a) Metering pump; b) Spinning solution; c) Hot spinning
air; d) Spinneret; e) Heated spinning cell wall; f) Twisting producing chemically cross-linked spandex by
point; g) Cell length, ca. 4 – 8 m; h) Spinning gas exhaust; using trifunctional starting materials is also pos-
i) Fresh gas; j) False-twisting device; k) Godet roll; l) Finish; sible.
m) Traverse; n) Windup device
Melt-Spinning Process. Only elastic yarns
that are exclusively based on pure polyurethane
can be prepared by the high-productivity melt-
spinning process. These materials do not have
the properties of commercial spandex based on
polyurea – polyurethane and are, therefore, of
little technical significance

3.6. Uses
Figure 16. Dorlastan fiber cross sections, 160 dtex (12 indi-
vidual capillaries) ∗
Production of Elastic Yarns and Fabrics.
∗ ca. 50 µm. Spandex fibers are processed and used exclu-
sively in combination with hard fibers to im-
Wet-Spinning Process (see Fig. 17). In the wet- part high elasticity to textiles. In most cases, the
spinning process, the elastomer solution is spun spandex is used in bare form (i.e., unwrapped).
into aqueous precipitation baths (d). In the pro- Because of its rubberlike hand and poor fric-
cess, the water-insoluble polyurethane coagu- tional properties, spandex intended for certain
lates, and the spinning solvent is carried off by end uses, such as woven elastic clothing fabrics
the water. As in dry spinning, the individual fila- [168], support stockings, and socks, is wrapped
ments are cemented to a multifilament. After the or corespun with hard fibers. Of these elas-
filament has passed through wash baths and dry- tic combination yarns [168], wrapped yarns are
ing cabinets, finish is applied and the filament is the most important. Wrapping can be carried
wound. Windup speeds are significantly lower out with one or two textile yarns. Corespun
52 Fibers, 4. Synthetic Organic

yarns are produced on special secondary spin-

ning machines on which staple fibers are twisted
around the stretched spandex yarn. Corespun
yarns are distinguished by a remarkably soft
hand. To improve the processibility of the com-
bination yarns, they can be changed by a com-
bined stretch – steam process so that they (tem-
porarily) lose their elastic extensibility. After be-
ing processed into fabric, the good elastic prop-
erties are restored by dyeing at the boil in the
relaxed state.
The most important types of processing used
to produce articles containing spandex are listed
in Table 13. As can be seen, both knit (process-
ing on circular or warp knitting machines) and
woven fabrics can be produced. Articles with
the highest extensibility can be prepared by the
circular knitting process [169]. The elastic yarn Figure 18. Curves of cyclic elongation of a tricot fabric
is processed directly from the bobbin, the yarn (longitudinal direction) containing 18.5 % 45-dtex Dorlas-
tan, unit mass 220 g/m2 , longitudinal extensibility 210 % ∗
being taken off over the end of the spool. [126]
To prepare warp knitwear, the elastic yarns ∗ 1 is first curve; 5 is fifth curve; –
– is elongation; –– is
must first be assembled [170]. To do so, up to recovery.
1500 yarns are wound parallel, side by side, un-
By using spandex, the textile industry can
der constant extension onto a warp beam. Here,
fabricate elastic textiles in great variety, having
processing is exclusively in the bare form. By
given shaping and support forces, and also meet-
varying the fineness, the hard fiber yarn, and
ing all requirements with respect to end-use be-
the pattern notation technique, the properties and
havior, comfort, and fashion.
appearance of the articles can be influenced in
many ways with this process and can be adapted
to both functional requirements and the demands
of fashion [171], [172]. 4. Polyolefin Fibers
Processing of elastic yarns in woven fabrics
has increased substantially. End uses are suit- Polyolefin fibers, yarns, and monofilaments are
coat and pants fabrics for articles with increased usually produced by melt spinning. Film yarns
wear comfort. and split yarns, obtained from films by uniaxial
The major end uses for coarser spandex yarns stretching, are also produced in large quantities.
and elastic wrapping yarns are tapes for various Polypropylene (PP) is the predominant raw ma-
textile and engineering applications. In Western terial for fibers and yarns. High-modulus yarns
Europe, 45 % of spandex production is used in of ultrahigh molecular mass high-density poly-
girdle and underwear manufacture, 20 % each ethylene (HDPE), commercialized in the mid
in swim wear and hosiery, and ca. 15 % in other 1980s, are an exception.
areas. Both PP and HDPE are used to make film
yarns and monofilaments; however, HDPE is
Textile Properties of Elastic Fabrics. The used to a much lesser extent. Areas of appli-
most important property of elastic fabrics is the cation for PP fibers include carpet yarns, home
combination of extensibility and elastic recov- furnishing fabrics, industrial fabrics, and non-
ery. Spandex can elongate until the hard fiber wovens. Polyolefin tapes and monofilaments are
construction obstructs further elongation. Ex- used in bags, tarpaulin, industrial fabrics, carpet
tensibilities vary from ca. 25 % (woven fabrics) backing, twine, rope, and bristles.
to > 200 % (knitwear). The elastic behavior of a The production of textile products from poly-
warp-knitted fabric is shown in Figure 18. olefins in 1985 was estimated to be ca. 1.7×106 t,
about 91 % (1.55×106 t) of which was PP and
 Fibers, 4. Synthetic Organic 53
Table 13. End uses of spandex continuous-filament yarns

End use Manufacturing Amount of Yarn type Fineness,

technology spandex, wt % density, dtex

Lingerie and lingerie bands circular knit 5 – 12 bare, wrapped, corespun 22 – 400
warp knit bare, wrapped 22 – 80
Girdles warp knit 10 – 40 bare, wrapped 22 – 800
Swim wear warp knit 10 – 32 bare, 22 – 80
circular knit 6 – 12 bare, wrapped 44 – 160
Hosiery bands, sock borders circular knit 10 – 20 bare, wrapped 135 – 400
Support stockings circular knit 10 – 60 bare, wrapped, corespun 22 – 480
Tapes tape weaving 10 – 50 bare, wrapped 320 – 5000
Outerwear weaving 2 – 10 rubber threads, 44 – 160
wrapped yarns

about 9 % (150 000 t) HDPE. About 30 % of Because its structure contains no polar
all polypropylene produced is processed into groups, PP is resistant to most chemical agents,
tapes, fibers, and monofilaments. In 1985, this in particular to acids and alkalies; insensitive to
amounted to ca. 630 000 t in Western Europe, water; and not dyeable with common types of
47 % of which went into tapes, split fibers, and dyes. Moreover, it has a low resistance to ther-
monofilaments; 32 %, into staple fibers; 13 % mooxidative and photooxidative degradation.
into filament yarns, and 8 % into spunbonds. The The problem of nondyeability has been solved
growth of polypropylene yarns, fibers, and non- by mass dyeing techniques (Section 4.1.2.5) and
wovens should continue to be above the growth the problem of degradation by the use of suitable
of polypropylene consumption in general as well additives (Section 4.1.2.4). Because of the ab-
as that of all other synthetic fibers. sence of polar groups, only van der Waals forces
exist between macromolecules; these forces are
much weaker than the hydrogen bonds found,
4.1. Polypropylene Fiber for example, in polyamide. Because mechani-
cal characteristics depend on these forces and
Polypropylene fiber was developed in Italy by on molecular entanglement, very high molecular
Montecatini during the second half of the 1950s masses (M r from ca. 170 000 to 300 000, com-
[173]. Several other companies initially played pared to ca. 20 000 for polyamide) must be used
an active role in its development, including Her- to obtain satisfactory strength (fiber tenacity).
cules, Reeves Brothers, Vectra, and Phillips in
the United States; ICI in Europe; and Toray, Mit- Rheological Aspects [174]. Polypropylene
subishi Rayon, and Toyobo in Japan. Some of fiber is produced by melt spinning, i.e., by ex-
them, like ICI, disappeared from the scene after truding the molten polymer through suitable
the first few years; others improved their line of spinnerets. Therefore, the rheological behavior
products and became extremely important in the of the polymer melt must be considered in select-
market. There are many producers; in Western ing processing conditions or even in choosing a
Europe they increased in number during the late certain polymer for specific spinning conditions.
1970s, when the Montecatini patents expired. The first aspect to be considered is that isotactic
PP in the molten state is highly non-Newtonian
and exhibits a strong pseudoplastic character;
4.1.1. Chemical and Physical Properties
the apparent viscosity of the melt is not con-
Chemical Structure. Polypropylene is a stant with varying shear stress but it decreases
hydrocarbon made up of −CH2 CH(CH3 )− when shear stress increases. The deviation from
units. These propylene units form a stereoreg- Newtonian behavior is markedly dependent on
ular helix, with the methyl groups at an angu- the relative molecular mass (M r ) and polydis-
lar distance of 120 ◦ (isotactic polypropylene). persity (molecular mass distribution M r D); for
A small percentage (ca. 2.5 – 5 %) is sterically polymers of comparable polydispersity, the melt
random (atactic polypropylene).
54 Fibers, 4. Synthetic Organic

viscosity increases with increasing viscosity – in the finishing step. Normally, the crystallinity
average molecular mass. An extremely useful, of the finished fiber does not exceed 70 %; val-
practical indication of M r is the melt flow index ues of 40 – 50 % are usual. Many physical prop-
(MFI), which is a measure of flow under stan- erties are influenced by crystallinity. Mechani-
dard conditions (ASTM D 1238: grams extruded cal properties, however, are affected less by the
in 10 min through a standard orifice under a pres- percentage of monoclinic material than by the
sure of 2.16 kg/cm2 at 230 ◦ C); MFI is inversely molecular orientation imparted during drawing;
proportional to melt viscosity. The MFI is mea- orientation is evaluated by measurement of bire-
sured at a shear rate close to those commonly fringence.
met in usual spinning processes.
The initial MFI of PP polymers used in fiber Mechanical Properties. Depending on
production ranges from 2 to 35, depending on spinning conditions (extrusion temperature,
the process involved and the type of fiber pro- quenching, spinning speed, and rate of deforma-
duced. In addition to pseudoplasticity, PP melt ton in the molten state), the mechanical prop-
exhibits appreciable signs of viscoelasticity. In erties of as-spun PP fibers can vary widely, as
a viscoelastic material the deformations under- shown schematically in Figure 19. The mechan-
gone by the melt have not only a viscous but ical properties of drawn fibers are influenced
also an elastic component, which can therefore substantially by the applied draw ratio and, con-
be recovered when the applied stress ceases, i.e., sequently, also vary widely (Fig. 20).
when the extruded polymer emerges from the
spinneret capillary. The residual elastic energy,
whose magnitude depends on the residence time
in the capillary, can cause, among other phenom-
ena, enlargement of the extrudate to a diameter
larger than that of the capillary (die swell). The
polymer swelling increases as the shear stress
increases and as the ratio of length to capillary
radius decreases.
Die swell also depends on the molecular mass
distribution (M r D): at comparable melt viscosi-
ties, die swell is larger for a polymer with broad
Mr D than for a polymer with a narrow Mr D.
Swelling increases as temperature decreases. All
these rheological characteristics are taken into Figure 19. Stress – strain curves of as-spun polypropylene
account when spinneret hole geometry, polymer fibers
type (MFI, Mr D), and extrusion conditions are
being selected.

Structural Characteristics [174, pp. 327 –

337], [175]. The stereoregular structure of iso-
tactic PP macromolecules makes an ordered
three-dimensional configuration (i.e., a crys-
talline structure) possible when the molten poly-
mer is cooled to the solid state. Under normal
conditions, isotactic PP crystallizes in the mono-
clinic system; if cooled rapidly to room temper-
ature, it exhibits a paracrystalline form, called
smectic. In practice, PP fiber is a partially crys-
talline material. The crystalline structure of the Figure 20. Stress – strain curves of drawn polypropylene
fiber depends on the conditions of extrusion and fibers
quenching, the take-up speed in the spinning
step, and the draw ratio and annealing conditions
 Fibers, 4. Synthetic Organic 55

The relationship between tenacity and draw rather limited number of holes; (2) short spin-
ratio depends on the polymer used and, in par- ning is based on low spinning speeds and spin-
ticular, its polydispersity. As polydispersity de- nerets with a large number of holes. In the first
creases, the tenacity obtained at a given draw ra- process, because of the high spinning speeds,
tio increases, but the drawability of the spun fiber postspinning operations are performed in a sep-
decreases at the same time. Therefore, polymers arate step; in the second process, because of the
with narrow M r D are not suitable for production low spinning speeds, spinning and postspinning
of high-tenacity fibers; they do, however, have are carried out continuously. Postspinning oper-
advantage in terms of spinning continuity at high ations are basically the same for both processes.
spinning speeds.
Conventional Spinning Process. The poly-
mer, to which stabilizers and pigments have
4.1.2. Production been added, is introduced into the extruder (a)
(Fig. 21). The molten material is fed to the spin-
4.1.2.1. Raw Materials nerets (e) by metering pumps (c), which control
the throughput of each spinneret. The extruder
Polypropylene fibers are obtained from PP ho- is heated electrically, while the melt distribu-
mopolymer. They may also be based on PP and tion manifold is heated by means of a diathermic
a propylene – ethylene random copolymer or a fluid (e.g., Dowtherm and Diphil). Filaments (f)
blend of polypropylene and polyethylene ho- emerging from the spinneret are quenched with
mopolymers. In the latter case, the definition cold air (air speed 1 – 2 m/s) and, when solidi-
“polyolefin fiber” or “olefin fiber” is more cor- fied, collected in cans (i). An antistatic and lu-
rect (see Section 4.2). However, polyolefin is bricating agent is usually applied to the filaments
also frequently used for PP homopolymer fiber. before they come in contact with any solid sur-
Polypropylene is used in the production face (g).
of side-by-side bicomponent polypropylene – The filament fineness depends on the
polyethylene fibers. The Customs Cooperation throughput of the metering pump, the number
Council of the European Economic Community of holes in the spinneret, and the take-up speed,
(EEC) adopted the following definition of textile according to the following relationship:
polypropylene:
1000 Q
Fibers composed of aliphatic saturated hy- d=
3.6 n·v
drocarbon linear macromolecules having in the
chain at least 85 % by weight of units with one where d is the fineness, decitex; Q is the pump
carbon atom in two carrying a methyl side chain throughput, kilograms per hour; n is the num-
in an isotactic position, and without further sub- ber of holes; and v is the take-up speed, me-
stitution. ters per second. The spinning speed of PP fiber
Availability. The availability of raw materials is usually 600 – 1200 m/min, and the tempera-
is not a problem, although the supply of propyl- ture of the molten polymer in the spinneret is
ene may be influenced by the demand for eth- 220 – 300 ◦ C, depending on molecular mass of
ylene because ethylene and propylene are co- the polymer, spinning speed, and desired charac-
products in the cracking of virgin naphtha. Other teristics of the fiber being produced. Spinnerets
sources, of lesser importance at the moment, used for staple production are 150 – 250 mm in
are liquefied refinery gases containing propyl- diameter and have between 200 and 2000 holes,
ene and propane gases. depending on the fineness of the fiber. In some
cases, rectangular spinnerets are used to achieve
higher productivity. The number of holes is lim-
4.1.2.2. Staple Fiber Production Process ited to avoid having the filaments stick together
(filament marriage). Polymers with a fairly low
Polypropylene can be produced by two differ- M r (MFI 5 – 20) are used commonly in the pro-
ent processes: (1) conventional spinning is based duction of standard fibers; higher M r (MFI ca. 2)
on high spinning speeds and spinnerets with a polymers are used only for high-tenacity fibers.
To obtain satisfactory spinning continuity, the
56 Fibers, 4. Synthetic Organic

Figure 21. Conventional spinning plant

a) Extruder; b) Melt distribution; c) Metering pump; d) Spinning pack; e) Spinneret; f) Filament; g) Oiling device; h) Take-up;
i) Can coiler; j) Quench box

polymer must be filtered before reaching the tended to impart bulk and cohesion to the fiber
spinneret; both sand filters and screen filters are for subsequent conversion to final products. The
used. fiber is compressed in the crimper (stuffer box)
and subsequently dried and heat-set in a hot-air
Postspinning Operations. Drawing, crimp- oven (100 – 130 ◦ C) to stabilize crimp and re-
ing, heat setting, cutting, and baling are the steps duce thermal shrinkage after drawing. A finish
that follow spinning in the production process. is usually applied to the fiber during the post-
Several tows coming from the spinning sec- spinning operations. Staple cutting and baling
tion are processed together to reach a total fine- operations are the final stages of production. The
ness of 200 – 300 ktex (0.2 – 0.3 kg/m). They are speed of these operations is limited by the crimp-
stretched between two sets of rolls; the draw ra- ing speed and is generally 150 – 250 m/min.
tio depends on the ratio of the roll speeds of
these two sets. The draw ratio for standard fibers Short Spinning Process. The rheological
is between 1 : 3 and 1 : 5. To obtain uniformly behavior of PP is such that, when spinning
drawn fibers, the tow is heated in a steam cham- speeds are fairly low (
120 m/min), and the
ber located between the two sets of rolls. Alter- stream of quenching air blows through the fil-
natively, heated rolls can be used in the first set. aments close to the spinneret, the filaments do
If high-tenacity fibers are desired, the drawing not stick together even with close hole spac-
operation is sometimes divided into two steps ing (ca. 1 mm). Then, the speed of consecutive
by means of a third set of rolls. Crimping is in- operations can be matched, and a continuous,
 Fibers, 4. Synthetic Organic 57

uninterrupted, one-step process can be achieved. In this case, the yarn is highly twisted, heat-set,
A consequence of the high hole density and the and detwisted in a continuous false-twisting pro-
reduction in height of the quenching section is cess to give each individual filament the shape
that plants can be made more compact for a of a spring. A subsequent heat-setting operation
lower cost. For this reason and reduced man- can be introduced in the detwisting zone to re-
power requirements, the short spinning process duce yarn elasticity. For coarser continuous fila-
has become very popular. ment yarns (carpet yarns), systems based on fluid
bulking jets are used. Consistent with the con-
tinuing trend toward reduced production costs,
machines have been developed in which the dif-
ferent operations are performed continuously in
a single step.

4.1.2.4. Stabilization

Polypropylene, although relatively stable to heat

and light in the absence of oxygen, has poor
resistance to thermooxidative and photooxida-
tive degradation [175, pp. 38 – 93]. Thermoox-
idative degradation occurs during conversion of
the polymer to a fiber. Photooxidative degrada-
tion occurs when the end product, which con-
tains PP fiber, is exposed to direct or diffuse so-
lar radiation in the presence of oxygen. As a
hydrocarbon, PP is transparent to UV light but
it is sensitive to it because of the presence of
traces of oxygen-containing groups, such as hy-
droperoxides and ketones, which absorb at 310 –
330 nm. Depending on the temperature during
exposure, thermooxidative degradation and pho-
tooxidative degradation often occur simultane-
Figure 22. Draw-twisting machine ously. Both processes generate polymer radicals,
a) Spun yarn; b) Pre-tension guide; c) Pre-tension rolls and which catalyze further molecular cleavage.
guides; d) Feed roll; e) Draw roll; f) Twisting take-up
Therefore, suitable antioxidants and light
stabilizers are added to protect the polymer
melt at high temperature and to impart suffi-
4.1.2.3. Continuous Filament Yarn cient aging resistance to the finished products.
Production Process (→ Antioxidants, Chap. 5.4.). These stabilizers
can be classified according to the mechanism by
In principle, spinning continuous filament yarn which they protect the polymer: (1) chain termi-
is similar to spinning staple fiber; the main dif- nators or free-radical scavengers, which termi-
ference is that in the former, each yarn is col- nate the chain reaction by giving rise to non-
lected on an individual bobbin. Drawing of the reactive radicals; (2) hydroperoxide deactiva-
yarn (Fig. 22) is usually performed by two pairs tors, which decompose hydroperoxides without
of rolls (f), which are generally heated elec- formation of radicals; (3) UV absorbers, which
trically. For some applications, continuous fil- screen UV radiation; and (4) quenchers, which
ament is used as it comes from the drawing ma- quench the excited states of ketone groups; and
chine (flat yarn), but in most cases, filament bulk (5) free-radical scavengers that trap the rad-
must be increased by means of a texturing sys- icals and regenerate themselves (HALS: hin-
tem. A mechanical texturing system is preferred dered amine light stabilizers). The following are
for the very fine yarns used in the textile industry. some of the chemicals used at present:
58 Fibers, 4. Synthetic Organic

Chain terminators phenolic antioxidants

is comparable to that experienced in use be-
Peroxide decomposers disulfides, trialkyl phosphites cause the rate of photooxidation is a function
UV absorbers derivatives of hydroxybenzo- of temperature. For indoor uses, such as car-
phenone and benzotriazole
Energy quenchers nickel chelate stabilizers pets and wall coverings, fiber bundles are ex-
Free-radical scavengers hindered amines [176] posed in a Xenotest or Weatherometer accord-
ing to ASTM G 26 – 84, DIN 54 004, ISO B 02.
The resistance to artificial light is expressed as
Some producers of stabilizers are: residual tenacity after exposure. Fiber exposed
Ciba-Geigy B. F. Goodrich Co.
to combined heat and light, e.g., on rear window
Borg Warner Chemicals Enichem shelves in cars, is tested in the Xenotest at high
Uniroyal Ethyl Co. temperature.
Gas-Fading Resistance. The fiber specimen is
The effectiveness of the stabilizer formula- exposed to nitrogen oxide containing gases de-
tion depends on the choice of individual com- rived from the combustion of butane. Color vari-
ponents. This choice must also take into ac- ation is assessed by comparing the exposed and
count the pigments used because they can af- original samples after four exposure cycles of
fect heat and light stability significantly and can controlled duration.
even interfere with stabilizers. In addition, atten-
tion must be paid to possible concomitant phe-
4.1.2.5. Pigmentation
nomena, such as gas fading, which is the color
change caused by nitrogen oxides present in air. Polypropylene cannot be dyed by conventional
These oxides can react with some components methods because it lacks polar groups that can
of the stabilizing system, resulting in nitration provide suitable sites for dyes. The techniques
of aromatic rings or addition of nitrogen oxides proposed thus far for making PP dyeable by tra-
to double bonds. Nitrogen oxides can also react ditional acid or disperse dye systems do not have
with certain finishes and cause color changes via near- or medium-term commercial potential, ei-
some of the reactions mentioned previously. ther because of the relatively high cost of addi-
The stabilizer formulation also includes tives involved or because of the as yet insuffi-
antacids, typically calcium stearate, which re- cient colorfastness. Only nickel-modified fibers
act with the HCl formed by reaction of catalyst are used commercially for space dyeing or print-
residue with substances containing active hydro- ing.
gen. Stabilizer systems that comply with interna- For these reasons, PP fiber is colored by
tional regulations for chemicals in food contact blending the polymer with suitable pigments
applications are also available. prior to extrusion; this system is known as “melt
dyeing” or “mass dyeing.” Because of various
Stabilizer Evaluation. The following test requirements, such as thermal stability at high
methods have been developed to select the most temperature, the range of pigments that can be
suitable stabilizers and predict actual fiber be- used is limited; however, mass-dyed PP fibers
havior. are characterized by high colorfastness to light,
Oxidation Resistance. Fiber bundles, hung on a heat, rubbing, and washing. Colorfastness may,
rotating frame under a small weight, are exposed of course, be affected by stabilizer – pigment in-
in a forced-draft oven at 110 ◦ C. Resistance teraction or by additives that facilitate extraction
to oven aging is expressed as days to failure. of the pigments. The main classes of pigments
For operating conditions, see ASTM D 3045-74 used are the following:
(reapproved 1979).
Light Resistance. Accelerated tests with instru- Inorganic: titanium dioxide (rutile or anatase)
iron oxides
ments based on a xenon lamp are preferred to Organic: insoluble azo pigments
those using a carbon-arc apparatus because the copper phthalocyanines
xenon lamp gives a spectrum similar to that of vat pigments
carbazole dioxyazine
summer sunlight, whereas the carbon-arc ap- carbon black
paratus is too high in UV radiation. Exposure
conditions are selected so that the temperature
 Fibers, 4. Synthetic Organic 59

Some pigment producers are: Static buildup in carpets

Resistance to mildew, microorganisms, and in-
BASF Bayer
Sandoz Farbwerke Hoechst sects
Ciba-Geigy Cabot Thermal bondability
Colorfastness of suitably pigmented fibers
Light resistance of suitably stabilized fibers
Fair
4.1.3. Uses Flammability
Frictional characteristics
Types of Fibers Produced. Polypropylene Oil-based soil removal
fiber is produced in a wide range of finenesses, Poor
both as staple and continuous filament. Staple Dyeability with common dyeing methods (need
fibers range from ca. 1 to 250 dtex per filament. for pigmentation)
The fiber cross section is primarily circular; the Heat and light resistance (need for stabilization)
fineness range of continuous-filament yarn is Resistance to dry-cleaning solvents
70 – 12 000 dtex. The filament cross section is Behavior during ironing
predominantly circular in the low to medium Some properties are inherent in the compo-
fineness for apparel, upholstery, and industrial nent material; others are imparted or enhanced
uses, and triangular or trilobal for the fibers used by the production process or by suitable addi-
in floor covering. For the latter application, the tives. A brief survey of the major properties fol-
basic fineness range is 1300 – 4000 dtex; higher lows, with an indication of their effect on fiber
fineness up to 12 000 dtex is obtained by comin- application.
gling. Relative density (0.91) is the lowest of all
commercial textile fibers; this is an advantage in
Commercial Mass. The International Bu- all applications because it means lightness and
reau for the Standardization of Man-Made high cover (especially in nonwoven construc-
Fibers (BISFA) has agreed on the following tion).
definition of commercial mass: “the commer- Chemical resistance, especially to acid and
cial mass shall be obtained by adding to the alkali, is outstanding. Polypropylene fiber was
oven-dry mass, i.e., after removal of finish, etc., treated at 20 ◦ C with the following chemicals;
the mass corresponding to the conventional al- the residual tenacity after 96 h is given (in per-
lowance” where “the conventional allowance for cent):
polypropylene staple fiber, sliver or top and tow
Nitric acid (66 %) 80 – 87
is 2.0 %.” Sulfuric acid (95 %) 95 – 100
Formic acid (75 %) 100
Properties and Applications. Polypropyl- Sodium hydroxide (40 %) 100
Concentrated aqueous ammonia 95 – 100
ene fiber has physical, chemical, and mechan- Trichloroethylene 80
ical properties that make it suitable for a wide Perchloroethylene 80
Xylene 80
range of applications. These properties can be Toluene 90
divided into the following groups: Benzene 90
Acetone 100
Good Sodium hypochlorite (5 % active 85
chlorine)
Relative density Hydrogen peroxide (12 parts) 90
Resistance to acid and alkali
Abrasion resistance
Moisture absorption Hot halogenated solvents swell PP fiber, with
Mechanical properties under dry and wet con- subsequent shrinkage on drying (trichloroethyl-
ditons ene), or even dissolve it (boiling perchloroethyl-
Dimensional stability ene). Moreover, some boiling aromatic solvents
Stain and soil removal dissolve the fiber (e.g., xylene, decahydronaph-
Easy washing thalene), and strong oxidizing agents attack it. In
Quick drying the last case, however, the fiber can be improved
60 Fibers, 4. Synthetic Organic

considerably by suitable stabilizer formulations. cause the limiting oxygen index of PP is 18.5.
The high chemical resistance is exploited in in- The self-ignition temperature is 570 ◦ C.
dustrial filtration. Frictional Characteristics. The coefficient
Abrasion resistance is comparable to of friction of PP fiber, both fiber-to-fiber and
polyamide. It increases with increasing crys- fiber-to-metal, is fairly high. Suitable lubricants
tallinity and molecular mass and is influenced are applied to keep it low so as to allow con-
by frictional properties. The high abrasion resis- version by textile processing. Cotton spinning
tance is exploited in floor covering, upholstery, is one of the most critical processes.
hosiery, and industrial applications. Electrical Properties. Polypropylene is a
Moisture regain is virtually nil (0.05 % at good insulator and exhibits an extremely low
65 % R.H. and 21 ◦ C). The insensitivity of PP power loss, even at high frequencies. The dielec-
fiber to water brings about the following ad- tric constant is 2.1 at 60 Hz and 2.2 at 1 MHz; the
vantages: dimensional stability, fabric dryness in power loss factor is 0.0002 at 60 Hz and 0.0003
contact with the skin, quick drying, and no vari- at 1 MHz; volume resistivity is 4.9×1014 Ω cm.
ation in mechanical properties under wet condi- Thermal Properties. The thermal conductiv-
tions. ity of PP fiber is the lowest among commercial
Temperature Behavior. Polypropylene fiber fibers (0.138 W m−1 K−1 ). This contributes to
does not distort when exposed to temperatures of high thermal insulation in textiles, although the
120 – 130 ◦ C during conversion processes; how- major contribution comes from air trapped in the
ever, it is sensitive to pressure at elevated temper- structure.
ature, so ironing can cause the fabric to stiffen. Allergic Phenomena and Nontoxicity.
The softening point is 150 ◦ C, and melting oc- Polypropylene itself does not cause skin irri-
curs at 168 ◦ C. The relatively low melting point tation or sensitization and is not toxic; surface
is exploited in thermal bonding, which has be- finishes must be selected correctly to retain these
come important in hygienic and medical appli- advantages.
cations (calender bonding is generally used, but
flow-through bonding with hot air can also be Applications. The three major fields of ap-
applied). High-temperature tentering treatment plication are in industrial, home textile, and ap-
is used to produce dense nonwovens suitable as parel end uses.
coating substrates. Industrial applications include rope, twine,
Dyeability. Because PP fiber is not dyeable conveyor belts, industrial sewing thread, filter
by common dyeing methods, pigmentation is cloth, paper reinforcement, geotextiles, coating
used. Although a nickel-modified fiber is avail- substrates, and carpet backing. Diaper facing is
able for printing or space dyeing with chelatable an example of a hygienic – medical product in
dyes, its use is limited. The absence of polar which PP has made rapid inroads.
groups in the PP molecule makes for easy stain Home textile applications include floor cov-
removal; on the other hand, PP is more easily ering (tufted, woven, and needle punched), up-
soiled by oil-based stains than other synthetic holstery fabric, wall covering, fiberfill, blankets,
fibers. warp yarns in woven carpets, and yarns for sec-
Resistance to Mildew, Microorganisms, and ondary backing for tufted carpets. Floor cover-
Insects. Polypropylene fiber is neither attacked ings constitute the most important outlet for PP
by mildew and molds nor damaged by insects. fiber, in both bulked continuous filament (BCF)
Static Buildup. Limited charges are sepa- and staple.
rated when a person walks on a PP carpet and, The apparel uses of PP are limited by lack
consequently, a low body voltage is generated, of dyeability, difficulty in ironing, and inability
lower than that at which uncomfortable shocks to be dry-cleaned. However, the fiber is estab-
can be felt. lished in knitwear, especially sportswear. Sta-
Flammability. Application of a flame causes ple and textured continuous filament yarns are
PP to shrink, melt, and burn if contact with the used. Other applications include fleece fabrics,
flame is sufficiently prolonged. Polypropylene hosiery, and hand knitting yarns.
burns slowly and drips like a candle. Burning
can continue even if the flame is withdrawn be-
 Fibers, 4. Synthetic Organic 61

4.1.4. Economic Aspects vestment costs and reduced labor requirements.

Another significant factor is the solution of prob-
Cost. Although the price of PP in fiber pro- lems regarding stabilization as well as the avail-
duction may be influenced by the demand for ability of economical and effective pigmentation
polymer in other areas of application, the price is methods. Pigmentation has eliminated the basic
generally lower than that of other fiber-forming drawback of the fiber, i.e., its nondyeability.
polymers because of the shorter “chemical path”
from virgin naphtha from which they are all de-
rived. Another positive aspect is the improve- 4.2. Polyolefin Film Yarns and Split
ment of bulk polymerization processes based on
Yarns
high-yield catalysts, which reduce production
costs considerably.
The production of polyolefin film yarns and split
Production. In 1985, world production of yarns is a relatively recent route to the manufac-
PP fiber was about 650 000 t [177], 250 000 t ture of textile products, compared to custom-
of which were produced in Western Eu- ary spinning processes that have been in use
rope (180 000 t of staple fiber and 70 000 t of for a long time. Basically, the process involves
continuous-filament yarn). Some producers and production of a primary film, which is subse-
trade names are listed in Table 14 [178], [179]. quently cut, stretched, and possibly fibrillated
mechanically. This method had been developed
Table 14. Trade names of polypropylene fibers and patented by the end of the 1930s [180] but
Country Producer Trade name ∗
was not exploited industrially on a broader basis
until the 1960s.
Austria Chemie Linz Asota (ST, Y) In principle, other thermoplastics can also be
former Czechoslovakia Chemosvit Prolen (Y)
Denmark Danaklon Danaklon (ST) produced by this means. However, it is impor-
Danaklon ES (ST) tant only for polypropylene and for high-density
Federal Republic of Faserwerke Bottrop Vegon (ST)
Germany
polyethylene (HDPE) (→ Polyolefins).
Steen Polysteen (ST) The usual size of individual PP film ribbons
Italy Filatura di Delebio Delebion (Y) is between 300 and 2500 dtex; split yarns often
Moplefan Meraklon (ST)
Meraklon CF (Y) have sizes up to 10 000 dtex. The smallest size
Meraklon BCF (Y) attainable by special processes is ca. 10 dtex.
Japan Chisso Chisso Polypro
Chisso ES (ST, Y)
The literature on PP film yarns and split yarns
Daiwabo Daiwabo Polypro has been reviewed [181–185].
(ST)
Mitsubishi Rayon Pylen (Y)
United Kingdom F. Drake Gymlene (ST)
Plasticizers Charisma, Duron 4.2.1. Raw Materials
(ST, Y)
United States Amoco Marquesa Lana,
Propex III (ST, Y) The choice of raw materials depends not only on
Hercules Herculon what is required of the finished product but also
Herculon Nouvelle
(ST, Y) on the processing properties. Basically, raw ma-
Phillips Marvess (ST, Y) terials with higher molecular masses (lower melt
∗ ST = staple fiber; Y = continuous filament yarn.
flow indices) are used to produce film yarns and
monofilaments than to produce melt-spun mul-
tifilaments. The choice between PP and HDPE
The amount of fiber produced is not com-
is governed by the following properties:
mensurate with other synthetic fibers, such as
polyester, polyamide, and acrylic fibers, but 1) Polypropylene has higher strength, i.e.,
is, nevertheless, significant and continues to greater tenacity, than HDPE (see Figure 23)
increase steadily. The reason for this steady, [186], [187]. In addition, PP exhibits less
though not explosive, increase is not only the “cold flow”; i.e., products of PP have
interesting performance of the product but also lower elongation under continuous mechan-
the favorable cost of the raw material and the ical loading than those of HDPE.
development of production systems with low in-
62 Fibers, 4. Synthetic Organic

2) Tapes and monofilaments of HDPE are more 4 g/10 min, are common. If the process involves
flexible than those of PP and give finished cooling via a water bath, PP types with low water
products with a softer hand. pickup (carry over) are required.
3) Polypropylene can withstand a higher ther- Coloration is achieved by pigment com-
mal load because of its higher melting tem- pounds; to minimize splitting and assist in weav-
perature (∼=160 ◦ C vs. ∼=130 ◦ C for HDPE). ing PP ribbons, inorganic fillers (e.g., chalk) are
4) On the other hand, HDPE has better resis- used.
tance to cold. Although stretching substan- In special cases, copolymers (i.e., blends with
tially improves the resistance of PP to cold, other polymers) or coextrudates can be used to
HDPE is at present preferred for applications achieve certain properties. Coextruded films per-
below freezing temperature because it offers mit the production of crimped tapes and yarns
a greater margin of safety. [188][189][190].
5) Tapes and monofilaments of HDPE have
lower coefficients of sliding friction than
those of PP. Consequently, they are better 4.2.2. Production of Tapes and Split Yarns
suited for processes in which good sliding
ability is needed (for example, processing on The stretching process in which the film strips
knitting machines). are drawn to many times their original length
6) The tendency of HDPE tapes to split is much (in most cases, six to ten times) is the central
lower than that of PP. Depending on end use, processing step. It leads to high molecular ori-
this can be an advantage or a disadvantage. entation in the longitudinal direction and to sub-
7) The UV stability of HDPE is inherently bet- stantial increase in strength with simultaneous
ter than that of PP. Nevertheless, very good decrease in break elongation. However, strength
weathering resistance has now been achieved in the transverse direction clearly decreases. At
with PP tapes and monofilaments by using high draw ratios, this effect can cause the tape to
high-efficiency UV stabilizers of the hin- “split,” i.e., to fibrillate even at low mechanical
dered amine light stabilizer (HALS) type. stress. This phenomenon, which is more pro-
nounced for PP than for HDPE tapes, is un-
desirable in some cases, e.g., for bagging and
packaging fabrics. In other cases, it is exploited
and reinforced intentionally (e.g., by profiling
the ribbons or by using fibrillators) to arrive at
products with lower fineness and more textile-
like properties (split yarns and fibers).
Figure 24 is a generalized scheme for the pro-
duction of film ribbons and split yarns. The pro-
cessing steps follow.

Figure 23. Tenacity (——) and break elongation (– – – –) of Production of Film. In general, extruders
film yarn of polypropylene (PP) and high-density polyeth-
ylene (HDPE) as a function of draw ratio [186]
(a) with screw diameters of 90 or 120 mm and
screw lengths ≥ 25 times the diameter are used.
The HDPE types used have densities between Screws with a compression ratio of ca. 1 : 3,
0.945 and 0.960 g/cm3 and melt flow index val- with a shear and mixing section, have proved
ues (MFI 190/2.16, i.e., MFI measured at 190 ◦ C useful. Cooled groove boxes in the feed section
under a load of 2.16 kg/cm2 ) between 0.3 and lead to more uniform granulate feed and higher
0.7 g/10 min; a broad molecular mass distribu- throughput. In this case, flat cut screws with
tion is preferable. combined high-efficiency mixing and shearing
Polypropylene tapes are produced almost ex- sections can be used. The type of film produc-
clusively from homopolymers. Depending on tion as well as the conditions of cooling and ex-
the process employed and end uses envisioned, trusion affect processing and properties of the
melt flow indices (MFI 230/2.16) between 1.5 end product [186], [191], [192]. Tapes of HDPE
and 6 g/10 min, and preferably between 2.5 and are usually produced from tubular films (b1 ), and
 Fibers, 4. Synthetic Organic 63

Figure 24. Production of film yarns and split fibers

a) Extruder; b1 ) Tubular film (air cooled); b2 ) Cast film (water quenched); b3 ) Cast film (chill roll quenched); c) Knife beam;
d) First godet stand; e) Stretching oven; f) Second godet stand; g) Setting oven; h) Third godet stand; i) Fibrillator (optional,
only used for split fiber production); j) Windup; k) Twister; l) Staple cutter

PP tapes preferably from cast films. The cast film cantilevered feed rolls. The stretching unit is
can be cooled in a water bath (b2 ) at 15 – 40 ◦ C. made up of two sets of godets (d) and (f) usually
This type of cooling is particularly effective be- consisting of seven godets each. The second set
cause it permits high operating speed, leads to runs at a higher speed than the first; the draw ratio
the formation of small crystallites, and is ad- is determined by the difference in speeds. Draw
vantageous with respect to stretching behavior ratios from 1 : 6 to 1 : 8 are used to produce tape
and strength of the tapes obtained. Raw materi- for weaving and warp knitting; for rope, cable,
als with low water carry over must be chosen, and twine, draw ratios are ca. 1 : 9 to 1 : 10.
and wiping, suctioning, and squeezing devices Operating speeds are ≤ 300 m/min.
must be provided so that no water is entrained Stretching in the short gap between rolls oc-
in the stretching section or the edge strip return. curs mainly through reduction in thickness with-
Film production by the chill roll process (b3 ) out appreciable loss in width. This leads to
is used only when exceptionally close thickness some orientation in the transverse direction and,
tolerance and high tape uniformity are required. hence, a reduction in splitting tendency. Stretch-
Throughput is normally lower in tubular film ing is generally carried out in hot air ovens (e)
installations than in cast film units because of or on heated plates.
lower cooling intensity; in addition, larger vari- The overall stretching process is exothermic.
ations in film thickness are to be expected. However, heat must be supplied to initiate it and
to assure uniformity at the high speeds required.
Cutting. Normally the film is cut prior to The required temperature depends on the raw
stretching. This is accomplished with blades ar- material, the operating speed, and the desired
ranged at the desired distance on a knife beam tape properties; for the most part, it is between
(c). In principle, it is also possible to stretch 130 and 180 ◦ C. Whereas the temperature of the
the whole film and cut it only after stretching tape itself cannot be measured, the uniformity
and setting. The high splitting tendency of PP of stretching conditions can be checked by mea-
makes it difficult to obtain a cut completely free suring yarn tension [195].
of nicks, so only HDPE is processed this way
[193], [194]. Setting. After stretching, setting (g), i.e.,
controlled shrinkage, is accomplished between
Stretching. Stretching is accomplished by the second and third godet stand by again sup-
guiding the film strips over mechanically driven plying heat (in a hot-air oven or with the aid
64 Fibers, 4. Synthetic Organic

of heated rolls). In this annealing process, the the speed of rotation of the roll, various fibrillar
orientation stresses introduced during stretching structures can be obtained [196–200].
are relieved. In so doing, subsequent undesired Strongly fibrillated tape yarn can also be ob-
and uncontrolled shrinkage is reduced or pre- tained without needle roll from profiled primary
vented. film. Profiling is produced either by a comblike
The setting temperature is either equal to the jet lip (Barfilex process [201]) during extrusion
stretching temperature or 10 – 20 ◦ C below it. A or by roll embossing [202], [203]. In both cases,
higher setting temperature leads to less shrink- the impressed longitudinal grooves act as preset
age but adversely affects tape strength. Setting break points, which tear at the high draw ratios
shrinkage results from the difference in dra- used (ca. 1 : 10). However, these processes are of
woff speeds between the second and third godet minor practical importance compared to needle
stand. For most applications, adjusting the set- roll fibrillation.
ting shrinkage to ca. 5 % is sufficient. For end Split fibers are obtained by cutting the fib-
uses in which particularly high dimensional sta- rillated tapes in staple cutters (l). This process,
bility is required (e.g., carpet backing), a higher however, is used rarely because of the develop-
setting shrinkage (10 – 15 %) must be selected. ment of short spinning technology to produce PP
spun fibers of appropriate deniers at a reasonable
Splitting and Fibrillating. Polypropylene cost.
tape has a relatively high tendency to split, and End use for fibrillated tapes (split yarns) in-
the propensity for fibrillation increases with in- clude twine, rope, reinforcement and weft yarn
creasing degree of stretching. The spontaneous in woven carpets, and coarse yarn for geotex-
splitting tendency is occasionally exploited in tiles.
the production of twine and packaging yarns.
The tapes split even during twisting (k) and Coloration and Finishing. Tapes and split
give a fibrous, textilelike end product. The split- yarns are almost exclusively bulk-dyed with the
ting tendency can be reinforced by adding other aid of pigment concentrates, which are added
polymers [196]. prior to extrusion. The problem of coloring poly-
olefins by bath dyeing has not yet been solved
satisfactorily.
Inorganic compounds such as chalk are added
to reduce splitting and facilitate weaving. Ultra-
violet stabilizers, required for many areas, are of-
ten provided by the manufacturer of the raw ma-
terial, but the processor can also blend in concen-
trates. In general, UV stabilizers of the HALS
type are used. They also impart good weathering
resistance to PP ribbons [204]. However, HALS
stabilizers may interact with certain pigments.
Antistatic agents and incorporated lubricants
are generally not effective for ribbons and
Figure 25. Networklike fibrillated yarn of propylene monofilaments. In addition, they can cause prob-
lems during film and ribbon production (e.g.,
Fibrillated yarns or fibers with still lower plate out and water carry over). Subsequent ex-
individual fineness and greater softness are ternal application (finishing) gives better results.
obtained by special fibrillation processes.
Stretched film strips are generally guided over a
needle roll revolving at controlled speed (i); the 4.2.3. Uses
direction of rotation of the roll coincides with
the running direction of the tapes. The tapes Tapes and split yarns of polyolefins are used in
are split into a networklike multiplicity of fib- textile products that require high strength; low
rils (Fig. 25). Depending on the number, fine- weight; chemical, moisture, and abrasion resis-
ness, and arrangement of the needles, as well as tance; as well as other properties. Because of
 Fibers, 4. Synthetic Organic 65

the ease of processing and the low volume cost The raw material is almost exclusively
compared to other fiber raw materials, their use HDPE, frequently via the split-knitting process
is especially economical in many cases. [193], [194]. Polypropylene tapes are difficult
To a large extent, PP and HDPE tapes have re- to fabricate on knitting machines because of
placed jute, hemp, sisal, and other natural fibers. poor sliding properties and tendency to split and
Film yarns and split yarns (tenacities commonly break.
4 – 6 cN/dtex) are used particularly in the manu-
facture of bags, flexible bulk containers and Twine, String, and Rope. Twine and string
other packaging fabrics and knits; industrial fab- for packaging are obtained from highly
ric (e.g., tarpaulin, geotextiles, filter fabrics); stretched, spontaneously splitting, or fibrillated
carpet backing; netting (protection against hail, tapes of PP, by twisting and plying. For high-
birds, solar radiation, etc.); awnings; camouflage strength ropes and cables, fibrillated ribbons, PP
shields; twine; rope and cable. monofilaments, and long staple fibers are used
[208].
Packaging and Industrial Fabrics. Wide
width fabrics are usually produced on flat looms Floor Covering. Split fibers can, like other
[205]. Circular looms are useful for bagging, fibers, be processed into needle felts, which are
because in addition to simpler preparation for used as floor or wall coverings. The use of split
weaving (no beaming; weaving directly from the fibers in these areas has, however, decreased
reel), elimination of the sideseam gives better considerably and given way to spun fibers.
bag strength and saves labor as well as material
[206].
By subsequent extrusion coating, mostly with 4.3. Monofilaments
LDPE or PP, water- and dustproof fabrics are ob-
tained. In addition, the coating prevents ribbon 4.3.1. Production
slippage and loosening of the fabric.
Monofilaments of PP or HDPE usually have a
Carpet Backing. Because of the relatively round or elliptical cross section, with a diameter
high thermal stress during carpet manufacture of 0.1 – 3 mm (mostly 0.1 – 0.5 mm).
(dispersion coating and drying), only PP rib- The steps in monofilament production are,
bon can be used. The major application is as for the most part, identical to those in tape
primary backing in the manufacture of tufted manufacture. Monofilament machines consist
carpets; to a lesser extent, PP is used as sec- of extruder, spinning unit (spinning head with
ondary backing and as binding warp yarns in spinning pump and spinneret), cooling bath,
conventional woven carpets. The splitting be- roll stretching units (usually two sets of seven
havior must be precisely controlled, especially rolls and one set of three rolls), hot-air ovens
in primary backings, and shrinkage must be low or a hot-water bath (for HDPE), and windups
(<1 % at 132 ◦ C, 20 s, European Association [184], [209]. Raw materials are generally pro-
for Textile Polyolefins method) [192]. Too little pylene homopolymers with melt flow indices
splitting leads to deflection of the tufting nee- between ca. 2 and 6 g/10 min (MFI 230/2.16).
dles and, hence, defects in the carpet as well as If improved abrasion and rubbing resistance as
breakage of individual tapes. Too much splitting well as better cold toughness are required, pro-
also affects fabric strength adversely. Tenter set- pylene copolymers are also used. Among the
ting, previously used to minimize shrinkage of HDPE types, those with densities of 0.950 –
the entire fabric, is employed only occasionally. 0.960 g/cm3 , MFI 190/2.16 values between 0.4
and 1.0 g/10 min, and narrow molecular mass
Knit Goods. Cloth for bagging or for shade, distribution have been found to perform best.
camouflage, and hail protection can be made
on warp knitting machines as well as on looms Extruder – Spinneret. Extruders with a
[193], [207]. In most cases, netlike, coarse-stitch screw diameter of 45 – 90 mm are used for the
products, e.g., bags and pouches for fruit, veg- production of monofilaments. Spinneret holes
etables, and other crops, are made. are arranged in concentric circles on the plate.
66 Fibers, 4. Synthetic Organic

Depending on the size of the unit and the diam- same machines used for film ribbons and split
eter of the monofilaments, ca. 50 – 100 monofil- yarns.
aments are extruded through one spinneret. In Areas of application include fishing nets
general, the spinneret hole diameter for poly- (HDPE); nets for protection from hail, birds,
olefins is three to four times the final diameter. etc.; packaging nets; sieves and filter fabrics;
rope and cable; bristles; reinforcing grids for
Cooling Bath. Monofilaments are produced construction sheeting; and tarpaulin.
exclusively with water bath cooling; the water Bristles for sweepers, road brooms, and the
temperature is 20 – 60 ◦ C, depending on work- like are sometimes mechanically split at the
ing material and thickness of the monofilaments. ends. Because sufficient weathering resistance
can be obtained with little or no UV stabilizer,
Stretching. Stretching of PP monofilaments HDPE is often used for protective netting.
occurs in hot-air ovens between two stretching
units with seven rolls each. The usual draw ratio
is 1 : 8 to 1 : 12, and the temperature is 120 – 4.4. High-Modulus Polyolefin Yarns
160 ◦ C. Because of their lower softening range,
HDPE monofilaments can be stretched in water Conventional processes for producing poly-
baths at, or slightly below, 100 ◦ C. Compared to olefin tapes, monofilaments, and fibers give a
stretching in hot-air ovens, this method has the structure that consists of more or less oriented
advantage of better and more uniform heat trans- crystals as well as amorphous regions. Consid-
fer. Stretch ratios are generally between 1 : 8 and erably higher values of the modulus of elasticity
1 : 11. and tensile strength are to be expected if chain
folding can be avoided, and as many molecular
Setting. As in tape production, setting occurs chains as possible can be oriented in the direc-
in hot air after stretching. It is also done under tion in which the load is applied. This ideal case
tension, which is controlled by suitable adjust- can be approximated most closely with HDPE.
ment of drawoff roll speed. Setting temperature Based on its relatively high packing density in
is in the range of stretching temperature; setting the crystal lattice, HDPE should give the high-
shrinkage is usually adjusted to 4 – 8 %. est theoretical stiffness and strength value [210].
On the other hand, HDPE can be relatively easily
Windup. in contrast to film yarns (which prepared with very high molecular mass, so the
are wound on packages with traverse laydown), number of chain ends and defects in the crystal
monofilaments are usually wound in parallel can be minimized. The theoretically attainable
on flanged disk spools. Windup speed is ca. stiffness and strength values of polypropylene
100 – 180 m/min. Monofilaments for bristles are are lower because of its helical structure. How-
wound on large-diameter reels or wheels to ever, PP is also of interest because of its higher
avoid too high a curvature. heat resistance.
The necessary “ultrahigh” orientation of the
Coloration and Finish. Coloring and fin- molecular chains can be achieved essentially
ishing are similar to the process steps for tapes. in two ways with high molecular mass poly-
However, addition of mineral fillers to reduce olefins: (1) drawing in the solid state (at a tem-
splitting is not required for monofilaments. To perature clearly below the melting range) [211–
avoid fibrillation of the outer layers, surface fin- 214], and (2) spinning of highly viscous solu-
ishes are applied (e.g., during twisting) to im- tions (gel spinning) and subsequent one- or two-
prove lubricity. stage drawing [215], [216].
Higher modulus and strength are attainable
by drawing in solution than by drawing in the
4.3.2. Uses solid state because products with higher molec-
ular mass can be used, and a higher degree of
Monofilaments of PP and HDPE are processed orientation can be achieved.
into fabrics, knit goods, rope, and cable on the
 Fibers, 4. Synthetic Organic 67

4.4.1. Production 5. Polyacrylonitrile Fibers

Two technologies are available; both are still in “Polyacrylonitrile fibers” is a collective name
the process of commercialization. Drawing in for all fibers that contain at least 85 % polymer-
the solid state is accomplished in draw jets at ized acrylonitrile [107-13-1]. These fibers are
ca. 100 ◦ C [217]. At draw ratios up to 1 : 30, also referred to as “acrylic fibers.” Most poly-
moduli of ca. 50 GPa are attained for HDPE and acrylonitrile [25014-41-9] (PAC) fibers consist
ca. 20 GPa for PP. This process is being com- of ternary copolymers with 89 – 95 % acryloni-
mercialized by the British Petroleum (BP) and trile, 4 – 10 % of a non-ionogenic comonomer,
Celanese companies. and 0.5 – 1 % of an iogenic comonomer
In gel spinning (Fig. 26), a highly viscous so- containing a sulfo (−SO3 H) or sulfonate
lution in Decalin, paraffin oil, or paraffin wax (−OSO3 H) group. Fibers of 100 % acryloni-
is first prepared in a kneading or stirring unit trile are also produced for industrial use [220].
[218]. It is then extruded through a spinneret Because polyacrylonitrile decomposes before
(c) into a prepicitating bath (d). After entering melting, it cannot be spun from the melt but only
the precipitating and cooling bath, the filaments from solution.
are in a gel state in which the molecules remain
largely disentangled. For orientation in the fiber History. In the early 1930s, H. Rein at I.G.
direction and subsequent crystallization with fi- Farbenindustrie carried out experiments to pro-
nal removal of solvent, a single- or multiple- duce fibers from polyacrylonitrile. Because of its
step drawing process follows (e). Drawing oc- insolubility in organic solvents, its nonmelting
curs under heat and with a stretch factor ≥30. properties, and its high softening point, advanta-
Preferably, HDPE with a molecular mass of ca. geous fiber properties were expected. Patents for
2×106 is used (UHMMPE). The yarns can sub- the use of dimethylformamide (DMF) as a sol-
sequently be cross-linked using radiation. vent for acrylonitrile polymerization were filed
in Germany in 1942 by I.G. Farben and in the
United States in 1944 by Du Pont. It was the
4.4.2. Properties and Uses first industrially useful solvent for the produc-
tion of polyacrylonitrile fibers. Soon thereafter,
By gel spinning, HDPE yarns with moduli dimethylacetamide (DMA) was also found to be
of elasticity of 50 – 100 GPa, and tenacities of a solvent. Technology for dissolving the polymer
≤ 35 cN/dtex can be produced [219]. Because in aqueous ions of certain organic salts was also
of their low density (0.97 g/cm3 ), these yarns developed. The first acrylic fiber was commer-
have an extremely high specific strength and are cialized by Du Pont in 1948. In the Federal Re-
very abrasion, light, chemical, and moisture re- public of Germany, production of acrylic fibers
sistant. In addition, they exhibit high energy ab- began in 1954 [221].
sorption and knot strength as well as good resis- The composition of the copolymer (cf. Sec-
tance to cold. Limitations in use include a rel- tion 5.3.1) determines the dyeing behavior of the
atively high tendency to creep and a relatively fibers. The non-ionogenic comonomer serves as
low melting temperature (ca. 150 ◦ C). Radiation an internal plasticizer and increases the rate of
cross-linking increases heat resistance and re- dye uptake. The sulfonate group of the ionogenic
duces the tendency to creep. comonomer makes possible chemically bond-
End-use possibilities are extremely high- ing ionogenic dyes, whose color-imparting ion
strength rope and cable, fabric for sails, indus- is a cation (basic dyes). The amount of iogenic
trial filters, bulletproof vests, and reinforcing comonomer determines the saturation value, i.e.,
layers for composites. the maximum amount of dye that can be chem-
Trade names: Deyneema (DSM – Toyobo, The ically bonded by the fibers. Acidic ionogenic
Netherlands – Japan); Spectra (Allied, United comonomers are replaced by basic comonomers
States); Tekmilon (Mitsui, Japan) if use of acid dyes is desirable.
Basic-dyeable acrylic fibers are the major
type of fiber consumed; those made of 100 %
68 Fibers, 4. Synthetic Organic

Figure 26. Gel-spinning process for the production of high-modulus UHMM HDPE ∗ yarns
a) Extruder; b) Spinning pump; c) Spinneret; d) Precipitating bath – extraction; e) Heating – drawing; f) Windup
∗ Ultrahigh molecular mass high-density polyethylene.

acrylonitrile and those dyeable with acid dyes possible light, airy textiles with good recovery,
lag far behind. warmth retention, and covering power. Because
The term “modacrylic” designates all fibers acrylic fibers do not swell, articles made from
that contain 50 – 85 % of bound polyacryloni- them remain permeable to air even when wet.
trile. Fibers with 40 – 60 % copolymerized vinyl The tensile strength of acrylic fibers and the
chloride and fibers with 30 – 45 % copolymer- abrasion resistance of articles made from them
ized vinylidene chloride are important because are greater than those of natural fibers.
of their flame-retardant properties. Commercial fibers have different dye affini-
Polyacrylonitrile fibers are wool-like in na- ties and dye uptake rates. For light shades, dis-
ture. An important step in their development was persion and basic dyes are used; for dark shades,
the improvement in dyeability by modification only basic dyes. Dyeing temperature is gener-
with suitable comonomers. Their wool-like na- ally ca. 100 ◦ C. Dyeings are distinguished by
ture and good dyeability have established a se- brilliance and fastnesses. The degree of luster is
cure place for acrylic fibers in the textile market determined by the type, brilliant or delustered.
along with polyester and polyamide fibers. Articles of acrylic fibers fall into the easy-
World production of acrylic fiber increased care category. They absorb little moisture, can
from 1 449 000 t/a in 1974 to 2 334 000 t/a in be washed at moderate temperature, and dry
1984 and to 2 383 000 t/a in 1992. In 1984, rapidly. They are resistant to many organic sol-
polyacrylonitrile fibers represented 14.9 % of vents, and stains can be removed easily. They do
all synthetic fibers produced and 6.5 % of to- not felt. Weathering and lightfastness are excel-
tal fiber production (synthetics, cotton, and lent and unsurpassed by any natural or synthetic
wool); world production of polyacrylonitrile fiber. This makes the fiber especially suitable for
fibers exceeded wool production (1 672 000 t) by outdoor uses such as awnings. The fiber is not at-
662 000 t [222]. tacked by bacteria, mildew, or insects, and does
not rot.

5.1. Physical Properties

5.2. Chemical Properties [223]
Textile Characterization. Articles of
acrylic fibers have a wool-like hand. Lower Good chemical resistance of the homopolymer
fineness fibers produce a softer hand; higher to hydrolysis permits industrial applications up
fineness make it harsher. The high bulk and to 140 ◦ C in a humid atmosphere, e.g., for fil-
low density (compared to natural fibers) make ter fabrics. The resistance of acrylic fibers to
 Fibers, 4. Synthetic Organic 69

industrial gases, smoke, and soot is very good. about equal amounts of isotactic and syndiotac-
Acrylic fibers are resistant to moderate concen- tic sequences [226].
tration of mineral acids and to oxidizing agents. For commercially useful acrylic fibers or
They are soluble in concentrated sulfuric acid yarns, homo- or copolymers of acrylonitrile are
and concentrated nitric acid. Resistance to weak used as raw materials. The raw materials for
alkali is sufficient. Acrylic fibers are insoluble acrylic fibers in textile applications are acryloni-
in most organic solvents, e.g., benzene, min- trile terpolymers.
eral oil, carbon tetrachloride, aliphatic hydrocar- The same initiator systems and similar re-
bons, aliphatic alcohols (e.g., ethanol), aliphatic action conditions can be used for the industrial
esters, and aliphatic ketones (e.g., acetone). unipolymerization of acrylonitrile as are used to
In the burn test, the fibers melt, ignite, and produce acrylonitrile copolymers, the raw mate-
burn with a yellow, sooty flame; a dark, hard, and rials for the usual acrylic fibers in textile appli-
brittle residue remains. In contrast, modacrylic cations.
fibers melt in the flame to dark, hard lumps; burn Interest has developed in very high molec-
partially; but extinguish again if the flame is re- ular mass acrylonitrile copolymers that contain
moved. small amounts of comonomers. These materials
For a summary of the properties of acrylic are used to produce high-strength acrylic yarns
and modacrylic fibers, see → Fibers, 1. Survey, [227].
Chap. 5. To obtain the desired properties in acrylic
fibers for textile applications, acrylonitrile ter-
polymers are used as raw materials. These poly-
5.3. Production mers contain 4 – 10 % comonomers, are free
of ionic groups, and are particularly suited
Production of polyacrylonitrile fibers includes for statistical copolymerization with acryloni-
the following processing steps (Fig. 27) [224]: trile. Examples are the methyl esters of acrylic
or methacrylic acid, vinyl acetate, or acry-
1) Polymerization (Section 5.3.1)
lamide. Depending on the need for raw ma-
2) Dissolving (Section 5.3.2)
terials for cationically or anionically dyeable
3) Spinning (Section 5.3.3)
acrylic fibers, an acidic or basic comonomer
4) Aftertreatment (Section 5.3.4)
is used as an additional component (cf. Sec-
tion 5.5). Monomers containing sulfonic acid
groups have proved particularly usefull as acidic
5.3.1. Polymerization or anionic comonomers, e.g., methallyl sulfonic
acid, styrene sulfonic acid, and 2-methyl-2-
The fiber raw materials for acrylic or modacrylic sulfopropylacrylamide, or soluble salts of these
fibers are produced by polymerization or copoly- sulfonic acids, respectively. Examples of basic
merization of acrylonitrile (→ Acrylonitrile). comonomers are dialkyl aminoalkyl methacry-
For further details concerning reactivity and ma- lates or vinylpyridines.
terial constants see [225]. Although the processing technology of the
Polyacrylonitrile can be made by anionic terpolymerization reaction is largely indepen-
or radical polymerization. Although polymer dent of monomer composition, special attention
solutions can be produced in high space – must be given to the structure of the dyeing
time yields by anionic polymerization, radical- comonomer when selecting the initiator or ini-
initiated polymerization or copolymerization of tiator system.
acrylonitrile is generally the method of choice
in the manufacture of raw materials for acrylic Precipitation Polymerization. In the pre-
or modacrylic fibers. Either solution polymer- cipitation polymerization of acrylonitrile in wa-
ization or precipitation polymerization is used. ter to produce acrylic fiber raw materials, use
Like all vinyl monomers, acrylonitrile can is made of the relatively good water solubility
polymerize with the formation of isotactic as of the monomer. To introduce end groups into
well as syndiotactic sequences. The processes the fiber raw material, which can be utilized to
used to produce acrylonitrile polymers give adjust dyeability properties initiator systems are
70 Fibers, 4. Synthetic Organic

Figure 27. Manufacture of acrylic fiber ∗ [224]

a) Polymerization; b1 ) Washing and filtering of polymer; b2 ) Washing of filaments; c) Drying; d) Dissolving; e) Wet-spinning
process; f) Dry-spinning process; g) Filter; h) Spinning bath; i) Spinning shaft; j) Drawing, drying; k) Crimping; l) Steaming;
m) Distillation; n) Water; o) Solvent
∗ Wet spinning – lower left; dry spinning – lower right.

used. The polymerization is initiated with water- of polymer end groups of the fiber raw material
soluble peroxy disulfate redox systems, such as have a major influence not only on the coloring
potassium, ammonium, or sodium peroxydisul- properties but also on the resistance to thermally
fate, combined with water-soluble salts of sulfur induced yellowing and the degree of whiteness
(IV) or derivatives of sulfur (II). Especially use- of the resulting acrylic fibers.
ful in the production of raw materials for cationi- To obtain cationic dyeable acrylic fibers, pre-
cally dyeable acrylic fibers is the initiator system cipitation polymerization is carried out at 40 –
peroxydisulfate – hydrogen sulfite. The decom- 70 ◦ C and at a pH of <6. Peroxydisulfate –
position reaction of this redox system has been hydrogen sulfite is used as initiator of polymer-
thoroughly studied [228]. ization with a severalfold molar excess of hydro-
The relationship between dyeability and the gen sulfite relative to peroxydisulfate. To purify
number of different end groups in the copoly- and demonomerize the polymer completely and
mers is known [229]. The type and concentration
 Fibers, 4. Synthetic Organic 71

gently, a compact polymer granulate, which can polymer and the solvent by growing a compact
be dried after washing and filtering, is produced. polymer granulate; intimate mixing of polymer
In the synthesis of fiber raw materials for and solvent stream, e.g., in screw mixers, tur-
acrylic fibers that are to be dyed with anionic bines, or paddle mixers; and, providing low sol-
dyes, redox systems, e.g., H2 O2 – thioglycerine vent temperature, which initially produces a sus-
[230], that do not result in anionic end groups pension with good distribution of polymer in the
are used. solvent.
A detailed description of redox polymeriza- A two-step process is used for dissolution
tion of acrylonitrile and a comprehensive review in aqueous salt solutions. The polymer is first
of the use of redox systems can be found in hand- suspended in a salt solution that does not dis-
books [231]. The constancy of distribution of solve the polymer; then the salt concentration is
molecular mass, chemical composition, and de- increased to the amount necessary for dissolu-
gree of whiteness is particularly significant to the tion. This process takes place in agitating pans,
final properties of acrylic fibers [220, p. 200]. either batchwise or continuously. The batch-
wise process requires several hours to produce
Solution Polymerization. The copolymeri- dimethylformamide solutions. The dissolving
zation of acrylonitrile in solution results in poly- temperature is between 60 and 100 ◦ C. In the
mer solutions that can be spun without additional continuous process, the holdup time in the agitat-
process steps after the elimination of residual ing pan is shorter (e.g., 5 – 30 min), but the tem-
monomers. The polymerization reaction con- perature of dissolution is correspondingly higher
ditions must be optimized so that monomer (e.g., up to 120 ◦ C) and the intensity of agita-
conversion is almost complete; low molecular tion is greater [233]. The solution can then be
mass fractions that could adversely affect the treated thermally in heat exchangers or exposed
mechanical and thermal properties of the re- to shearing forces in screws or turbines.
sulting acrylic fibers must be avoided as much The concentration of the spinning solutions
as possible. Examples of suitable solvents are is higher for dry spinning than for wet spinning.
dimethylformamide, dimethyl sulfoxide, nitric When dimethylformamide is the solvent, 25 –
acid, and concentrated aqueous solutions of am- 30 % solutions are normally used for dry spin-
monium thiocyanate or zinc chloride. In radical ning and 20 – 25 % solutions for wet spinning.
polymerization, these solvents – but especially Concentration and viscosity of the spinning so-
the polymer solutions – are effective chain-trans- lution are monitored constantly.
fer agents. For that reason, specially selected ini- To keep the spinning solutions free of gel par-
tiator systems and special reactors are used for ticles or other impurities, which is a prerequi-
the large-scale commercial solution polymeriza- site for long spinneret life, they are filtered in
tion of acrylonitrile [232]. filter presses. Heat, amines, oxygen, and ions
The choice of precipitation polymerization of heavy metals (especially iron) damage initial
or solution polymerization often depends on the color (degree of whiteness). Therefore, an inert
prior history of the acrylic fiber producer. Both atmosphere, acid, and reducing and complex-
processes have advantages and disadvantages, ing stabilizers are needed [234], [235]. Additives
and economics – size of installation, type of have also been developed to protect against salt-
spinning process in use and raw material situ- like clouding of the solutions (in dimethylform-
ation – is often the deciding factor. amide) because of the polymerization catalyst
[236], [237].
Stable viscosity is desirable so that spinning
5.3.2. Dissolving remains a steady-state process; it is obtained by
optimizing the temperature of dissolution (ca.
The solvents used in dry and wet spinning are 70 – 100 ◦ C) or by using suitable additives [238],
listed in Table 15. [239].
Gelation occurs at low temperature via sec-
Commercial process. A dough, which is as ondary valence forces and at high temperature
free of clumps as possible in order to avoid long via cross-linking reactions. The higher the vis-
dissolution times, is prepared from the powdery cosity of the solution and the molecular mass of
72 Fibers, 4. Synthetic Organic
Table 15. Distribution of installed capacity by solvents, 1985

the polymer, the greater is the tendency to gel; change of solvent in the yarn for water. Coagu-
more uniform polymers have less tendency to lation conditions determine the strength of the
gel [240]. sheath – core structure of the yarn, as well as
Aqueous zinc chloride solutions and solu- its porosity and cross-sectional shape. Wet-spun
tions in dimethyl sulfoxide and ethylene carbon- yarns are aftertreated immediately without in-
ate also tend to gel. Because partial hydrolysis of termediate storage.
the nitrile groups occurs when nitric acid is used Dry-Jet Process.
as the solvent, these spinning solutions should In a variation of the wet-spinning process,
not be heated above 5 ◦ C. the solution thread line leaving the spinneret is
first passed through air before entering the pre-
cipitating bath. Fibers with higher strength and
5.3.3. Spinning elongation, smoother surface, and greater uni-
formity can be made by this process [241].
The polymer contained in the spinning solution
is shaped into a yarn by either wet or dry spin- Dry Spinning. The only solvent used in
ning. In both processes, the spinning solution dry spinning of polyacrylonitrile fibers is di-
is pressed through small holes in the spinneret, methylformamide having the following proper-
thus giving the polymer its threadlike shape. The ties:
processes differ in the state of aggregation of
the medium that the spinning solution enters on bp (101.2 kPa) 153 ◦ C
Heat of vaporization 571.24 kJ/kg
leaving the spinneret. In wet spinning, a precip- Water <0.3 %
itating bath of water and the solvent is involved; Amines <0.01 % dimethylamine
Iron <0.05 ppm
in dry spinning, hot air or a hot inert gas.

Wet Spinning. The solvents used industri-

The pH of a 20 % aqueous solution at 25 ◦ C
ally for wet spinning are listed in Table 15. Ex-
should be 6.5 – 9.
amples from the patent literature of spinning
The degassed and filtered spinning solution
conditions for various solvents are given in Ta-
is heated to 100 – 150 ◦ C and spun into vertical
ble 16.
spinning shafts through spinnerets (200 – 2000
The 10 – 25 % polymer solutions are deaer-
spinneret holes; hole diameter, 0.1 – 0.5 mm).
ated, filtered, and pumped through the 10 000 –
Several spinning shafts make up a spinning ma-
80 000-hole spinnerets into the precipitating
chine. The walls of the shafts are heated to 150 –
bath, where the solution thread line is coagu-
220 ◦ C; hot air or a hot inert gas (200 – 240 ◦ C),
lated to a highly swollen gel yarn by the ex-
 Fibers, 4. Synthetic Organic 73
Table 16. Solvents and conditions for wet spinning

Solvent a (wt %) Concentration b , wt % Composition c , wt % Temperature,c ◦ C

DMF (100) 17 – 25 DMF (40 – 60)

5 – 25
H2 O (60 – 40)
DMA (100) 20 DMA (40 – 65) 20 – 30
H2 O (60 – 35)
DMSO (100) 20 DMSO (50) 10 – 40
H2 O (50)
NaSCN (50) 10 – 15 NaSCN (10 – 15)
0 – 20
H2 O (50) H2 O (90 – 85)
ZnCl2 (54) 10 ZnCl2 (14) 25
NaCl (4) NaCl (1)
H2 O (42) H2 O (85)
HNO3 (70) 10 – 13 HNO3 (30) 3
H2 O (30) H2 O (70)
Ethylene carbonate (90 – 85) 15 – 20 ethylene carbonate 40 – 90
(20 – 40)
H2 O (10 – 15) H2 O (80 – 60)
a
DMF: N,N-dimethylformamide; DMA: N,N-dimethylacetamide; DMSO: dimethyl sulfoxide.
b
Of the spinning solution.
c
Of the precipitation bath.

passes through the shaft in the same direction leached out during aftertreatment and recovered
as the yarn. The oxygen and water content of by distillation.
the spinning gas should be as low as possible to The spinning conditions (temperature of so-
avoid discoloration of the spun yarn and decom- lution, temperature of shaft, temperature and
position of dimethylformamide. Dimethylform- amount of spinning gas, and drawoff speed)
amide evaporates in the spinning shaft and is greatly affect both further processing of the spun
exhausted together with the spinning gas at the yarns (e.g., drawability) and properties of the
bottom of the shaft. The performance of a spin- end product (e.g., strength and elongation).
ning shaft is, in the final analysis, determined by
the geometry of the engineering apparatus and Melt spinning. Mixtures of polyacrylonitrile
by the amount of heat transferred to the spin- and water (ca. 13 – 33 % relative to the poly-
ning threads via the hot gas and radiation from mer), in contrast to anhydrous polyacrylonitrile,
the heated walls of the shaft. Of special signif- can form a molten, single-phase system with-
icance for the quality and performance of the out decomposition of the polymer. Fibers from a
spun material is the air guidance in the immedi- polyacrylonitrile – water mixture were prepared
ate vicinity of the spinneret [242–244]. as early as 1948 and again around 1970 – 1971
Solidified, dried spun yarns are drawn off at [220, p. 260 ff]. The advantage of such a pro-
a rate of 200 – 500 m/min. Spun yarns from the cess could be the absence of solvent and lower
shafts of one spinning machine are collected and costs. However, more than 15 years of research
deposited in a can. (In the manufacture of con- and development have not yet resulted in a com-
tinuous filaments, spinnerets with a maximum of mercial process. Possible reasons for this are the
200 holes are used. In this case, an oily finish is high viscosities of the melts and the difficulty of
applied to the spun material below the spinning preventing the melt from becoming two-phase
shaft, and it is wound up on bobbins.) at any point in the process.
The dimethylformamide that has evaporated
is condensed, distilled, and recycled. The spun 5.3.4. Aftertreatment
material still contains 7 – 30 % DMF, which is
The aftertreatment steps are as follows:
74 Fibers, 4. Synthetic Organic

1) Washing behavior is applied to production of shrinkable

2) Drawing fibers. Fibers already shrunk can be made shrink-
3) Finish application able by a postdrawing treatment.
4) Crimping In addition to water drawing, steam drawing
5) Drying or drawing on feed wheels is also possible.
6) Cutting
7) Steaming Finishing. Finish application occurs in an
8) Packaging immersion bath. Most commonly, active an-
ionic compounds are applied to the fibers from
Cutting is omitted in the production of tow. an aqueous medium. Examples are ethoxylated
During aftertreatment, the spun material ac- fatty acids, salts of ethoxylated sulfonic acids,
quires the necessary physical properties, such as or phosphoric acid esters of long-chain aliphatic
strength, modulus, elongation, shrinkage, crimp, alcohols. Finish application prevents the buildup
and crimp stability. Large-scale aftertreatment of static charges during further processing of the
units are capable of processing tow up to fibers and imparts the proper degree of adhesion
770 ktex (770 g/m) at rates up to 120 m/min in and smoothness to the surface. The finish con-
dry spinning and up to 80 m/min in wet spin- tent of the finished fiber is 0.2 – 0.4 %. It can be
ning. The daily production of a large unit is 110 – determined by extracting with ether or a mixture
120 t; smaller units (30 t/d) are also used [245]. of methanol – benzene, evaporating the solvent,
and weighing.
Washing. Washing removes residual solvent
and salts by leaching with hot water (e.g., 80 ◦ C) Crimping. In general, crimping is carried
in multilayer or drum washing machines. A out in a stuffer box after drying (stuffer box
closed construction is used to protect the envi- crimping). A steaming zone, in which saturated
ronment. The washing machine consists of many steam condenses on the tow, heats the tow and
individual zones. The wash water travels in a di- makes it more formable. Two crimping rolls,
rection opposite to the direction of travel of the kept at constant temperature by circulating cool-
yarn tow. The wash water is distilled or other- ing water, pull tow bands of up to 3×106 dtex
wise processed to recover the solvent. Washing into the crimping chamber, stuff them, and push
usually precedes drawing because of the longer them continuously from the chamber at a pre-
holdup time in the washing baths resulting from determined pressure. In certain crimping units,
the relatively low tow speeds prior to drawing, steam can be introduced into the stuffer box to
which makes the washing process correspond- shrink the tow and increase the crimp stability
ingly more intense. (setting).
The type of crimp is important in processing
Drawing. Drawing imparts the required fibers because of its effect on cohesion and on
strength to the yarn and occurs in two or more the hand of the yarns produced from the fibers.
steps in drawing tanks between drawing units. Crimp is determined by the conditions of crimp-
The preferred drawing medium is water just be- ing (temperature and stuffing box pressure), the
low the boil (e.g., 99 ◦ C). The draw ratio is bet- percentage of comonomer in the polymer, and
ween 1 : 2 and 1 : 10. Wet-spun yarns must be other factors that affect the thermal plasticity or
drawn more (because of the absence of pre- friction, e.g., moisture content or type of finish.
orientation) than dry-spun yarns to attain the
same strength. The rule “the higher the draw, Drying. Screen drum dryers, screen belt dry-
the higher are the strength and modulus and the ers, or calenders are used for drying. Drying tem-
lower is the break elongation” applies to both peratures of 120 – 170 ◦ C are common.
processes. During tensionless drying, i.e., drying loosely
After being drawn, the yarns have a boil-off laid tow bands or cut fibers, the shrinkage built
shrinkage, which, depending on the draw ratio, into the fiber in the drawing process is released
is between 15 and 45 %. Shrinkage increases as and removed. This process can be enhanced by
draw temperature decreases and passes through steaming. When dried under tension, the fibers
a maximum with decreasing draw ratio. This
 Fibers, 4. Synthetic Organic 75

must subsequently be relaxed, usually by steam- processes have eliminated storage following the
ing. Drying reduces the moisture content of the dry-spinning process [246].
fibers to 1 – 2 % and increases their density. Because of the relatively high spinning speed
Although polyacrylonitrile does not crystal- (compared with wet spinning), the tow speed
lize like polyamide or polyester, an improvement after drawing must be 500 – 2000 m/min. A vi-
or increase in regions of near-order by drying or brating trough is used to transport the spun
annealing can, nevertheless, be demonstrated by tow during washing. Drawing is carried out in
X-ray analysis. Because of the consolidating ef- steam; crimping, in an aerodynamic crimper
fect of drying, uniform drying is especially im- with a gaseous medium (at 1.5 – 1.6 MPa and
portant for uniform dyeability of the fibers. 50 – 210 ◦ C). Finish application can occur be-
fore, during, or after crimping. The steaming
Steaming. Steaming generally occurs in process is carried out in a vibrating trough in
screen belt steamers or in autoclaves. Steaming a steamer; drying, in a belt dryer.
with saturated steam shrinks the fibers and in- In this process, products of uniform quality
creases the crimp stability. To ensure that the are obtained; solvent emission and waste are re-
shrinking process is complete, a high and uni- duced; and manufacturing costs are lower [246].
form steam atmosphere (>95 % steam) is re- In one variant of this process, washing is also
quired. eliminated [247].
Steaming increases the elongation of the
fibers and slightly reduces their strength. Steam- Producer Coloring. The manufacture of
ing under pressure is especially effective in in- colored fibers is of economic interest if large
creasing the rate of dye uptake. amounts of one color are to be produced. Fiber
producers can make colored fibers in the follow-
Cutting and Packaging. In the production
ing ways:
of endless tow for processing on stretch – break
machines, the crimped and dried tow bands are 1) Spin dyeing,
packaged in cartons or bales. The mass of such 2) Gel dyeing,
tows ranges from 50 to 110 g/m. The bundle 3) Dyeing of spun material
mass is 100 kg per carton and up to 800 kg per
bale. Spin Dyeing [248]. Dyes, either cationic or
In the production of staple fibers, the crimped pigment dyes, are added to the spinning solu-
and dried tow bands are cut into staple fibers tion prior to spinning.
with slotted wheels or rotary cutters. The usual The dyes are free of adulterants. They are
cut lengths are 40, 60, 80, 100, or 150 mm, de- soluble in the solvent used and should be insol-
pending on end use. Cut fibers are compressed uble in water (the subsequent washing medium).
and packaged into bales of ca. 200 – 300 kg in Dye solutions also contain polymer to adjust
packing presses. their viscosity to that of the spinning solution.
The aftertreatment of filament yarns of poly- In general, combinations of dye solutions are
acrylonitrile involves processes similar to those metered into the polymer solution to achieve a
for tow and fibers: drawing and setting. Equip- given color; they are homogenized by means of
ment is tailored to the particular filament count statically or mechanically operating mixers.
of the product. In addition, the filaments are Ionic bonding of the color-imparting cation
twisted to tighten the yarn and packaged on to the sulfite or sulfate groups of the polyacry-
cones, which are shipped at a mass of 1.5 – lonitrile polymer is rapid and quantitative. Uni-
2.0 kg. Commercial counts of industrial fila- formly dyed tows with brilliant color and good
ments are 220 dtex/96 filaments, 440 dtex/192 textile fastness are obtained by both the dry-
filaments, or 890 dtex/384 filaments. spinning and the wet-spinning processes.
Organic pigments are used when especially
high lightfastness is required, e.g., in textiles
5.3.5. Special Processes used outdoors. The pigments are dispersed in
Continuous Dry Spinning Process. Mod- a dilute solution of polymer. In so doing, sta-
ern continuous dry spinning and aftertreatment bilizers are added to prevent coagulation of the
76 Fibers, 4. Synthetic Organic

dispersed dyes. This is followed by metering into section determines the luster, moisture regain,
the spinning solution as with cationic dyes. and mechanical properties of the fiber [253].
Gel Dyeing. Dyeing during aftertreatment
generally occurs while yarns are in the gel state
after wet spinning. Dyeing is possible because
cationic dyes rapidly diffuse into the highly
swollen yarn. It can occur in the precipitating
bath, the drawing tank, or a separate bath. It must
be carried out prior to drying, which collapses
the structure of the swollen yarn.
Dyeing by both the extraction method and
the padding method has been patented. Impor-
tant variables are temperature, concentration of
dye, and time in the dye bath; these determine the
amount of dye required and the wash- and light-
fastness of the dyed material [249]. The choice
of dyes is also important in the quality of dyeing
[250].
Gel dyeing has the following advantages
[251]:
1) Good dye uniformity within the batch and
from batch to batch
2) Same tow quality as with undyed fibers be-
cause all physical perturbations are avoided
3) Economical batch size (≥5 t) because hardly
any material is wasted during dye change Figure 28. Acrylic fibers, cross sections and surfaces
A) Dry spun, delustered; B) Surface of A; C) Wet spun;
Dyeing of Spun Material. Dry-spun yarns D) Bifilar, dry spun, single component, delustered; E)
Modacrylic, dry spun; F) Modacrylic, wet spun, delustered
can also be dyed during aftertreatment, but the
rate of dye uptake must be increased by suitable
measures [252].
Uses. Fibers dyed in the course of fiber manu- Stress – Strain [220, pp. 73, 208]. The
facture are used in clothing, home furnishings, stress – strain curve of acrylic fibers (Fig. 29) is
and outdoor textiles. Yarns, pigment-colored characterized below their glass transition tem-
during spinning, are recommended for outdoor perature (50 – 95 ◦ C with decreasing moisture
textiles (awnings, sunshades, camping and ter- content) by a steep initial region A, followed
race furniture, camping tents, and boat covers). by zone B, where small changes in stress result
in large changes in elongation. Above the glass
transition temperature, A no longer exists; the
fiber is more extensible, with slowly increasing
5.4. Analysis
resistance until a yield stress σ c , at which struc-
turally determined resistance to plastic sliding
Cross Section (Fig. 28). The cross-sectional
processes are overcome, is attained.
structure of polyacrylonitrile fibers and
modacrylic fibers is determined by the com-
position of the polymer, the spinning process,
and spinning conditions. The shape of the cross
 Fibers, 4. Synthetic Organic 77

low load, conclusions can be drawn concerning

their degree of heat-setting. In Figure 31, brands
1 and 2 were more intensively heat-set during
manufacture than brand 3, in which extension
of the yarns above 110 ◦ C is prevented, princi-
pally by release of shrinkage tension.

Figure 29. Stress – strain diagram of polyacrylonitrile (PAC) Figure 31. Thermomechanical deformation of acrylic fiber
fibers [220] tow of three different brands ∗ [220]
A) Yield points below glass transition temperature – – – – Brand 1; − · − Brand 2; —— Brand 3
T < T e ;B) Yield points above glass transition temperature ∗ Pretension 0.015 cN/dtex; rate of heating 10 ◦ C/min.
T > T e T e = second order transition temperature; σ B and
σ C = points at which small increases in stress result in large
changes in elongation Analytical Procedure. The cross section of
the fiber material provides a good indication
The stress – strain curve is affected by the
that an acrylic fiber is present. Dumbbell-shaped
type and amount of comonomer, the molecular
cross sections indicate a dry-spun acrylic fiber;
mass and molecular mass distribution and the
beanshaped cross sections, a wet spun fiber (cf.
conditions of spinning and aftertreatment. Fig-
Figure 28).
ure 30 shows the effect of the draw ratio.
Type reactions can be used to recognize and
distinguish an acrylic fiber from other synthetic
fibers. Each of these reactions, must be carried
out on a freshly prepared sample; acrylic fibers
should be [223]:
1) soluble in concentrated nitric acid at room
temperature,
2) insoluble in concentrated formic acid at room
temperature, and
3) insoluble in boiling cyclohexanone.
Analysis of polymer composition is carried
out by IR spectroscopy [254]. A first indi-
cation of the composition of the copolymer
is obtained from analysis of the acrylonitrile
Figure 30. Effect of three different draw ratios on elongation content. To determine the brand, the exact
and stress composition of the polymer is required. The
major neutral comonomers are vinyl acetate,
Thermomechanical Analysis [220, pp. 77, methyl methacrylate, and methyl acrylate. Ma-
209]. In thermomechanical analysis (TMA), the jor ionogenic comonomers are styrene sulfonate,
change in length of a fiber under a constant methallyl sulfonate, and itaconate, or in acid-
preload is observed at a constant rate of heat- dyeable types, cyclic or aliphatic amines. In ad-
ing. From the changes in length of fibers under dition, the following are present in flame resis-
78 Fibers, 4. Synthetic Organic

tant types (modacrylic fibers): vinyl bromide, Cut lengths are 28, 40, 50, 60, 100, 120, and
vinyl chloride, and vinylidene chloride [255]. 150 mm.
The number of ionogenic groups can be de- Physical modifications important to the qual-
termined titrimetrically. Acid groups can be de- ity of the goods are also used in classification.
termined potentiometrically in DMF solution The following distinctions are made with respect
with 0.1 M NaOH [256]; basic groups, in ni- to fiber shrinkage:
tromethane with perchloric acid in dioxane so-
N-fiber 0 – 2 % shrinkage
lution [257]. The quantitative determination of S-fiber ca. 20 % shrinkage
sulfur-containing polymer building blocks can HS-fiber ca. 40 % shrinkage
also be accomplished by ignition in an oxygen
flask and determination of the sulfate formed or
by determining the sulfur with X-ray fluores- The type of crimp is another criterion that af-
cence analysis [258]. Indications of the “phys- fects the quality of the goods. Qualitative data
ical history” of an acrylic fiber are obtained by on crimp and crimp stability (low, medium, or
physical methods, e.g., thermomechanical anal- high) serve as characterization parameters.
ysis (previously discussed) or by determining The range of finenesses for tow for stretch-
the degree of relaxation with a solubility test breaking is 1.5 – 17 dtex. Tow can be bright,
[259]. delustered, or spun-dyed.
The percentage of acrylic or modacrylic The number of combinations of various char-
fibers in fiber blends can be determined by selec- acteristics for basic dyeable fibers alone runs
tive dissolution in DMF or DMA [260]. For com- into several hundred. Some inkling of the ex-
prehensive information on analysis, see [220, traordinary diversity of possible applications of
pp. 379 – 423]. the most important synthetic staple fiber can be
obtained by considering that the processor has
available more than 20 different brands with
5.5. Types of Fibers [261] varying properties, that polyacrylonitrile fiber
types can be blended with each other or with
Classification. The multiplicity of acrylic other synthetic or natural fibers to achieve cer-
fibers can be classified by various systems. tain properties, and that the quality of the goods
Chemical composition determines certain prop- is substantially affected by the many possible
erties that are used in classification; fibers can yarn and fabric constructions.
be
Industrial Fibers. Fibers for industrial use
1) basic dyeable, consist mostly of 100 % or almost 100 % acry-
2) dark dyeable, lonitrile. Molecular mass is made as high as pro-
3) acid dyeable, cessibility will permit because the higher the
4) self-crimping, or molecular mass, the higher the strength. The
5) flame retardant. fibers absorb very little moisture and, therefore,
Characteristic descriptions, such as brilliant, do not swell. They are resistant to hydrolysis, es-
delustered, bright, and spun-dyed, are also used. pecially in acid medium, and are heat resistant
Subdivision into spun fiber and tow accounts up to 140 ◦ C.
for various processing possibilities: (1) spun Uses. Fibers are used in filter hoses and fil-
fiber for woolen, cotton, worsted, and open-end ter pockets in dry filtration, e.g., in the separa-
(rotor) spinning processes; and (2) tow for pro- tion of fly ash in coal-fired power stations. An-
cessing on stretch – break machines followed by other end use is in dryer felts in paper machines,
spinning. Classification can be by fineness (de- which absorb water that could not be squeezed
nier) range (in decitex): out of the paper sheets. Fibers of 100 % acry-
lonitrile are also used as asbestos replacement.
1) Finest: 0.4, 0.6, 0.9 For this end use, particularly high modulus and
2) Fine: 1.6, 2.2, 2.6 strength are required [262]. Nonmelting fibers
3) Medium: 3.3, 5.0, 6.7 that are nonflammable in air are obtained by
4) Coarse: 11.0, 15.0, 17.0
 Fibers, 4. Synthetic Organic 79

heat-treating acrylic fibers in an oxidizing atmo- of modacrylic fibers is their reduced flamma-
sphere at 300 ◦ C. These fibers can also replace bility. Whereas polyacrylonitrile fibers melt in
asbestos [263]. Filaments of 100 % polymerized the flame, ignite, and continue to burn after re-
acrylonitrile are good starting materials for high- moval of the flame, modacrylic fibers are self-
strength carbon fibers [264]. extinguishing once the flame is removed. In ad-
dition, they do not exhibit an undesirable drip-
Dyeing Modifications. Dyeability is gener- ping of molten fiber. The burnt residue is solid
ally achieved in polyacrylonitrile fibers by in- and black. In case of fire a disadvantage is
clusion of a neutral, plasticizing comonomer the formation of hydrogen chloride. Fibers con-
(5 – 10 %) and an ionogenic comonomer (e.g., taining vinyl chloride exhibit even less flamma-
methallyl sulfonic, 0.5 – 1.0 %) that has an affin- bility than vinylidene chloride fibers.
ity for dyes. By increasing the amount of Bromine-containing monomers, e.g., vinyl
comonomer with dye affinity to 3 – 4 %, fibers bromide or vinylidene bromide, are also used.
are obtained with a four- to fivefold increase The development of polymerizable phosphorus
in rate of dye uptake. Such fibers can be dyed compounds has become known as well.
at a temperature as low as 85 ◦ C rather than at In addition to acrylonitrile and halogen-con-
the boil. Dye migration is especially good in taining comonomers, modacrylic fibers gen-
such fibers, and the time required to fix dyes erally contain other comonomers that are in-
is markedly reduced. Use of a rapidly absorb- tended to improve the dyeability of the fibers.
ing fiber is based on the differential dyeing ef- These are mostly monomers with acid groups,
fect, which occurs when the fiber is dyed with e.g., sodium styrene sulfonate [2695-37-6] or
a conventional fiber. Special-effect yarns can be sodium methallyl sulfonate [149-44-0]. Neu-
produced from homogeneous or inhomogeneous tral comonomers, e.g., alkyl acrylamides, which
blends of fibers or rovings, e.g., yarns of mixed improve dyeability by loosening fiber struc-
colors, slub yarns, and flake twist yarns. Com- ture, can also be included. The manufacture of
binations of yarns result in twisted yarns with modacrylic fibers in essence follows the same
multicolor effects. process steps as the manufacture of polyacry-
Another dye modification is represented by lonitrile fibers.
acid-dyeable fibers that contain 5 – 15 % of a Because of the type and high percentage of
basic comonomer with affinity for acid dyes. comonomer, modacrylic fibers exhibit higher
Possible comonomers are the vinylpyridines, plasticity, which is expressed as lower sticking
e.g., 2-methyl-5-vinylpyridine [29994-42-1], or temperature or higher shrinkage (for other prop-
even aliphatic amines, e.g., 2-(dimethylami- erties, see → Fibers, 1. Survey, Chap. 5.). At-
no)ethyl methacrylate [2867-47-2]. Yarns of tempts were made to eliminate this disadvantage
acid-dyeable acrylic fibers are processed and by reducing the halogen content of the polymer
dyed together with yarns of basic-dyeable and including additives in the spinning solution
acrylic fibers. Dyeing is carried out in the same that act synergistically to reduce flammability.
dye bath containing both acid and basic dyes. Such additives are antimony trioxide, organic
In this way, interesting color effects can be antimony compounds, or halogen compounds of
achieved such as two-color effects or tone-on- antimony or tin. Halogen compounds can form
tone effects. If an undyed – colored combination the oxide and can be dispersed in the fiber so
is desired, only acid dyes are used, to which a finely that they do not act as delusterants. Even
conventional acrylic yarn is relatively insensi- compounds of metals, e.g., barium titanate, or
tive. phosphorus compounds, e.g., derivatives of the
acids of phosphorus, serve as flame retardants.
Modacrylic Fibers [265]. Modacrylic fibers Modacrylic fibers tend to lose their luster
contain 50 – 80 % bound acrylonitrile. The under hot – wet treatment, even during dyeing.
comonomer that makes up the difference is es- Salts are added to the dye bath or dyeing is done
sentially a halogen-containing monomer. Vinyl at lower temperature to prevent this. However,
chloride [75-01-4] and vinylidene chloride the best route is to reluster the dyed fibers with
[75-35-4] are the most frequently used halogen- dry heat. Luster stability has been improved by
containing comonomers. The main advantage changes in spinning and aftertreatment technol-
80 Fibers, 4. Synthetic Organic

ogy, by specific changes in polymer composi- Fibers with high swellability can be pro-
tion, and by the addition of luster stabilizers. duced by the inclusion of comonomers
Uses. Reduced flammability favors the use of with hydrophilic groups. Examples of such
modacrylic fibers wherever there are fire haz- comonomers are acrylic acid, methacrylic acid,
ards or where the danger in case of fire is par- or 2-(dimethylamino)ethyl methacrylate. The
ticularly severe. This includes such uses as chil- saponification of comonomers on the fiber pro-
dren’s sleepwear; home furnishings, especially duces hydrophilic carboxyl groups. A popu-
drapes; wall coverings in public buildings; and lar route to the production of water-absorbent
automobile upholstery. A large area of applica- fibers is the spinning of mixtures of polyacry-
tion is in pile fabrics, carpets, and imitation furs. lonitrile and other polymers. Addition of cellu-
Modacrylics are also used in wigs. lose acetate favors pore formation. Addition of
Modacrylic fibers are processed by them- hydrophilic polymers, e.g., saponified acryloni-
selves or in blends with other fibers, e.g., acrylic trile, favors water absorption.
fibers, polyester fibers, or poly(vinyl chloride)
fibers. By blending and proper construction of Bicomponent Fibers. The side-by-side type
the finished article, special processing require- of bicomponent fibers in which both compo-
ments, as well as the requirements of flamma- nents are placed eccentrically in the cross sec-
bility tests, can be met. tion and run along the entire length of the fiber,
is commercially important (see Fig. 28D). Dif-
Absorbent Fibers [220]. To produce fibers ferential shrinkage of the components form-
with greater wear comfort, special attention ing the fiber produces three-dimensional crimp
has been paid to developing moisture-absorbent when the shrinkage is released. The differential
fibers. Such fibers must be able to absorb mois- shrinkage of the two components is achieved by
ture from the air and from water, either by virtue a difference in the amount of comonomers. If
of their ability to swell or by means of a sys- the concentration of hydrophilic, usually ionic,
tem of pores in the interior of each fiber. With groups differs in the two components, reversible
acrylic fibers, the formation of a pore system is crimp results. This refers to a crimp that can be
especially significant. removed by washing and regenerated by drying.
The system of pores must be protected by a If the concentration of hydrophilic groups of the
sheath of proper thickness to ensure that the fiber two components is essentially equal, the crimp
can be processed without problem. The sheath is irreversible, i.e., permanent. The shrinkage of
must have a multiplicity of fine channels that the fiber, and hence the crimp, can be released
can conduct water into the porous interior of during fiber manufacture by drying or steaming
the fiber. The properties of such a fiber include or during subsequent processing, e.g., dyeing of
high adsorptivity, no swelling, high threshold the fiber or yarn.
of clammy feel, rapid transport of water, rapid Bicomponent fibers are produced both as
evaporation, and low density [266]. staple fibers and as tow. Knit fabrics of these
The manufacture of absorptive fibers by both yarns are distinguished by good volume, pleas-
dry- and wet-spinning processes has been de- ant, wool-like hand, and good stitch definition.
scribed. In dry spinning, an appropriate precipi- Bicomponent fibers are also used in carpets be-
tant can be added to the spinning solution. This cause of covering power [269], [270]. The mar-
results in the formation of a sheath around the ket for these fibers is primarily in Japan and the
filament and an internal system of pores during United States.
spinning [267]. In wet spinning, highly swollen
yarns with many pores are first formed during Shrinkable Fibers. Shrinkable fibers can be
coagulation in the precipitating bath [268]. By produced from tow by processing on stretch-
skillful tuning of processing conditions, these break machines. In general, the fiber shrinkage
pores can be retained in the final product. Water- produced on these machines is 15 – 24 %. If suit-
soluble substances can also be allowed to diffuse able measures are taken during tow production
into the swollen filaments, which are then dried. and stretch-breaking, fiber shrinkages of 24 –
By subsequent leaching of water-soluble com- 40 % are attainable.
pounds, a system of pores is created.
 Fibers, 4. Synthetic Organic 81

Shrinkable staple fibers are generally offered In the European Economic Community
at two levels of shrinkage: (1) shrinkable fibers (EEC) (Belgium, Federal Republic of Germany,
with ca. 20 % shrinkage and (2) high-shrink France, Italy, Luxembourg, The Netherlands,
fibers with 35 – 40 % shrinkage. The desired and Great Britain), the consumption of acrylic
level of shrinkage can be obtained most easily fibers in 1983 is shown in Table 17.
during the manufacture of shrinkable fibers by Acrylic fibers are used both by themselves
suitable choice of draw ratio and draw temper- and in blends with others fibers. The major end
ature with subsequent mild drying. Care must use of acrylic fibers in clothing is in sweaters;
be taken, however, to produce a shrinkable fiber in home furnishings, they are used in furniture
free of voids so that no electrostatic problems covers and blankets [222].
occur in further processing and no changes in Acrylic fibers represent the largest percent-
coloration or luster occur in the processed fiber. age (33 %) of fibers processed on knitting ma-
Good technical properties are also desirable. chines (Western Europe, 1983), ahead of cotton
Criteria for a void-free structure are negative with 22.8 %. Other areas in which acrylic fibers
birefringence and density >1.180 g/cm3 [271]. represent the leading raw material, ahead of all
Shrinkable fibers are processed in blends with other fibers, are furniture pile fabrics (80.0 %),
nonshrinkable fibers to give high-bulk yarns, knitted and woven furs (79.8 %), and awnings
which are distinguished by their high volume. (85.0 %) [224].
High-shrinkage fibers are also used in imitation The United States used ca. 207 000 t of
furs as bottom hair, in the production of multi- acrylic fibers in 1985. Preferred areas of appli-
step plushes, and in felts. Manufacturing meth- cation were sporting goods (ca. 24 %), sweaters
ods are described in detail in many patents [220]. (ca. 17 %), hosiery (ca. 13 %), and knitting yarns
Important measures are consolidation of the yarn (13 %).
by removal of solvent, drying, and heat treat- World capacity of acrylic fibers is ca.
ment in water or steam, partly prior to drawing 2.8×106 t/a. About one-third of this capacity
and partly between two drawing steps. The rate is in Western Europe (major countries: Federal
of drawing is also important. Republic of Germany, Great Britain, Italy, and
Spain) and another third in Asia (major coun-
tries: Japan, South Korea, Taiwan, and Turkey).
5.6. Economic Aspects Important countries in North America are the
United States and Mexico, and in the Eastern
With 2 334 000 t (Western Europe 784 000 t), Block, the former Soviet Union. The major pro-
acrylic fibers amounted to 19 % of synthetic fiber ducers are shown in Table 18.
(polyester, polyamide, and polyacrylic) produc-
tion in 1984. Acrylic fibers are produced almost
exclusively as staple fiber and tow. Acrylic fibers 6. Poly(vinyl chloride) and
represented exactly one-third of the synthetic Poly(vinylidene chloride) Fibers
staple fibers in 1984 (6 977 000 t) [222].
According to standard ISO terminology,
Table 17. Consumption of acrylic fibers in the EEC (1983) the generic name for poly(vinyl chloride)
Consumption, [9002-86-2] (PVC) and poly(vinylidene chlo-
ride) [9002-85-1] (PVDC) fiber is chlorofiber;
Use t/a % this designates products containing at least 50 %
From yarns vinyl chloride or vinylidene chloride units. In
Fabrics 93 600 22.4 the United States, the Textile Fiber Products
Knit goods 205 000 49.1
Carpets 26 300 6.3 Identification Act defines any fiber containing
Other 43 700 10.5 at least 85 wt % of vinyl chloride units as vinyon
From fibers and any fiber composed of at least 80 wt % of
Fiberfill 1 300 0.3
Nonwovens 5 300 1.2 vinylidene chloride as saran.
Other 42 600 10.2 Compared to acrylic or polyester fibers, the
1987 world production and consumption of
chlorofibers is small, ca. 20 000 t/a.
82 Fibers, 4. Synthetic Organic
Table 18. Major producers of acrylic fibers

Trade Name Producer Country Process

Acrilan Monsanto USA wet

Aksa Acrilik Kimya Sanayii Turkey wet
Beslon Toho Beslon Co. Japan wet
Bulana Kombinat “Dimitar Domov” Bulgaria wet
Cashmilon Asahi Chemical Industries Japan, wet
Argentina,
Ireland,
India
Courtelle Courtaulds Fibres Great Britain, wet
France
Creslan Amer. Cyanamid USA wet
Crilenka Courtaulds Fibers Spain wet
Crysel Celulosa y Derivados Mexico wet
Dolan Hoechst FRG dry (wet)
Dralon Bayer FRG, Peru dry (wet)
Euroacryl Anicfibre Italy wet
Exlan Japan Exlan Co. Japan wet
Fisisa Fibras Sinteticas Mexico wet
Hanilon Hanil Synthetic Fiber Industries South Korea wet
Kanebo Acryl Kanebo Synthetic Fibres Japan wet (dry)
Kanekaron (Modacryl) Kanegafuchi Chemical Industries Co. Japan wet
Leacril Montefibre Spain wet
Societa Italiana Prodotti Acrylic Great Britain,
Italy
Malon Organsko Hemijska Industrija Skopje Former Yugoslavia wet
Melana Uzina de Fibre Sintetice Savinesti Romania wet
Nitron Chemiefaserkombinat; former States of USSR wet
Navoi Polotsk,
Saratow
Orlon Du Pont USA dry
Tairylan Formosa Plastic Taiwan wet
Toraylon Toray Japan wet
Townflower Tong Hwa Synthetic Fiber Taiwan wet
Velicren Snia Fibre Italy wet
Vonnel Mitsubishi Rayon Japan wet
Wolpryla VEB Chemiefaserwerk “Friedrich Engels” GDR wet

In terms of comfort, flame retardancy, chemi- dard polymer used in plastic compounds. Bulk
cal resistance, and shrinkability, these fibers may polymerization at 60 – 70 ◦ C is generally pre-
be considered specialty items, essentially having ferred because contamination from polymeriza-
the properties of the homopolymer, e.g., chem- tion additives is low; this results in an atac-
ical composition, low crystallinity, high dipole tic polymer with a molecular mass of 70 000 –
moment, and low moisture regain. The obstacles 85 000. The melting point of pure homopolymer
to commercial development of these fibers re- is close to the decomposition point. Dry or wet
sult mainly from the low softening point, which spinning from solution is, therefore, the only in-
leads to poor dimensional stability at elevated dustrial route available to produce commercial
temperature and poor downstream processabil- fibers.
ity compared to other synthetic fibers.
Dry Spinning. To avoid thermal decomposi-
tion with dehydrochlorination, the spinning tem-
6.1. Fibers from Pure Poly(vinyl perature must be kept relatively low; therefore,
chloride) Homopolymer the boiling point of the solvent also must be low.
Only a few common solvents are suitable for
6.1.1. Fibers from Pure Atactic the homopolymer. Blends of equal volumes of
Homopolymer carbon disulfide and acetone (bp 38 ◦ C) and ben-
zene and acetone (bp 64.5 ◦ C) were patented and
The poly(vinyl chloride) generally employed for
are presently used in production [272]. The spin-
fiber production is simply a variant of the stan-
 Fibers, 4. Synthetic Organic 83

ning composition consists of polymer, solvent, in water or steam [277]. The residual shrinkage
and additives. Polymer content varies with the is removed by relaxing the fiber tension-free at
molecular mass of the polymer and ranges from the boil or slightly above.
25 to 30 wt %. The additives have definite func- The next steps in the production of standard
tions, e.g., improving heat stability, lightfast- fiber are oiling, drying, crimping, and cutting,
ness, whiteness, and luster [273]. Certain pro- by conventional technology. Some commercial
ducers of homopolymer chlorofiber overcome interest has been shown in high-shrinkage (30 –
the difficulties in conventional dyeing caused by 65 %) chlorofibers with their attendant high
the low shrinkage temperature of the fiber by shrinkage stress. Shrinkable fibers are obtained
adding dye to the spinning dope. by varying the draw ratio and avoiding the an-
Early swelling of the complex polymer grain nealing and relaxation steps.
and high dope viscosity make dope preparation
difficult. The three possible ways to overcome Wet Spinning. At present, one industrial
this problem are (1) flash mixing of polymer plant (Kustanai, former States of USSR)
and solvent with a short residence time in the uses the wet process to produce commer-
shearing system [274], (2) premixing the poly- cial chlorofiber. Suitable common solvents are
mer with a nonsolvent [275], and (3) kneading N,N-dimethylacetamide (DMA) and N,N-di-
under high shearing force with long residence methylformamide (DMF). Special additives are
time. required to limit discoloration of the solution.
When the solution is processed at ambient With these solvents, the rate of coagulation is
temperature, the microcrystalline regions of the high and voids appear in the coagulated gel, per-
polymer are not dissolved and the solution is col- manently impairing fiber performance. To exert
loidal. Dissolution at a temperature >100 ◦ C and positive control over the coagulation rate, water
processing the solution above the boiling point is added to the solvent before the solution is pre-
of the solvent result in a more homogeneous so- pared; the solvent is then heated to improve sol-
lution and a large decrease in viscosity, with con- ubility [278]. High solvent content (up to 85 %)
comitant advantages in further processing [276]. and low temperature (5 – 15 ◦ C) are suitable for
After the dope is dissolved, it is filtered in one the coagulating bath.
or two steps. After the gel has coagulated, it is drawn at a
The solution is heated or cooled to the spin- low draw ratio and then washed on a multiple-
ning temperature and extruded through a 1000- stage countercurrent machine to recover the sol-
to 2000-hole spinneret in a long tube with hot vent as a concentrated aqueous solution. A sec-
air moving concurrently with the filaments. The ond draw of 400 – 600 % is carried out at boil-
emerging filaments are cooled, wetted by an ing or intermediate temperature; the tow is then
aqueous lubricant, and wound up or collected dried under tension. Annealing can be carried
at 300 – 700 m/min. The spinning parameters out during or after drying. The tow is then re-
are important because they determine charac- laxed tension-free, oiled, cut into staple, and
teristics of the as-spun filament, such as cross- baled.
sectional shape and specific surface. In wet processing, obtaining a homogeneous
structure and avoiding discoloration and resid-
Staple Route. After spinning, the tow is pre- ual solvent are inherently difficult. The proper-
heated at a temperature (80 ◦ C) lower than the ties of the fibers are generally inferior to those
glass transition temperature and drawn 400 – produced by the dry process.
800 % at a temperature (85 ◦ C) higher than
the glass transition temperature. The drawing
medium may be hot water or low-pressure 6.1.2. Fibers from Blends of Poly(vinyl
steam. chloride) Homopolymer
After drawing, the fiber is thermally unstable
and has a strong tendency to return to its original To avoid the inherent limitations of homopoly-
length; the shrinkage and shrinkage stress may mer fibers without loss of specific and outstand-
be as great as 70 % and 0.6 cN/dtex, respectively. ing properties, spinning blends of homopolymer
For this reason, the tow is annealed under tension and minor amounts of a polymer with fibrillar
84 Fibers, 4. Synthetic Organic

structure to act as reinforcement has been pro- Comfort. Chlorofibers exhibit high thermal
posed. Postchlorinated PVC (CPVC) or cellu- and tactile comfort [283], [284]:
lose acetate [279] can be used without modifi-
cation of the process. Other blends require spe- high thermal resistance (0.23 – 0.25 m2
◦
cial processes. Dry-spun fibers, which contain C W−1 cm−1 )
ca. 80 – 85 % PVC homopolymer and 15 – 20 % constant thermal resistance with humidity trans-
CPVC, exhibit the structure of a matrix rein- fer
forced with fibrils and have greatly improved water transfer
heat dimensional stability, mechanical proper- high rate of evaporation of perspiration
ties, and creep [280]. Such fibers are produced feeling of warmth
on a commercial scale by Rhône-Poulenc. If no lag time between sweat production and evap-
cellulose acetate or cellulose is used to replace orative heat loss
CPVC, the level of heat stability increases [279], Flame Retardancy. Chlorofibers have a very
[281]. Researchers in the former Soviet Union high level of flame retardancy as shown by the
proposed wet-spinning a blend of homopoly- limiting oxygen index (LOI) of 46 % at 50 ◦ C
mer with 4-phenylbenzimidazoterephthalamide and 49 % at 150 ◦ C. They do not ignite and
in dimethylacetamide [282]. In all these cases, spread flame, nor do they melt and form droplets
the PVC homopolymer is the matrix. in contrast to many other synthetic fibers. They
A Japanese firm (Kohjin Co.) produces a may be blended with other flammable, staple
fiber (Cordelan) in which PVC and PVC – PVA fibers, such as wool and polyester, and retain
[poly(vinyl alcohol)] graft-polymer particles are their flame retardancy over a specific range of
dispersed in a PVA matrix. This fiber gains heat blend ratios. They can also be blended with ther-
dimensional stability, with concomitant reduc- mally resistant fibers, such as aramid and pre-
tion in chemical resistance, thermal insulation, oxidized acrylic fiber, and exhibit outstanding
and flame retardancy. heat resistance in terms of ignition temperature
(640 – 680 ◦ C) and ignition flux (6.4 W/cm2 ).
Chemical Resistance. Homopolymer fibers
6.1.3. Products, Properties, and Uses withstand weathering and are resistant to most
chemicals with the exception of polar or-
Products. Three major grades of products ganic compounds (chlorinated hydrocarbons,
are available: (1) shrinkable products with dif- aromatic hydrocarbons, ketones, and a few oth-
ferent levels of shrinkage, (2) stabilized products ers).
for tow dyeing for apparel, and (3) highly sta- Surface processing. Woven or nonwoven
bilized products for piece dyeing and home fur- fabrics of chlorofibers may be processed by ther-
nishings (matrix-fibrils). Table 19 lists the physi- mal molding. Under the combined action of tem-
cal characteristics of these grades. The stabilized perature and pressure, any shape can be achieved
grades are available in a wide range of fineness with a woven or knitted fabric composed of chlo-
from 2.4 to 15 dtex and of cut lengths required rofibers. These fibers may be heated and welded
for cotton, woolen, or worsted spinning systems. by high-frequency heating because of their low
Chlorofiber can be spun on cotton, woolen, or dielectric loss factor (0.013 at 50 Hz).
worsted systems as 100 % highly stabilized fiber Trade Name, Producer (Plant Location):
or as blends of shrinkable and stabilized fibers. Retractyl-Fivravyl, Thermovyl L9, and ZC,
The fibers may be dyed at the boiling tempera- Rhovyl (Tronville-en-barrois, France); Tevi-
ture or slightly below by use of selected disperse ron, Teijin (Iwakuni, Japan); (Kustanai, former
dyes. Only highly stabilized fibers can be yarn- States of USSR); (Canton, Chunking, Foochow,
or piece-dyed. Shanghai, Sengli, and Tientsin, all People’s Re-
public of China).
Properties and Related End Uses. The
main end uses for chlorofibers are related to
comfort, flame retardancy, chemical resistance,
and surface processing.
 Fibers, 4. Synthetic Organic 85
Table 19. Physical properties of stabilized grades of PVC products

Property Shrinkable fibers Stabilized fibers Highly stabilized fibers

3
Density, g/cm 1.4 1.38 1.38
Break strength, cN/dtex 2.5 – 3.0 1.6 – 2.2 2.1 – 2.5
Break elongation, % 15 – 20 85 – 105 45 – 55
Initial modulus, cN/dtex 30 – 40 10 – 11 12.5 – 13.5
Shrinkage in air, %
at 100 ◦ C 40 – 55 0.2 0
at 110 ◦ C 45 – 65 15 – 25 5 – 10
at 115 ◦ C 50 – 70 25 – 30 10 – 15
Temperature of maximum 80 – 100 135 – 140 135 – 140
shrinkage stress, ◦ C
Shrinkage stress, cN/dtex 0.04 – 0.06 0.02 – 0.03 0.015 – 0.02
Moisture regain 0.05 – 0.1 0.05 – 0.1 0.05 – 0.1
(at 65 % R.H., 25 ◦ C), %

6.2. Fibers from Postchlorinated The properties of the filament are as follows:
Poly(vinyl chloride) (CPVC) Linear mass 3.6 – 4.2 – 5.6 dtex
Break strength >1.6 cN/dtex
Poly(vinyl chloride) homopolymer (56.7 % Break elongation >40 %
chlorine) can be postchlorinated to a 73.2 % Density 1.44 g/cm3
Shrinkage in boiling water 72 %
maximum chlorine content by free-radical chlo- Limiting oxygen index 51.5 %
rination. Solubility in common solvents, espe-
cially in acetone or blends containing acetone,
depends on the chlorine content of different Fibers of CPVC have properties similar to
molecular chains and the distribution of blocks homofibers, with slightly higher shrinkage and
of poly(vinyl chloride) and 1,2-dichloroethane flame retardancy and lower chemical resistance
in each chain. and ease of dehydrochlorination [285].
The solution process is believed to be the Some attempts have been made to im-
most suitable method of obtaining concentrated prove certain limiting characteristics: (1) graft-
spinning solutions, with maximum solubility at ing methyl methacrylate to increase moisture re-
a chlorine content of 63 %. Soviet (Chlorin) and gain, (2) grafting acrylonitrile to improve ther-
German Democratic Republic (Piviacid) fiber mal stability, and (3) blending CPVC with cel-
producers claim a solution process using either lulose acetate at a ratio of 85 : 15 to increase the
tetrachloroethane or dichlorobenzene as solvent. shrinkage temperature [278].
The processing steps include solution prepara-
tion, chlorination, precipitation of polymer with
nonsolvent, polymer washing, and solvent re- 6.3. Fibers from Vinyl Chloride
covery [278]. Copolymers
The quality specifications of spinnable poly-
mer are: Copolymers of PVC with a 13 – 15 % vinyl ac-
Chlorine content 63 – 65 wt % etate content and a vicosity index of 57 – 58 ex-
Specific viscosity at 0.2 %
in cyclohexane 0.2
hibit a lower glass transition temperature (73 ◦ C)
Degree of polymerization 900 – 1000 than homopolymers, and the bondability im-
Ash content 0.03 – 0.08 wt % proves at temperatures lower than the melting
Iron content 1×10−3 wt %
point.
The process used is dry spinning. A solu-
tion of copolymer (≤50 wt %) in acetone, con-
Filament or staple fiber based on CPVC is
taining heat stabilizers and additives, is prepared
spun by the dry or wet process in acetone. In
at ambient temperature, filtered, and extruded at
wet spinning, the coagulation bath consists of
a temperature dependent on the polymer content
water and a small amount of acetone; the spun
(50 – 80 ◦ C). A hot aqueous treatment without
gel is drawn 300 – 700 % in one or two steps.
86 Fibers, 4. Synthetic Organic

tension, crimping, or oiling, and low-tempera- 120 dtex) and multifilaments (10 – 78 dtex).
ture drying follow if the fiber is to be used in Typical properties are:
the dry-laid nonwoven process; for the wet-laid
Density 1.65 – 1.75 g/cm3
nonwoven process, crimping is omitted. Break strength 1.5 – 2.0 cN/dtex
The relevant key properties are: Break elongation 15 – 25 %
Initial modulus 6 – 10 cN/dtex
Chlorine content 46 % Moisture regain >0.1 %
Break strength 0.6 – 0.7 cN/dtex Softening point 115 – 135 ◦ C
Break elongation 150 – 200 % mp 170 – 177 ◦ C
Softening point 69 ◦ C Shrinkage temperature 70 ◦ C
mp 155 – 160 ◦ C Dielectric constant at 60×106 Hz 3–5
Decomposition temperature 230 ◦ C Dielectric loss tan δ 0.05
Shrinkage in water 18 – 28 % at 80 ◦ C
Shrinkage tension 0.003 cN/dtex
Shrinkage temperature 60 ◦ C
Poly(vinylidene) chloride has excellent resis-
tance to acid, alkali (except ammonium hydrox-
Bonding may be carried out between 80 and ide), and weathering but poor heat resistance.
150 ◦ C or between 150 and 170 ◦ C with trans- The products cannot be dyed easily; disperse
formation of the fiber into melt droplets. Ther- dyes may be used but fastness is poor.
mal bonding is used to produce nonwovens,
blended with other natural, regenerated, or syn-
thetic fibers at a ca. 30 % maximum content. 7. Poly(vinyl alcohol) Fibers
Trade Name, Producer (Country): Wacker MP-
Faser, Wacker Chemie (France); Vinyon HH, W. O. Hermann and W. Haenel applied for the
Celanese Co. (United States). first patent on poly(vinyl alcohol) [9002-89-5]
(PVA) fiber in 1931. They reported that the fiber
could be made from PVA by the well-known
wet- and dry-spinning methods, and that the wa-
6.4. Fibers from Poly(vinylidene
ter resistance of the fiber could be improved by
chloride) and Copolymers [278], [286], physical and chemical aftertreatment. However,
[287] they did not investigate further the production
of a water-resistant textile fiber because their in-
The homopolymer of PVDC has a softening terest was limited mainly to the solubility of the
point of 185 – 200 ◦ C. Its two outstanding prop- fiber in water. Water-soluble PVA monofilament,
erties, high crystallinity and insolubility, make it made by dry spinning and called “Synthofil,”
difficult to process. Therefore, to ease process- was manufactured for a short time in Germany.
ing conditions, copolymers with small quantities In 1940, I. Sakurada and his colleagues im-
of vinyl chloride are used. proved the hot-water resistance of wet-spun PVA
The usual copolymers contain 85 – 90 wt % fiber by heat-treating it in hot air and acetalizing
vinylidene chloride (saran). Copolymers are it with formaldehyde; they developed the tech-
processed by melt spinning or extrusion. Be- nology for production of a water-resistant textile
cause they are heat sensitive and have a lim- fiber [288].
ited thermal life at the extrusion temperature, Wet-spun staple fiber based on this technol-
specially designed extruders and alloys are re- ogy was first available commercially in Japan in
quired. Depending on end use, plasticizers, heat 1950; the fiber was called “Vinylon.” Initially,
and light stabilizers, and colored pigments may Vinylon was distinguished from other synthetic
be added to the copolymer. Monofilaments or fibers by its hydrophilic properties and it was
multifilaments are extruded at 160 – 175 ◦ C, marketed as a substitute for cotton in both cloth-
quenched in water at 10 – 15 ◦ C with a short dis- ing and industrial fibers. Improved production
tance between the spinneret and the level of the technology led to remarkable improvement in
quenching bath, and then drawn 500 – 600 %. the mechanical properties of the fiber. In 1959,
high-tenacity filament produced by dry spin-
Products, Properties, and Uses. The range ning, and later by wet spinning, became avail-
of products includes monofilaments (70 – able. The use of Vinylon has become almost en-
 Fibers, 4. Synthetic Organic 87

tirely industrial. In addition to the water-resistant 7.2. Production

fiber, a water-sensitive variety has been pro-
duced for water-soluble fiber and binder fiber 7.3. Poly(vinyl alcohol) for Fiber
for making paper.
The staple fiber has been also produced com- Poly(vinyl alcohol) for fiber is produced by
mercially in the Democratic People’s Republic polymerization of vinyl acetate in methanol and
of Korea since 1961 and the People’s Republic subsequent alkaline hydrolysis of poly(vinyl ac-
of China since 1965. etate). The material must have a degree of poly-
merization of 1200 – 2500 and a narrow molec-
ular mass distribution. These properties are at-
7.1. Physical and Chemical Properties tained by adjusting polymerization conditions,
and especially by conducting the polymerization
The mechanical properties of commercial PVA at a lower temperature and keeping the conver-
fibers (Vinylon) produced in Japan are shown sion of vinyl acetate in methanol below 70 %.
in Table 20 [289] (see → Fibers, 1. Survey, For the production of industrial fiber, PVA
Chap. 5.). The tenacity and modulus are the with a degree of polymerization of ca. 1700
highest among commercial general-purpose is generally used. The amount of residual
synthetic fibers. Fiber having a tenacity of acetyl groups in PVA should be <0.1 mol % for
12 cN/dtex and a modulus of 274 cN/dtex has heat treatment to produce a sufficiently water-
been produced for cement reinforcement. Re- resistant fiber.
sistance to abrasion and fatigue is also excel-
lent. The fiber absorbs slightly more water than
polyamide fiber; and its mechanical properties in 7.3.1. Wet Spinning
the wet state are somewhat lower. Formalization
is effective in improving water resistance of the Sodium Sulfate Coagulation Bath Method.
fiber but may lower the mechanical properties. Staple fiber and tow are produced by wet spin-
The elastic recovery is slightly lower than that ning.
of acrylic fiber but better than cotton or rayon. In ordinary wet spinning, PVA is dissolved
Acetalization with benzaldehyde is an effective in water to a concentration of 14 – 16 % by heat-
technique for improving the elastic recovery of ing. After filtration and deaeration, the spinning
PVA fibers used in clothing. The resistance of solution is kept above 70 ◦ C to avoid gelation.
PVA fiber to various chemicals is generally su- It is extruded through spinnerets into a coag-
perior to that of polyamide and polyester fibers. ulation bath containing a saturated solution of
In particular, its excellent alkali resistance is im- sodium sulfate at 40 – 50 ◦ C. The coagulation
portant in the reinforcement of cement products speed is much slower than that of viscose, and
[290]. Because of its high polarity, PVA fiber ad- a longer residence time in the bath is necessary.
heres well to matrix materials in fiber-reinforced For the coagulation operation to run smoothly,
composites for resin, rubber, and cement. Its and to minimize floor space requirements, a ver-
weather resistance is the highest of the various tical spinning machine is preferred [291]. The
synthetic fibers. spun fiber tow is usually drawn while passing
The fiber is softened by heating above 230 – through a second hot coagulation bath and then
240 ◦ C, but it has no definite melting point. dried.
Commercial fibers with sufficient hot-water re- The wet-spun and dried fiber is soluble in hot
sistance, and water-soluble fibers that dissolve water. It is further drawn and heat-treated in hot
in 20 – 90 ◦ C water, are produced by applying air or by hot rollers at 210 – 240 ◦ C. The tem-
the appropriate heat or acetalization treatments. perature of the heat-treatment process must be
For use in wearing apparel, the formalized staple higher than that of the hot drawing process. In
fiber, mainly blended with cotton, is dyed with heat treatment, a small amount of shrinkage is
direct, vat, sulfur, or metallized dyes. usually allowed in order to stabilize fiber struc-
ture. This treatment orients and crystallizes the
polymer chains in the fiber, reducing the fiber
solubility in hot water.
88 Fibers, 4. Synthetic Organic
Table 20. Mechanical properties of Vinylon fibers [289]

Property Staple and tow Filament

Regular tenacity High tenacity Regular tenacity High

tenacity

Tenacity, cN/dtex
Standard 3.5 – 5.7 6.0 – 9.3 2.6 – 3.5 5.3 – 10.6
Wet 2.8 – 4.6 4.7 – 7.9 1.9 – 2.8 4.4 – 9.3
Wet – standard ratio, % 72 – 85 78 – 85 70 – 80 75 – 90
Loop tenacity, cN/dtex 2.8 – 4.6 4.4 – 5.1 4.0 – 5.3 6.2 – 11.5
Knot tenacity, cN/dtex 2.1 – 3.5 4.0 – 4.6 1.9 – 2.6 2.4 – 4.4
Elongation, %
Standard 12 – 26 9 – 17 17 – 22 6 – 22
Wet 12 – 26 9 – 17 17 – 25 8 – 26
Young’s modulus, cN/dtex 22 – 62 62 – 221 53 – 79 62 – 221
Resilience at 3 % elongation, % 70 – 85 72 – 85 70 – 90 70 – 90
Relative density 1.26 – 1.30 1.26 – 1.30 1.26 – 1.30 1.26 – 1.30
Commercial regain, % 5.0 5.0 5.0 5.0
Water absorbency, %
20 ◦ C, 20 % R.H. 1.2 – 1.8 1.0 – 1.5 1.2 – 1.8 1.0 – 1.5
20 ◦ C, 65 % R.H. 4.5 – 5.0 3.5 – 4.5 3.5 – 4.5 2.5 – 4.5
20 ◦ C, 95 % R.H. 10.0 – 12.0 8.0 – 10.0 10.0 – 12.0 8.0 – 10.0

The heat-treated fiber is further acetal- dration from the outside of the extruded jet of
ized in an aqueous solution containing 1 – 5 % spinning dope. This makes it difficult to obtain
formaldehyde, 10 –20 % sulfuric acid, and 5 – a clear fiber with high tensile strength.
20 % sodium sulfate at 50 – 80 ◦ C for 10 – When PVA dope is spun into an aqueous
60 min to reach a degree of formalization of solution of concentrated alkali, fiber with a
25 – 35 mol %. Acetalization is affected not only round cross section and a homogeneous, com-
by reaction conditions but also by conditions pact structure can be obtained [292]. The fiber is
of the drawing and heat-treatment processes ap- transparent and can be highly drawn to give im-
plied to the fiber. Acetalization greatly improves proved tensile strength and modulus, and better
the boiling-water resistance of the fiber and also water resistance. In this case, the spinning dope
changes its mechanical and chemical properties extruded in the coagulation bath is gelated in-
to some extent. stantaneously by contact with the alkaline coag-
In the production of staple fiber, the heat- ulant, so dehydration proceeds homogeneously.
treated tow is usually crimped mechanically and This wet-spinning method is used in Japan. In
cut, the cut fiber is formalized. For industrial commercial practice, the aqueous coagulation
application, the formalized tow is subjected di- bath contains sodium hydroxide at a concentra-
rectly to a stretch-break spinning system (Per- tion >200 g/L and at a temperature of 40 –50 ◦ C.
lock or Converter system) to convert it to spun The alkaline coagulation method was modi-
yarn. This yields spun yarn with high tenacity fied to give more highly drawn fiber with a higher
and high toughness. modulus by using aqueous acidic spinning dope
Short-cut fiber, destined to be water- containing a small amount of boric acid [293].
swellable binder fiber or water-resistant sub- Because of the presence of boron, cross-linking
strate fiber for making paper, is produced by appears to occur between the polymer chains
cutting wet-spun and dried tow, or tow that has of PVA during fiber formation. This suppresses
been heat-treated and sometimes formalized, to entangling of the polymer chains and makes co-
the proper length of 3 – 12 mm. agulation more homogeneous.
The spinning dope, containing boric acid of
Alkaline Coagulation Bath Method. Fiber 0.5 – 2.0 wt % (relative to PVA) at pH 3 – 5.5,
that has been wet-spun in a sodium sulfate co- is spun into an aqueous alkaline coagulation
agulation bath has a cocoon-shaped cross sec- bath containing 20 – 100 g/L of sodium hydrox-
tion and skin – core of inhomogeneous structure ide and 100 – 300 g/L of sodium sulfate at pH
because coagulation proceeds with rapid dehy- 13.5 – 14.0. After removal from the coagula-
 Fibers, 4. Synthetic Organic 89

tion bath, the spun fibers are treated with acid, (i.e., draft ratio = winding rate/extrusion rate),
washed with water, dried, and drawn to a draw and gradually dried while the drying tempera-
ratio >10 to give high tenacity (>9 cN/dtex) and ture is raised. The dried filaments have a circular
high modulus (>177 cN/dtex). cross section, a homogeneous structure, and low
This technology was developed initially for strain; they can be drawn to the highest draw ra-
production of high-tenacity, high-modulus fila- tio and heat-treated near the melting point. The
ment yarn for use in belt cord for radial tires. resulting filament has adequate hot-water resis-
The yarn is modified further to produce high- tance and is used commercially without formal-
modulus fiber, which can be substituted for as- ization.
bestos in cement reinforcement; this fiber has a This method is suitable for producing heav-
tenacity of 12 cN/dtex and a modulus of 274 cN/ ier filament for industrial applications. It was
dtex [294]. originally developed for the production of heav-
ier monofilaments of 110 – 1100 dtex. It is now
Wet Spinning with Organic Solvent. also applied to the production of multifilaments,
Polyvinyl alcohol has a high crystalline modulus such as 1330 dtex/200 filaments.
comparable to that of polyethylene. This high
modulus has not been exploited extensively to High-Draft Spinning. In high-draft spin-
date in the preparation of fiber. Various investi- ning, aqueous spinning dope containing PVA
gations have been carried out into the prepara- at a concentration of 28 – 41 % is spun at 90 –
tion of PVA fiber with a much higher modulus. 95 ◦ C into a spinning tube consisting of a draft-
In many cases, this has involved modified wet- ing zone at 30 – 80 ◦ C and 55 – 95 % R.H., and
spinning methods that use organic solvents. a drying zone at >80 ◦ C and <50 % R.H. While
When a hot, dilute solution of PVA in passing through the spinning tube, the filament
polyol is cooled slowly, highly crystallized is highly drafted and dried so as to be taken
PVA is deposited [295]. This phenomenon has off at a winding speed of 200 – 500 m/min. The
been connected with gel-spinning – ultrahigh- dried filaments are hot-drawn and heat-treated,
drawing procedures. When the gel fiber from a and sometimes further acetalized.
solution of PVA in glycerin, having an ultra-high This method can give finer filaments
degree of polymerization of 38 000, was hot- (<5 dtex) for textile applications. Some filament
drawn at high temperature, the resulting fiber for apparel, made from a mixture of PVA and
had a tenacity of 17 cN/dtex and a modulus of aminoacetalized PVA is produced commercially
555 cN/dtex [296]. and can be dyed with acid dyes. This method is
now used primarily to produce water-soluble fil-
ament. Filament soluble in water at 20 – 90 ◦ C
7.3.2. Dry Spinning is produced commercially by using PVA with
low degrees of polymerization and saponifica-
Dry spinning of PVA is used in the production tion, and by adjusting heat-treatment conditions
of filament yarns. The two classifications of dry [299].
spinning are low-draft spinning [297] and high-
draft spinning [298].
7.3.3. Mixed Spinning
Low-Draft Spinning. Aqueous spinning
dope, which has a concentration of 41 – 45 % and The technology for spinning bicomponent fiber
an extremely high viscosity, is used in low-draft from PVA and poly(vinyl chloride) (PVC) in an
spinning. It is prepared by dissolving PVA gran- emulsion was developed in 1961 [300].
ules, conditioned with water, by heating them in Vinyl chloride is emulsion-polymerized in an
an extruder under pressure. aqueous solution of PVA, and the emulsion is
The high-vicosity spinning dope at a temper- mixed with PVA to give a spinning dope con-
ature of 130 – 160 ◦ C, is spun in air at ca. 50 ◦ C. taining PVC and PVA in ca. 1 : 1 mass ratio. The
The cooled and solidified filament is wound in fiber is produced in essentially the same way as
a low-draft ratio of 0.3 – 1.0 based on the extru- regular PVA fiber, by using the sodium sulfate
sion rate of the spinning dope from the spinneret
90 Fibers, 4. Synthetic Organic

coagulation bath method. The fiber is charac- The producers of Vinylon and Polychlal
terized by its flame retardance and is produced fibers in Japan, and their brand names, are as
commercially in Japan under the name Polych- follows:
lal. Vinylon: Kuraray Co. (Kuraray Vinylon,
Cremona,Kuralon),
Unitika Chemical Co. (Unitika
Vinylon, Mewlon),
7.4. Uses Nitivy Co. (Vilon, Solvron;
water-soluble)
In Japan, about 90 % of Vinylon fiber produc- Polychlal: Kohjin Co. (Cordelan)

tion, ca. 30 000 t/a, is consumed in industrial ap-

plications that require such advantages as high
tenacity, excellent weather resistance, and effec-
tive reinforcing effect in matrices. The main in-
dustrial uses are fishing nets, ropes, belts, can- 8. Polytetrafluoroethylene Fibers
vasses, and sewing threads. Perlock-type spun
yarns from 100 % Vinylon tows and filament Polymerization technology for polytetrafluoroeth-
yarns are used predominantly. The water-soluble ylene [9002-84-0] (PTFE) has been known since
filaments are used to produce chemical lace fab- 1941 and has become well established, leading
rics. to utilization of the polymer not only as a plastic
The development of special grades has in- but also in fiber form [301]. This is undoubt-
creased the demand for Vinylon remarkably. The edly because it combines interesting chemical
water-swellable, short-cut fibers are popular as (inertness) and physical (low friction, tempera-
binders in the production of paper and wet-laid ture resistance, and triboelectric characteristics)
nonwoven fabrics. Another short-cut fiber, mod- properties.
ified to have the highest tenacity and modulus as Tetrafluoroethylene is polymerized under
well as a special surface structure that enhances pressure in the presence of persulfate or perox-
its adhesion to matrices, is used as a substitute ide in water; oxygen is excluded. The reaction
for asbestos to reinforce cement products. These is exothermic and increases in velocity with in-
special grades are exported to the world market. creased pressure. The viscosity of the polymer,
Only 10 % of Vinylon production is used do- as well as its molecular mass cannot be mea-
mestically in Japan for apparel, mainly by blend- sured readily; however, indications are that the
ing Vinylon with cotton and other fibers. The polymer chain is linear. At the normal polymer-
main apparel application is work clothing that ization level, molecular masses are estimated to
requires durability and chemical resistance. be between a few hundred thousand and several
In Korea and China, significant quantities of million.
PVA fiber are blended with cotton and used for
apparel. In these countries too, fiber applications
in the future will shift gradually to industrial 8.1. Physical and Chemical Properties
uses.
Some of the physical properties of
polytetrafluoroethylene are as follows:
7.5. Economic Aspects mp 327 ◦ C
Glass transition temperature ca. 120 ◦ C
Poly(vinyl alcohol) fibers are produced in Japan,
2.1 g/cm3
the Democratic People’s Republic of Korea, and Melt viscosity (380 ◦ C) 10 GPa

the People’s Republic of China. In Japan, pro-

duction levels reached a maximum of 76 000 t These fibers are similar to the polymer
in 1971 and decreased to 36 000 t by 1984, (i.e., highly crystalline 93 – 98 %) and, be-
while production capacity remained constant cause of the high energy of the C−F bond,
at 80 000 t/a [289]. Korea and China are pre- display appreciable resistance to heat and
sumed to have production capacities of more chemicals (see → Fibers, 1. Survey, Chap. 5.;
than 50 000 and 150 000 t/a, respectively. → Fluoropolymers, Organic). As a result, the
 Fibers, 4. Synthetic Organic 91

polymer is difficult to burn. The fibers also are perature through a multihole spinneret (hole di-
distinctive because of their good light and weath- ameter 0.15 mm) into a coagulating bath con-
ering durability, and their utility at temperatures taining 6 % sulfuric acid, 16 % sodium sulfate,
up to 290 ◦ C. Phase changes that occur below and 0.3 % zinc sulfate. The spinning velocity is
30 ◦ C are responsible for the cold flow charac- about 12 m/min.
teristics of the material, although the fibers are After coagulation, the yarn is washed with
reported to be more dimensionally stable than water at 90 ◦ C, dried at 190 ◦ C, and then raised to
bulk polymer because of their molecular ori- 340 – 360 ◦ C, the temperature at which polymer
entation. Decomposition products are generated particles are sintered and the viscose residue de-
above 290 ◦ C at a rate of 0.0002 %/h. Copoly- grades and is partially burned. After a brief con-
mers, containing minor amounts of other fluo- tact time at 360 – 390 ◦ C, the yarn is stretched
rinated monomers, are also available. These are four to eight times its original length.
melt extrudable but, because of their high melt The resultant continuous-filament yarn has a
viscosities, only into monofils of ≥100 dtex. A tenacity of 1.8 cN/dtex and an elongation of 20 –
50 – 50 copolymer with ethylene (Tefzel, Du 30 %. The filament mass is 6 dtex. The fibers are
Pont) has a lower melt viscosity and can be ex- brown and can be bleached in boiling sulfuric
truded at commercially attractive speeds; how- acid containing nitric acid or by exposure for
ever, its temperature –chemical characteristics several days in an air oven. The latter must be
are altered by the presence of the nonfluorinated done cautiously by raising the temperature step-
comonomer. wise to 350 ◦ C, to avoid exotherms because of
the sudden oxidation of the viscose residues.

8.2. Production
8.3. Uses
Polytetrafluoroethylene can be sintered above
its melting point into a tough, viscous melt. Polytetrafluoroethylene fibers are utilized in wo-
However, melt spinning is not feasible with ven and nonwoven forms as filter media for
the homopolymer because the temperature re- aggressive liquids and gases (i.e., strong acids,
quired to overcome the viscosity leads to poly- bases, and oxidizing agents), including air pollu-
mer degradation. Because economically attrac- tion control fabrics. Fibers are also used in gas-
tive solvents for the polymer have not been found kets and pump seals because of their chemical re-
(a few fluorinated hydrocarbons dissolve several sistance and low-friction characteristics. In elec-
percent of polymer above 300 ◦ C), either paste trical systems, they are utilized as insulators for
extrusion below the melting point of the polymer wires and components, and as cleaners – wipers
or dispersion spinning to form fibers is used. To in xerographic devices, where their high-tempe-
promote agglomeration during extrusion of plas- rature and triboelectric characteristics are impor-
ticized (with 20 wt % kerosene) homopolymer, tant. Because of their great chemical stability,
extrusion is done under conditions favorable to these fibers are used as the binder component
production of particulates in ribbon form, so that in asbestos chlor-alkali cell diaphragms. The
at least 30 % have a width of 0.1 nm, an as- low-friction characteristics and high length –
pect ratio of at least 5 : 1, and a cross section diameter ratio of the fibers are important in their
of <0.001 nm2 . Sintering, followed by draw- use as solid lubricants in engineering plastics.
ing and heat-setting results in solid or expanded Monofils have found application in demisters in
films (depending on process conditions), which the production of mineral acids.
are then split into filaments of ca. ≥100 dtex. In addition, dispersion of fibers on woven or
An alternate process is used to produce nonwoven substrates imparts chemical stability
finer filaments. A 60 % solid dispersion of to the surface and results in layered composites
polytetrafluoroethylene polymer, stabilized with with excellent dielectric properties and corro-
aryl or alkyl polyglycol ethers, is blended with sion resistance for utilization in xerography.
viscose solution (5 %). The latter acts as a ma-
trix during early phases of the process. The mix- Trade Names. Teflon [98846-34-5], Teflon
ture is filtered and then extruded at room tem- FEP [58516-09-9], Teflon TFE, Teflon PFA
92 Fibers, 4. Synthetic Organic

[71767-39-0], Tefzel [25038-71-5], Tefaire (Du 12. C. F. Horn et al., Angew. Chem. 74 (1962)
Pont, United States); Goretex (Gore, United 531 – 540.
States); Polyflon (Daikin Kogyo, Japan); Toy- 13. Monsanto, FR 1 419 132, 1964 (J. E. Tate).
oflon (Toyo Rayon, Japan); Fluon (ICI, Great Monsanto, US 3 402 152, 1968 (E. T. Erignac,
Britain). R. T. Wright).
14. D. O’Sullivan, Chem. Eng. News 62 1984,
no. 21, 21 – 22.
15. BASF, US 4 060 517, 1977 (F. Mertes et al.).
8.4. Toxicology and Occupational
16. P. W. Morgan, S. W. Kwolek, Macromolecules
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17. J. S. Ridgeway, J. Polym. Sci., Polym. Chem.
Adequate ventilation should be provided during Ed. 12 (1974) no. 9, 2005 – 2016.
processing of PTFE fibers. At elevated process- 18. Du Pont, US 3 502 624, 1970 (C. F. Black).
ing temperatures, PTFE fluoropolymer fibers 19. F. Happy (ed.): Applied Fiber Science, vol. 2,
liberate vapors that may be harmful. Generally, Academic Press, New York 1981, pp. 1 – 44.
adequate ventilation and care to prevent such 20. F. Happy (ed.): Applied Fiber Science, vol. 1,
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nate smoking tobacco with PTFE fibers. A mix- 21. Du Pont, US 3 184 436, 1965 (E. E. Magat).
ture of tobacco and PTFE polymer would be 22. I. M. Kolthoff, P. J. Elving, F. H. Stross (eds.):
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avoided by not carrying tobacco into areas where pp. 273 – 313.
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24. W. Schnabel: Polymer Degradation –
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86. N. H. Bezaz, Chemiefasern/Text.-Ind. 32/84
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94 Fibers, 4. Synthetic Organic

87. H. Lückert, M. Busch, Chemiefasern/Text.-Ind. 115. H. Reinbold, Chemiefasern/Text.-Ind. 35/87

33/85 (1983) 29 – 38. (1985) 420 – 422.
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 Fibers, 5. Synthetic Inorganic 1

Fibers, 5. Synthetic Inorganic

Erich Fitzer, Institut für Chemische Technik der Universität Karlsruhe, Karlsruhe, Federal Republic of
Germany (Chaps.1 and 5)
Rudolf Kleinholz, Gevetex Textilglas-GmbH, Herzogenrath, Federal Republic of Germany (Section 2.1)
Hartmut Tiesler, Grünzweig + Hartmann und Glasfaser AG, Ladenburg, Federal Republic ofGermany
(Section 2.2)
Martyn Hugh Stacey, ICI Chemicals & Polymers Ltd., Runcorn, United Kingdom (Chaps. 3 and 6)
Roger De Bruyne, N.V. Bekaert S.A., Zwevegem, Belgium (Chap. 4)
Ignace Lefever, N.V. Bekaert S.A., Zwevegem, Belgium (Chap. 4)
Michael Heine, Institut für Chemische Technik der Universität Karlsruhe, Karlsruhe, Federal Republic of
Germany (Chap. 5)

1. Survey . . . . . . . . . . . . . . . . . . 3 2.1.5. Toxicology and Occupational Health 21

1.1. General Description of Inorganic 2.1.6. Economic Aspects . . . . . . . . . . . 22
Fibers . . . . . . . . . . . . . . . . . . 3 2.1.7. Producers . . . . . . . . . . . . . . . . 22
1.1.1. Commercial Forms and Terminol- 2.2. Glass Fibers for Insulation . . . . 22
ogy . . . . . . . . . . . . . . . . . . . . 3 2.2.1. Physical Properties . . . . . . . . . . 22
1.2. Crystalline Structure 2.2.2. Chemical Properties . . . . . . . . . . 23
and Mechanical Properties . . . . 4 2.2.3. Raw Materials and Chemical Com-
1.3. Testing Methods for Inorganic position . . . . . . . . . . . . . . . . . 23
Fibers . . . . . . . . . . . . . . . . . . 6 2.2.4. Production . . . . . . . . . . . . . . . . 24
1.4. Inorganic Fibers for Thermal In- 2.2.5. Environmental Protection . . . . . . 27
sulation . . . . . . . . . . . . . . . . . 7 2.2.6. Quality and Analysis . . . . . . . . . 28
1.5. Inorganic Fibers for Reinforce- 2.2.7. Applications . . . . . . . . . . . . . . 28
ment Purposes . . . . . . . . . . . . . 8 2.2.8. Toxicology and Occupational Health 29
1.5.1. Principles of the Fiber Reinforce- 3. Refractory Fibers . . . . . . . . . . 29
ment . . . . . . . . . . . . . . . . . . . 8 3.1. Properties and Raw Materials . . 30
1.5.2. Commercial Continuous Inorganic 3.1.1. Physical Properties . . . . . . . . . . 30
Fibers . . . . . . . . . . . . . . . . . . . 9 3.1.2. Chemical Properties . . . . . . . . . . 33
1.5.3. Surface Chemistry, Surface Treat- 3.1.3. Resources, Raw Materials . . . . . . 33
ment, and Surface Properties . . . . 11 3.2. Production . . . . . . . . . . . . . . . 34
1.5.4. High-Temperature Behavior of Inor- 3.2.1. Boron Monofilament . . . . . . . . . 34
ganic Fibers . . . . . . . . . . . . . . . 12 3.2.2. Silicon Carbide Fibers . . . . . . . . 35
2. Glass Fibers . . . . . . . . . . . . . . 13 3.2.3. High Alumina Fibers . . . . . . . . . 36
2.1. Textile Glass Fibers . . . . . . . . . 13 3.2.4. Zirconia Fibers . . . . . . . . . . . . . 37
2.1.1. Chemical Composition and Proper- 3.3. Environmental Protection . . . . . 38
ties . . . . . . . . . . . . . . . . . . . . 14 3.4. Uses . . . . . . . . . . . . . . . . . . . 38
2.1.2. Manufacture . . . . . . . . . . . . . . 16 3.4.1. High-Temperature Insulation and
2.1.2.1. Glass Filaments . . . . . . . . . . . . 16 Filtration . . . . . . . . . . . . . . . . . 38
2.1.2.2. Glass Staple Fibers . . . . . . . . . . 18 3.5. Miscellaneous Uses . . . . . . . . . . 39
2.1.3. Textile Glass Products: Processing 3.6. Economic Aspects . . . . . . . . . . 39
and Application . . . . . . . . . . . . 18 3.7. Toxicology and Occupational
2.1.3.1. Product Designation . . . . . . . . . . 18 Health . . . . . . . . . . . . . . . . . . 40
2.1.3.2. Correlation Between Processing and 4. Metal Fibers . . . . . . . . . . . . . . 40
Application . . . . . . . . . . . . . . . 18 4.1. Production . . . . . . . . . . . . . . . 40
2.1.3.3. Description of Textile Glass Prod- 4.1.1. Bundle Drawing . . . . . . . . . . . . 40
ucts . . . . . . . . . . . . . . . . . . . . 19 4.1.2. Melt Spinning . . . . . . . . . . . . . 41
2.1.3.4. Applications . . . . . . . . . . . . . . 20 4.1.3. Other Processes . . . . . . . . . . . . 42
2.1.4. Product Standards . . . . . . . . . . . 21 4.2. Bundle-Drawn Fibers . . . . . . . . 43

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11 001
2 Fibers, 5. Synthetic Inorganic

4.2.1. Form and Dimensions . . . . . . . . 43 5.3. Production . . . . . . . . . . . . . . . 56

4.2.2. Composition . . . . . . . . . . . . . . 43 5.3.1. PAN Precursor Fiber . . . . . . . . . 57
4.3. Uses . . . . . . . . . . . . . . . . . . . 43 5.3.2. Stabilization . . . . . . . . . . . . . . . 58
4.4. Manufacturers . . . . . . . . . . . . 45 5.3.3. Process Parameters . . . . . . . . . . 59
4.5. Melt Spun Fibers . . . . . . . . . . . 45 5.4. The Pitch Fiber Process . . . . . . 59
4.5.1. Properties . . . . . . . . . . . . . . . . 45 5.4.1. Isotropic and Anisotropic Pitch
4.6. Uses . . . . . . . . . . . . . . . . . . . 45 Fiber Precursors . . . . . . . . . . . . 59
5. Carbon Fibers . . . . . . . . . . . . . 45 5.4.2. The Mesophase Formation . . . . . . 60
5.1. Properties . . . . . . . . . . . . . . . . 47 5.4.3. Process Steps . . . . . . . . . . . . . . 60
5.1.1. Mechanical Properties . . . . . . . . 47
5.5. Comparison of the Carbon Fibers-
5.1.2. Chemical Composition . . . . . . . . 47
Based on PAN and on Pitch . . . . 63
5.1.3. Structure . . . . . . . . . . . . . . . . . 48
5.6. Commercial Availability and Eco-
5.1.4. Physical Properties . . . . . . . . . . 51
nomic Aspects . . . . . . . . . . . . . 64
5.1.5. Chemical Properties . . . . . . . . . . 51
5.2. History . . . . . . . . . . . . . . . . . 54 5.6.1. Companies and Trade Names . . . . 64
5.2.1. Rayon-Based Carbon Fibers . . . . . 54 5.6.2. World Capacity . . . . . . . . . . . . . 64
5.2.2. PAN-Based Carbon Fibers . . . . . . 55 5.7. Future Importance . . . . . . . . . . 65
5.2.3. Pitch-Based Carbon Fibers . . . . . 55 6. Refractory Ceramic Fibers . . . . 67
5.2.4. Vapor-Grown Carbon Fibers . . . . 56 7. References . . . . . . . . . . . . . . . 67

1. Survey cept for metal fibers, they are also character-

ized by brittleness. Based on these general prop-
1.1. General Description of Inorganic erties, they are less important as textiles per
Fibers se; however, they are superb for reinforcement
of other materials, in the so-called composites
The inorganic fibers are treated in five chapters: (→Composite Materials).
Glass Fibers, Refractory Fibers, Metal Fibers, They are excellent as thermal insulation at
Carbon Fibers and Refractory Ceramic Fibers. high temperatures and in corrosive environ-
In this introduction, the similarities with or- ments.
ganic synthetic fibers, as well as special charac-
teristics, are treated generally.
Unlike organic fibers, there are no natural 1.1.1. Commercial Forms and Terminology
sources for inorganic fibers, with one exception,
asbestos fibers, which are a separate keyword The term fiber can be used for a formed mate-
(→Asbestos). As synthetic products, inorganic rial that has a length-to-diameter ratio of at least
fibers have obvious similarities with the syn- 10 : 1, and with a cross-sectional area below
thetic organic fibers, first of all in the morphol- 0.005 mm2 and a thickness below 0.25 mm [1].
ogy and terminology of the commercially avail- This standardized nomenclature also includes
able forms and in their field of technical appli- whiskers, which are mainly single-crystal ma-
cation. Synthetic organic (Chardonnet silk, a re- terials, and are treated under a separate keyword
generated cellulose fiber (see Fibers, 1. Survey) (→Whiskers). Nonmetallic fibers include both
and inorganic fibers were first fabricated a hun- continuous (endless) and short fibers. Diameters
dred years ago. The critical difference between range between 5 and 15 µm, but some are much
inorganic and organic fibers is seen in the differ- thicker, for instance, the fibers made by chem-
ing properties, which correspond in general to ical vapor deposition on a substrate fiber such
those of organic polymers on the one hand and as B or SiC fibers which have diameters of ca.
to those of inorganic and metallic materials on 100 – 150 µm. The diameter is of critical impor-
the other hand. tance in regard to the tensile strength, because
Nonmetallic inorganic fibers are stronger, all materials showing brittle fracture increase in
stiffer, higher melting, and thus more heat re- strength as the diameter decreases (Fig. 1).
sistant, and in all cases nonflammable, but, ex-
 Fibers, 5. Synthetic Inorganic 3

to produce monofilament fibers. Such monofil-

ament fibers are used to reinforce polymers,
although of decreasing importance. However,
such fibers may be useful in the reinforcement
of light metals. The CVD technique can be used
with success to fabricate yarns of high-melting
substrate fibers with a coating on the individual
monofilament, e.g., SiC or B4 C on boron or TiN,
SiC, etc. on carbon.

1.2. Crystalline Structure and

Figure 1. Tensile strength of monofilaments (carbon fibers)
Mechanical Properties
as a function of fiber diameter. a) Hercules AS4 (Hercules);
b) Torayca T300 (Toray); c) Torayca M40 (Toray) Glass and mineral fibers are characterized by
their amorphous structural state, while metal and
Short fibers can be fabricated by a melt spin- some oxide fibers such as the DuPont A1203
ning process directly to staple fibers (see pp. 16 fiber are characterized by their polycrystallinity.
and 23 – 24) or by chopping (cutting) of con- In the case of most refractory ceramics pro-
tinuous fibers. Commercial short-fiber products duced from organic precursors, and also in
include wool, mats, and felts. The spinning of the case of carbon fibers, the structure is not
short fibers to continuous yarn, as with natural fully amorphous, but the crystals in the fibers
organic fibers, is generally not practiced for syn- are so imperfect that the term polycrystallinity
thetic inorganic fibers. can be used only with reservation. As a con-
Continuous fibers are fabricated by melt spin- sequence, postheat-treatment of such fibers
ning, if the fiber materials are meltable, such as is above 1000 ◦ C easily initiates crystallization
the case for glass or mineral fibers. The advanced processes as demonstrated on quite pure Si3 N4
inorganic fibers, such as carbon fibers and also fiber (experimental-type Tonen in 1988, [2])
those of refractory ceramics, are made from or- in Figure 2. The room temperature strength of
ganic precursor fibers via thermal degradation. the fabricated fiber with final pyrolysis tem-
For the spinning of the precursors the meth- peratures of 1000 ◦ C in nitrogen is 2450 MPa,
ods for fabrication of synthetic organic fibers an impressive value, but after heat treatment at
are used. This precursor technique can produce
both monofilaments and multifilaments, as de-
scribed in “Organic Fibers” (Fibers, 4. Synthetic
Organic). Only filament yarns which consist of
up to 300 000 filaments are commercially avail-
able (see “multifilament tow” in Chap. 5.6.2).
For reinforcement in advanced composites, tows
of 3000 to 12 000 monofilaments (3 – 12 K tows)
are used.
Meltspun glass fibers are also fabricated as
filament tow and applied in rowings of some
thousands of monofilaments. The terms rovings
and tows are synonymous for filament yarn. Fab-
rics from filament yarns are commercially avail-
able. They are fabricated by weaving, braising,
or similar techniques without binder to textiles,
tubes, filter sieves, cables, etc. The chemical va-
por deposition (CVD) method of fabrication, a Figure 2. Composition and X-ray diffraction of an
method developed to produce boron fibers and experimental-type silicon nitride fiber with the composition
still used for B and SiC fibers, can only be used in mass fraction: 59.2 % Si, 39.1 % N, 0.5 % C, 1.1 % O,
0.1 % H; θ = Bragg angle [2]
4 Fibers, 5. Synthetic Inorganic

1600 ◦ C, a perfect β-Si3 N4 crystal structure de- modulus of the fibers because of the extreme
velops, and room-temperature strength drops be- anisotropy of the graphite-like carbon structure.
low 1000 MPa, a considerable lowering of the In no case can three-dimensional crystallinity,
mechanical properties. Figure 3 shows further as in the graphite structure, be achieved by
examples where the decrease in strength due to postheat-treatment of carbon fibers, not even
thermally activated crystallization is even more above 2700 ◦ C. Therefore, carbon fibers never
extreme. consist of polycrystalline graphite and the term
“graphite fibers,” as used commercially in the
United States, is scientifically unjustified and
misleading.
A characteristic of inorganic fibers, whether
amorphous or polycrystalline is that they all ex-
hibit brittle fracture without plastic deformation.
Figure 5 shows some examples. Only metallic
fibers behave differently.

Figure 3. Decrease of tensile strength of various inorganic

fibers made by the precursor method (room temperature ten-
sile strength) HTT = heat treatment temperature

The well-known strength decrease of glass

fibers at elevated temperatures is caused by fa-
cilitated flow processes because of lowered vis-
cosity (Fig. 4).

Figure 5. Stress – strain diagram of some inorganic fibers

The strain-to-failure (elongation at fracture)

for the brittle fibers follows precisely the ratio
strength to tensile modulus. This explains why
high-modulus inorganic fibers show the lowest
values of strain to failure, values below 0.5 %.
For reinforcement of polymers, as in advanced
composites, an elongation up to 2 % is required
by aircraft designers. This requirement is met by
the low-modulus glass fibers but not by the ad-
vanced carbon and ceramic fibers. Glass fibers,
therefore, are privileged in engineering applica-
tion if fracture toughness and impact resistance
Figure 4. Decrease in tensile strength and composition of are required without the need for extreme stiff-
glass fibers at elevated test temperatures ness. If high tensile moduli have to be main-
tained, the elongation can be improved only by
The drop in strength by postheat-treatment increasing the fiber strength (Fig. 5).
is also observed for carbon fibers and ex- It has been well known since Griffith that
plained by thermal healing of structural de- the fracture in brittle materials is initiated by ten-
fects within the polyaromatic layers, thus break- sile stresses far below the intrinsic strength of
ing cross-linkages between them. This heal- the material due to notches of a minimum – the
ing process enormously increases the tensile so-called critical length [3]:
 Fibers, 5. Synthetic Inorganic 5

length, are tested as monofilaments in a paper

E·γ frame as demonstrated in Figure 7. Each com-
σ=
C mercial testing machine can be used for this
The probability for the presence of such a purpose. A gauge length of 25 mm is the stan-
notch decreases with decreasing volume of the dard [5]. The critical problem is the determina-
tested sample. For fibers having the same diam- tion of the monofilament cross section. In the
eter, the measured values for the tensile strength case of circular morphology, the measurement
increase with shorter gauge length and if the of the monofilament diameter by a scanning mi-
same testing length is used, with smaller diam- croscope gives reproducible results. The diam-
eter of the same fiber type. Figure 1 shows the eters of the monofilaments in a bundle can vary
tensile strengths of monofilaments of commer- ± 10 % [6]. If the fibers have irregular morphol-
cial fibers as a function of the fiber diameter. ogy, only integration of the cross sectional areas
As a consequence, the efforts to develop new of the monofilaments in samples cut perpendic-
high strength inorganic fibers for reinforcement ularly to the fiber axis using optical or electronic
are directed to smaller diameter filaments, for microscopy comes into question. Figure 8
instance 5 µm. However, this way to improve The only commercial method is the strand
strength and elongation is limited by the dan- method [7].
ger of carcinogenicity of all fiber materials thin-
ner than 3 µm that have length to diameter ratio
larger than 3 ( l/d> 3)
if the fiber material is persistent in vivo. A
hypothesis concerning cancerogenic potency on
geometric parameters was published in 1978
(Fig. 6) [4].

Figure 6. Carcinogenicity of thin inorganic fibers [4]

As a further consequence, the testing method,

especially the gauge length of the fiber to be
tested for tensile strength, has to be strictly stan-
dardized.

1.3. Testing Methods for Inorganic Figure 7. Paper frame method for testing room temperature
tensile strength of thin monofilaments
Fibers A) Paper frame with the monofilament test sample fixed by
an adhesive on the frame; B) The paper frame in the holding
Inorganic fibers are characterized mainly by equipment of the testing machine; C) The paper frame after
tensile strength. Longfibers, at least 30 mm in cutting; D) The test specimen after measurement
6 Fibers, 5. Synthetic Inorganic

but can only be measured if the fibers are inbed-

ded in a unidirectional composite with a resin
as matrix and a fiber volume fraction of 60 %.
Isotropic fibers have high compressive strength,
but the fibers with anisotropic structure and high
preferred orientation parallel with the fiber axis
show lower compressive strengths. The worst
compressive strengths appear for the ultra-high-
modulus types; here, the mesophase pitch-based
carbon fibers are surpassed in a negative sense
by the high-modulus organic fibers.
The determination of the linear thermal ex-
pansion of fibers is straight-forward; however,
the determination in the perpendicular direc-
Figure 8. Distribution of tensile strength of monofilaments tion is extremely difficult. For carbon fibers
of a carbon fiber tow [6] this is important because of the high degree of
The cross section of the bundle may also be anisotropy and the variety of degrees in pre-
determined by the mass per length of the tow ferred orientation. Data from direct optical mea-
and by the pycnometer density or alternatively surements are compiled in Table 1. An indi-
by the He density of the fiber material. The pre- rect method is the comparative dilatation mea-
condition for this cross section determination is surement using the pure resin and the fiber-
a circular morphology. reinforced composite.
The term “dtex” (1 tex = 1 g per 1000 m) is Table 1. Thermal expansion of inorganic fibers
used to characterize the mass of a filament fiber;
this is the same as for synthetic organic fibers Fiber type Thermal expansion, K−1 ∗
(→ Fibers, 4. Synthetic Organic). α · 10−6 α⊥ · 10−6
A special test is the loop test, which is ap-
plicable for thicker monofilaments (see Fig. 9). Glass fiber
E glass 5.4 5.4
This test can be modified to the knot test for fast S glass 1.6 1.6
qualitative characterization of the flexibility of Carbon fiber (−0.5) – 0.2 10 – 15
CVD Monofilaments
filament fibers. SiC fibers 3.1 – 4.5 3.1 – 5.2
Oxide fibers 7.0 – 8.6 7.0 – 8.6

∗ parallel () or perpendicular (⊥) to the fiber axis

1.4. Inorganic Fibers for Thermal

Insulation
Figure 9. Loop test for low modulus A) and high modulus The use of inorganic fibers for insulation is based
B) monofilaments
  indicating
 flexibility of inorganic fibers not only on the low thermal conductivity of the
Dloop ∼ dε = d·E σ
fiber fiber material itself (one to two orders of magnitude
D = loop diameter, d = fiber diameter, ε = fiber elon- less than that of metals) but also on the large vol-
gation, E = fiber modulus, σ = fiber strength ume between the fibers. These two aspects are
discussed in detail in the chapter 2. Application
The tensile modulus is measured during the of glass fibers is limited as shown in Table 13, but
tensile strength test or nondestructively by the refractory oxide fibers allow use at much higher
ultrasonic method, which gives good compara- temperatures. Saffil fibers Al2 O3 and ZrO2 wool
tive results. from ICI are examples (see Section 3.2.4). Up-
The compressive strength of the various inor- per application temperature is ca. 1650 ◦ C. Even
ganic fibers is a further characteristic property, carbon felt can be used as thermal insulation; in
 Fibers, 5. Synthetic Inorganic 7
Table 2. Thermal conductivity of insulation layers from inorganic fibers

Measured at ◦ C in W/mK

Al2 O3 -Blanket (Saffil) 200 0.1

1000 0.26
1400 0.5
Zirkonia-Blanket (Saffil) 200 0.05
1000 0.22
1400 0.42
Silica-Wool 200 0.04
(Quarz and Silica) 800 0.14
Mullite-Texture (Nextel) RT 0.09
200 0.12
1000 0.87
Zirkonia-Insulation-Plate
Type ZYZ3 (Zircar) 400 0.09
800 0.11
1100 0.14
1400 0.19
1650 0.23
Carbon-Felt (Sigri)
HTT = 1000 ◦ C 20 0.06
HTT = 2000 ◦ C 20 0.08

For comparison thermal conductivity of various materials, measured at room-temperature in W/mK

Cu Al Steel C-Fiber Glass Polyethylene
370 175 46 12 – 23 0.9 0.23

Effect of insulation layers

Type Thickness Hotface Coldface

Mullite 1 layer (ca. 3 mm) 1000 ◦ C 500 ◦ C

(in air) 3 layers (ca. 9 mm) 1000 ◦ C 300 ◦ C
Carbon Felt 40 mm 1600 ◦ C 360 ◦ C
(in argon) 40 mm 1200 ◦ C 260 ◦ C

spite of the high thermal conductivity character- fibers, where the rule of mixtures can be ap-
istic of all carbon materials, the upper applica- plied (Fig. 10A). Comparison of the precalcu-
tion temperature in a non-oxidizing environment lated and actual composite properties reveals the
is 2000 ◦ C (see Table 2). efficiency of the translation of the fiber prop-
Mostly short fibers, such as wools, felts, tex- erties into the composite. With good adhesion
tiles, and similar fabrics, are used. Mechanical between fibers and matrix, efficiencies of 80 –
properties and variation in individual fiber thick- 100 % can be achieved, especially as far as the
ness is of little importance. moduli are concerned. Exact precalculations are
described in [8] and elsewhere.

1.5. Inorganic Fibers for Reinforcement

Purposes Figure 10 (see next page). Principles of reinforcement in
unidirectional composites
1.5.1. Principles of the Fiber Reinforcement A) Rule of mixture for strength data in fiber direction
E c = Young’s modulus of composite, E F,M = Young’s mod-
Controlled inclusion of fibers into a homoge- ulus of fiber and matrix, x F,M = Volume fraction of fiber
neous matrix produces a fiber-reinforced com- and matrix, η E = Yield of fiber modulus in the composite, a)
Fiber; b) Composite; c) Matrix
posite. The properties of the composite can be B) Angle dependence of strength a) in unidirectional long
precalculated from the properties of the tow fiber reinforced composites and b) in isotropic short fiber
components, their volume fractions, and the ge- composites [9]
ometrical arrangement of the fibers within the C) Stiffening effect by short carbon fibers in alu-
minum and thermoplastics a) C-Fiber/Thermoplastics; b) C-
isotropic matrix. The simplest case is the unidi- Fiber/Aluminum
rectional (UD) reinforcement with continuous
8 Fibers, 5. Synthetic Inorganic

Estimation of the strengths by precalcula- adhesion between fibers and matrix and the na-
tion, even in unidirectional reinforced samples, ture of the interphase contribute to the extent of
is more difficult, because the fracture processes the reinforcement effect. In addition, chemical
overlap with the reinforcement effect. If we con- and physical compatibility must be considered.
sider a polymer matrix with strain-to-failure ex- Nevertheless, the simple rule of mixtures is still
ceeding that of the fibers, which is generally the useful and reasonably valid.
case, the crack starts in the fibers. The degree of The precalculated reinforcement for UD
composites is achieved only in the fiber di-
rection. For other directions, reinforcement is
less effective. The strength of a UD composite
across the fiber axis is that of the pure polymer
(Fig. 10B) [9].
Short fibers arranged statistically in all di-
rections, produce reinforcement of 1/6 of that
precalculated for UD composites by the rule
of mixtures, but this strengthening is isotropic.
However, it should be demonstrated in each case
whether or not reinforcement is worthwhile for
a specific material combination. For example,
as shown in Figure 10C, addition of short car-
bon fibers to an aluminum matrix is not effec-
tive [10]. Precise stiffness and strength informa-
tion is a prerequisite for the successful design of
fiber-reinforced matrices.

1.5.2. Commercial Continuous Inorganic

Fibers

Mechanical Properties For a better under-

standing of the character, properties, and the
importance of today’s inorganic fibers and fu-
ture trends, a brief history is helpful. The fiber
reinforcement of polymers started during the
1930s but was not commercially successful until
the 1940s, only after the interface problem had
been solved by means of coupling agents. In the
1950s the U.S. Air Force and later the NASA
supported development of reinforcing fibers to
achieve light weight and high stiffness for future
airplanes. Boron, a light but high-melting ele-
ment, was selected as the most promising candi-
date. A new production technology was devel-
oped: chemical vapor deposition on thin tung-
sten wires. The boron fibers fabricated in this
way are monofilaments with diameters between
120 and 150 µm and have more the character of
thin wires than that of fibers. Therefore chemists
started to develop filament fibers from the neigh-
boring element carbon, which is also light and
has a high melting point, and from which fibers
have been demonstrated 100 years earlier as fila-
 Fibers, 5. Synthetic Inorganic 9
Table 3. Mechanical and physical properties of the representative inorganic fibers

Fiber type Room temperature properties

Density, Tensile Tensile

g/cm3 strength, modulus,
MPa GPa

Glass fiber 2.50 – 2.62 3400 – 4500 70

Carbon fiber 1.76 – 2.10 2000 – 7000 240 – 700
CVD ∗ Monofilaments
SiC fibers 2.55 – 3.50 2000 – 3700 200 – 420
Oxide fibers (whisker) 3.90 1200 – 1400 340 – 400

∗ CVD = chemical vapor deposition

ments for electric light bulbs. The high stiffness fibers, and Al2 O3 fibers. The physical and
was achieved by hot working, similar to the pro- mechanical properties are compiled in Table 3.
cessing of metal wires. Real technical success The specific strengths and tensile moduli are
was achieved, however, only after this high-tem- presented in a more schematic way in Fig. 11
perature forming process became superfluous [12]. All mechanical properties are determined
upon introduction of the preferred orientation in at room temperature and under standard condi-
the process step before thermal decomposition tions. Composites with these stiffnesses are brit-
of the polymer fiber to the carbon fiber. These tle, however. The impact resistance of the vari-
carbon fibers, which can be handled like glass ous fibers is therefore an important criterion for
fibers, have completely replaced boron fibers in their application. Carbon fibers behave worst in
their function of stiffening polymer composites. this respect in spite of the other overwhelmingly
They are widely used today in combination with excellent properties, as shown in Table 4 (see
glass fibers in so-called advanced hybrid com- next page). One way to overcome this brittle-
posites. Boron fibers on wire substrates have ness is to mix the carbon fibers with glass fibers
also been used to reinforce light metals. But in (Fig. 12). Organic polyaramide fibers (Kevlar
this field, too, a new competitor has appeared, from DuPont or Twaron from ENKA) are in-
namely, CVD-SiC fibers, thick monofilaments, cluded in Table 4 and Figure 12 to allow com-
much like thin wires. Silicon carbide is oxida- parison.
tion resistant in air up to 1400 ◦ C, but has a den-
sity of 3.5. It is heavier than the light metals or
boron. It is a superior fiber component in SiC
and Si3 N4 ceramics, especially for toughening.
The troublesome CVD technique and the stick-
ing of the monofilaments, both dangerous for the
workers, have led to the development of a new
competitor, SiC and Si3 N4 filament yarns, which
are fabricated much like carbon fibers by ther-
mal degradation of polymeric precursor fibers,
carbosilanes, and silazanes. For oxide compos-
ites, refractory oxide fibers are best. Fabrication
techniques starting from organometallic precur-
sor fibers as shown above, have so far produced
only low-strength fibers, but improvement can
be expected. Fabrication from ultrafine crys-
talline powder produces higher strength fibers
[11].
Commercially available today are glass
Figure 11. Mechanical room temperature properties of in-
fibers, carbon fibers (HT and HM types), CVD organic fibers in a stress – modulus diagram [12]
boron, SiC monofilaments, SiC and Si3 N4
10 Fibers, 5. Synthetic Inorganic
Table 4. Qualitative comparison of mechanical properties of glass, polyaramid, and carbon fibers

Static load Dynamic load

Strength Modulus Impact Fatigue Ilss Temperature Density

Tensile Flexural Compressive Tensile Flexural Compressive resistivity

Glass
+ ◦ + − − − + − + ◦ −
Aramide
◦ − − ◦ ◦ ◦ ◦ ◦ ◦ − +
Carbon
+ + ◦ + + + − + + + ◦

+ = better than average; ◦ = average; − = less than average

Ilss = interlaminar shear strength

layer to protect the fiber surface and to im-

prove the handling of the brittle fiber mate-
rial. The most common sizing materials are
poly(vinyl alcohol) and uncured epoxy or poly-
imide resins. Glass fibers are coated by coupling
agents, usually silanes, to improve adhesion in
the matrix resins, which are usually unsaturated
polyesters and, in advanced composites, epoxy
resins. Glass fibers have silanol groups on the
surface, which can react easily with functional
groups in the resin. As such, interfaces within the
Figure 12. Improvement of impact strength of carbon fiber-
composites are very sensitive to attack by water,
reinforced composites by polyaramide (Kevlar) and glass and the glass fibers must be protected by lin-
hybridization, respectively ear organic molecules that have a hydrophobic
group on one end of the molecule. The mecha-
nism of protection is indicated in Figure 13 [13].
1.5.3. Surface Chemistry, Surface Carbon fibers are thoroughly wetted by the
Treatment, and Surface Properties various polymers if they possess such functional
surface groups as acid and basic surface oxides
All commercial inorganic fibers are sized, i.e., [14]. Also, the adhesion in the composite is ex-
coated with a thin organic, usually polymeric, plained by chemical interchange with these sur-

Figure 13. The effect of coupling agents for glass fibers in polymers (schematic) [13]
 Fibers, 5. Synthetic Inorganic 11

face groups. The surface oxides are formed on Even in the case of reinforcement of aluminum,
the carbon fibers as the last step during fabrica- boron fibers must be coated by diffusion barri-
tion. All commercial carbon fibers are surface- ers, thin layers of SiC or B4 C deposited from
treated and sized in this way. The process pa- the vapor as the last step of the fabrication pro-
rameters of the surface treatment strongly influ- cess (Fig. 15) [16, 17]. SiC fibers are compatible
ence the degree of surface oxidation, and thus the with polymers, and generally with most inor-
character of the interfaces within the composite. ganic materials, if 1000 ◦ C is not exceeded. Re-
Surface treatment is, however, usually a propri- fractory oxide fibers would be ideally suitable
etary process kept secret by the supplier. The for combination with light metals if properties
suitability of the commercially surface treated and economic considerations justify it.
and sized fibers must be tested and confirmed
by the user.
Adhesion between fiber and matrix plays an
important role in respect to the impact resistance
of the composite. Dependant on the strain-to-
failure of the fiber, impact resistance can be im-
proved or worsened by a high degree of adhe-
sion, which in turn is determined by the degree
of surface oxidation [15]; Figure 14 shows some
correlations.

Figure 14. Impact strength of carbon fiber-reinforced uni-

Figure 15. Boron fiber fabrication on tungsten substrate by
directional composites as a function of fiber strain for the
the CVD process (chemical vapor deposition) [16]
untreated and surface-treated state
U: Untreated; S: Surface treated

The chemical compatibility with the matrix

1.5.4. High-Temperature Behavior of
is another criteria for inorganic reinforcement
Inorganic Fibers
fibers. Glass fibers are compatible with poly-
mers, with most oxides, but not with concrete. Glass fibers are limited to temperatures below
Carbon fibers are also compatible with poly- ca. 300 ◦ C. Carbon fibers are not resistant to
mers, and in addition they are compatible with oxidation above 400 ◦ C, but are thermally sta-
concrete. They are not compatible with most ble up to 2000 ◦ C in non-oxidative environ-
metals, with the exception of lead and tin. They ments. They can be applied in all high-tem-
are incompatible with oxides above 400 ◦ C. Sur- perature polymers without restriction. For the
face coatings as diffusion barriers improve the highest temperatures, the performance of PAN-
chemical compatibility. Boron fibers are com- based carbon HM-fiber must be considered as
patible with polymers, but react with metals. exemplary. They can be used in composites with
12 Fibers, 5. Synthetic Inorganic

carbon as matrix without limitation (carbon – 2. Glass Fibers

carbon composites [18]), but diffusion barriers
are needed in the cases of matrices of oxides, 2.1. Textile Glass Fibers
metals, and non-oxidic refractory compounds
[19]. Some examples are given in Figures 16, Textile glass fibers have gained in importance in
17, and 18 [20]. All other refractory fibers lose spite of the availability of other, newer reinforc-
their room-temperature strength values if heat- ing fibers, such as carbon or aramid fibers [21–
treated above 1200 ◦ C because of crystallization 25]. A large part of this growth is a result of glass
processes (see Figs. 3 and 4). Inorganic fibers re- fiber-reinforced plastics (GRP). The market for
sistant to high temperatures are a fertile field for GRP in the Federal Republic of Germany has
further development. grown from ca. 10 000 t in 1960 to ca. 200 000 t
in 1985.
Glass fibers that can be processed by con-
ventional textile techniques such as weaving are
called textile glass fibers, to contrast them with
insulation glass fibers. Textile glass fiber is a
collective term for fine fibers possessing an ap-
proximately uniform, mostly circular cross sec-
tion made from molten glass. The terminology
of textile glass and processing aids is standard-
ized in national and international standards.
Depending on the manufacturing process,
textile glass fibers are subdivided into (1) glass
filaments and (2) glass staple fibers, which are
defined as follows in ISO 6355:
1) A glass filament is a textile glass fiber of prac-
tically unlimited length of a given diameter
drawn from molten glass.
2) A glass staple fiber is a textile fiber of limited
Figure 16. Reinforcement effect by carbon fibers with sili- length (spun fiber) and of a given diameter.
con carbide coatings in quartz glass [20]
σ F , σ C , σ M = stress of fibre, composite, and matrix respec- Textile glass is used both for textile purposes,
tively; εF , εC , εM = strain of fibre, composite, and matrix e.g., decoration, insulation, filtration, as well as
respectively for reinforcement of a matrix to form a com-
posite. Matrices can be plastics (both thermo-
setting and thermoplastic), bitumen, rubber, ce-
ment, gypsum, or other materials. Of all glass
filaments ca. 90 % are used to reinforce a ma-
trix.
Textile glass fibers can also be categorized
by the type of products and the diameter of the
filaments:
1) Textile products, such as textile glass yarns
and plied yarns with filament diameters of
5 – 13 µm
Figure 17. Strengthening and toughening of mullite by sil- 2) Plastic products such as mats, rovings,
icon carbide-coated carbon fiber chopped strands, and milled fibers with fil-
A) Al2 O3 Matrix; a) 10 %, b) 54 % and c) 32 % coated ament diameters of 9 – 24 µm
B) Mullite – Matrix; a) 28 %; b) 41 % and c) 34 % coated
The textile products are mostly woven and are
then available as fabrics for reinforcing plastics
 Fibers, 5. Synthetic Inorganic 13

Figure 18. Toughening of alumina by silicon carbide coated carbon fibers a) Uncoated C-Fibers; b) SiC-Coated C-Fibers

and other applications such as thermal insulation Brunfaut. The inventor of the bushing, how-
and decoration. ever, was Louis Schwabe, who first produced
Plastic products can be manufactured to parts glass yarns by drawing the melt through fine
by hand lay-up, winding, molding, etc. (Chap- holes. In 1908, a rather coarse, endless glass fiber
ter 4). was demonstrated in Hamburg by W. v. Paczin-
History.The technique of ornamenting glass sky. True industrial production of textile glass
vessels with glass yarns was used in ancient fibers was realized in the United States in 1930
Egypt around 1600 b.c. and developed fur- and in Germany in 1939.
ther by the Romans. In the Middle Ages, this
technique–based on drawing heated rods into
fine filaments–was further refined in Venice and 2.1.1. Chemical Composition and Properties
Murano.
The first indications of the use of glass yarns Chemical Composition. The chemical
in fabrics are found in the work of the physi- composition of glass fibers essentially deter-
cist Ferchault de Reaumur in 1713. The first mines the properties and the applications. Ta-
known factory for the manufacture of glass yarns ble 5 shows the known types of textile glass
was founded in 1866 in Vienna by Jules de fibers and their compositions.

Table 5. Chemical composition of textile glass (nominal values, wt %)

Component Types of glass

Multi-purpose Acid resistant Alkali resistant High strength Good dielectric properties

E A C E-CR [31] R S D Quartz

SiO2 53 – 55 70 – 72 60 – 65 58 60 60 60 – 65 73 – 74 100
Al2 O3 14 – 15.5 0 – 2.5 2–6 12 – 13 0.7 25 20 – 25
CaO 20 – 25 5–9 14 21 5 6 0.5 – 0.6
MgO 20 – 25 1–4 1–3 4.5 9 10
B2 O 3 6.5 – 9 0 – 0.5 2–7 <0.1 0 – 1.2 22 – 23
F 0 – 0.7 <0.15
Na2 O ≤1 12 – 15 8 – 10 0.6 14 0 – 1.1 1.3
ZrO2 ≤1 18
K2 O ≤1 1 0.4 1.5
Fe2 O3 ≤1 0.3 0.1
TiO2 ≤1 2.1
14 Fibers, 5. Synthetic Inorganic

The following types are recognized: where high tensile strength is needed, e.g., in
containers under high internal pressure.
E glass. An alumino-borosilicate glass with a
The raw materials for the components are
mass fraction of alkali ≤1 %, which is gen-
largely natural minerals. They are subject to
erally used in glass-reinforced plastics and in
stringent quality control when received, since
electrical applications
the raw materials must be within narrow, well-
A glass. An alkali-lime glass with little or no ad-
defined limits to produce textile glass fibers hav-
dition of boron trioxide and a mass fraction
ing uniform properties.
of alkali ≥1 %, for special applications
E-CR glass. An alumino-lime silicate glass with
Properties. Textile glass fibers are distin-
a mass fraction of alkali ≤1 %, especially
guished by particularly high tensile strengths.
suited for the reinforcement of plastics be-
Measurements on filaments drawn directly from
cause of acid resistance
the bushing yield values of 3400 MPa for E glass
C glass. An alkali-lime glass with high boron tri-
and 4400 MPa for R glass (Table 6).
oxide content, with good chemical resistance
The modulus of elasticity, which is 1/3 that
for special applications
of steel and quite adequate for many applica-
D glass. A borosilicate glass, a specialty glass
tions, and the density of 2.6 g/cm3 , which is high
with high dielectric properties
compared to plastics, are not sufficient for large-
R glass. An aluminosilicate glass without added
surface, light-weight parts (airplane construc-
calcium and magnesium oxides, glass that
tion). For such parts, fibers of lower density and
meets high mechanical requirements
higher modulus of elasticity (aramid and carbon
S glass. An aluminosilicate glass without added
fibers) were developed.
calcium oxide but with a mass fraction of
Textile glass fibers have a linear stress – strain
magnesium oxide of ca. 10 %
curve up to the break, so that the break elonga-
The most widely used are E-glass fibers, tions εB can be calculated from the modulus of
which are encountered in all areas of indus- elasticity E and the tensile strengths σ B (Fig. 19,
try and everyday life, especially in combination see next page). Good resistance to weathering
with plastics (Chapter 4). In glass staple fibers, and heat, nonflammability, good dielectric prop-
C glass is used primarily [29]. erties, low thermal expansion, and, depending
More recently, acid-resistant E-CR-glass on the type of textile glass, good resistance to
fibers have been used in special projects such as corrosion, are additional characteristics of tex-
pipes for flue-gas desulfurization plants. Alkali- tile glass fibers. The thermal conductivity of tex-
resistant glass fibers are primarily intended for tile glass products is determined by the density
cement reinforcement. of fiber packing. The properties of textile glass
High-strength textile glass fibers such as R- fibers to a great extent determine the properties
and S-glass fibers are preferred in applications of the composites (→Composite Materials).

Table 6. Properties of textile glass (nominal values)

Property Types of glass

Multi-purpose Acid resistant Alkali resistant High strength Good dielectric properties

E A C E-CR [31] R S D Quartz

3
Density, g/cm
Bulk glass 2.61 2.46 2.46 2.55 2.16 2.2
Fiber glass 2.59 2.45 2.70 2.68 2.53 2.48 2.14
Modulus of elasticity,
MPa 73 000 74 000 71 000 72 000 76 000 86 000 85 500 55 000 6200 – 7200
Tensile strength, MPa
Freshly drawn fiber 3 400 3 100 3 100 3 330 3 700 4 400 4 590 2 500 400 – 500
Fiber in composite 2 500 2 400 3 750 1 550
Dielectric constant
at 1 MHz 5.8 – 6.4 6.8 7 5.6 – 6.2 4.9 – 5.3 3.85 3.78
 Fibers, 5. Synthetic Inorganic 15

2.1.2. Manufacture
2.1.2.1. Glass Filaments
Glass filaments are produced continuously by
the bushing fiberizing process. There are two
commercial processes for the manufacture of
glass filaments: the marble melting process and
the direct melt process.
In the older indirect marble melting process,
the production of glass and the glass spinning Figure 19. Stress – strain curves of five fibers
process are separate. E glass is initially produced a) Carbon fiber, high modulus; b) Carbon fiber, high strength;
in the form of glass marbles (15 – 20 mm diame- c) Aramid fiber, high modulus; d) R-glass fiber; e) E-glass
ter), which are then re-melted in a second phase fiber σ B = tensile strength; εB = break elongation
in the glass forming process (two-stage process).
of heated feeders (channels) in which the bush-
This process is still in use today for making fine
ings are placed. In this one-step process, there
filament yarns.
is no separation between glass manufacture and
In the direct melt process, molten glass flows
glass forming (Fig. 20). Temperatures in the pro-
directly from the melting furnace into a system

Figure 20. Direct melting

a) Mixing silos; b) Furnace feed; c) Furnace; d) Heat exchanger; e) Melt; f) Bushing; g) Sizing applicator; h) Cake winder;
i) Spun cake
16 Fibers, 5. Synthetic Inorganic

duction of E glass are 1310 – 1390 ◦ C in the fur-

nace and 1225 – 1260 ◦ C in the feeders [24].
In principle, the fiber forming process in-
volves attenuating glass filaments continuously
from a Pt – Rh bushing by applying a mechanic
drawing force at offtake speeds of up to 80 m/s
(Fig. 21). Bushings may have 400, 800, 1200,
1600, or more holes of 1 – 2.5 mm diameter. A
single filament is drawn from each hole. The
filaments are collected into a bundle (strand)
and wound as a spun cake or directly pro-
cessed into rovings, continuous strand mats, or
chopped strands. The deformation during draw-
ing is high: for example, with bushing-tip diam-
eters of 2 mm and a filament diameter of 10 µm.
A typical ratio of cross sections is 40 000 : 1 Figure 22. Bushing
(Fig. 22). a) Bushing nipple; b) Drawing bulge D = hole
diameter; d f = diameter of glass filament

where
F p = force due to hydrostatic pressure
F g = force of gravity
F σ = force due to surface tension
F η = force due to viscosity
F d = drawing force
F a = sum of frictional forces
The viscosity of the melt must be increased
sharply by cooling with air and water to enable
a filament to be formed in the shortest possible
time after the melt leaves the bushing tip.
An aqueous solution, called size or sizing,
is applied to the cooled filaments; this solu-
tion consists basically of film formers, lubri-
cants, and, if necessary, coupling agents. After
the forming packages are dry, the sizing (0.5 –
Figure 21. Spin-draw process (schematic)
1.5 wt %) has two functions:
a) Bushing; b) Water spray; c) Sizing application; d) Strand
guide; e) Spun cake 1) Reducing the glass – glass coefficient of fric-
tion from ca. 1.0 to 0.2 to make further pro-
cessing of the yarn possible. Due to the high
Formation of the filaments involves two basic coefficient of friction, textile glass strands
processes: without size cannot be processed further
1) efflux of molten glass from the bushing tips since they cannot be pulled off the cakes.
under the condition that 2) Imparting properties that are prerequisite for
further application of the textile glass prod-
Fp +Fg >Fη +Fσ ucts as plastic reinforcement (plastic prod-
ucts) or as textile products with optimum
2) drawing of the meniscus at the bushing tip
weaving and desizing properties.
to a continuous filament by a force under the
condition that
Fd +Fg >Fa +Fσ
 Fibers, 5. Synthetic Inorganic 17

2.1.2.2. Glass Staple Fibers C = C glass

D = discontinuous
The principles discussed with regard to the draw- 11 = nominal fiber diameter in µm
ing of glass filaments also apply to glass staple 200 = tex ∗
fibers, but the manufacturing processes them- Z140 = Z-twist, 140 turns per meter
selves are different.
∗ One tex is equivalent to 1 g/1000 m. For
In the bushing blowing process, the molten
glass filament products the relationship between
effluent is fibrillated by streams of gas. Adhe-
the number of holes in the bushing N, the fila-
sive sizing is added, and the fibers are collected
ment diameter d f , and the tex number is:
on a rotating perforated drum or on a suction belt
(nonwovens) under reduced pressure. tex = 0.002d2f ×N
In the drum drawing process, fibers are drawn
either from bushings or from rods by a rotat- where d f is in µm. The density of glass G is
ing drum and scraped off. During the drawing taken to be 2.5 g/cm3 .
process, sizing is applied to the fibers for later The other textile glass products are desig-
cementing. The fibers broken by scraping are nated in a similar manner.
swirled in a funnel. Typical properties of products used in textiles
In both processes the fibers are finally con- and plastics are summarized in Tables 7 and 8.
solidated in a finishing tube and drawn off as a
sliver. The sliver can be converted directly into
fabrics, yarns, or plied yarns. 2.1.3.2. Correlation Between Processing and
Application

2.1.3. Textile Glass Products: Processing Textile glass fibers can be processed as follows:
and Application
1) Textile processes such as weaving, knitting,
2.1.3.1. Product Designation and braiding, suitable for textile glass yarns,
plied yarns, and rovings
Glass filament and glass staple yarns have a stan- 2) Plastic processes for reinforcing thermo-
dard form of designation. setting and thermoplastic resins, suitable for
Glass Filament Yarns (ISO 2078 and textile glass fabrics, layers, knits, mats, rov-
ISO 3598) EC9-34 Z28 – sizing x ings, milled fibers, tissues, and chopped
strands
E = E glass 3) Processes for reinforcing other matrix mate-
C = continuous rials, e.g., bitumen, paper, rubber, gypsum,
9 = filament diameter in µm and plaster, suitable for textile glass fabrics,
34 = tex ∗ yarns, surface mats, rovings, and chopped
Z28 = Z-twist, 28 turns per meter strands
Glass Staple Yarns(ISO 2078 and ISO 3598) The processes used in plastic reinforcement
CD11-200 Z140 are summarized in Table 9 (see next page).

Table 7. The tex number of textile glass yarns as a function of filament diameter and number of filaments in a strand

Filament diameter Number of filaments per strand

µm Nominal U.S. 50 100 200 400 800 1600

µm System

5.2 5 D 2.8 5.5 11

6.4 6 DE (17) 34 68 136
7.4 7 E 11 22
9.2 9 G 34 68 136 272
11.3 11 J 51 102 204 408
13.0 13 K 136 272 544
18 Fibers, 5. Synthetic Inorganic
Table 8. The tex number of glass yarns for plastic reinforcement as a function of filament diameter and number of filaments in a strand

µm Nominal µm U.S. System Number of filaments per strand

50 ∗ 100 ∗ 200 ∗ 400 800 1600 2000 4000

10.0 10 H 10 20 40 80 160 320

11.3 11 J 12.5 25 50
14.2 14 L 160 320 640
17.3 17 N 480 960 1200 2400
19.4 19 OP 600 1200
24.5 24 ST 2400 4800

∗ Strands separated during spinning

Table 9. Processing of glass-reinforced plastics (GRP)

The entire line of products is presented in Fig-
Process Textile glass products ure 23 (see next page).
Textile glass yarns usually have a protective
Glass-reinforced
thermosetting resins: twist and are sold with textile or plastic sizes.
Manual processes Textile sizes based on starch/fats are especially
Hand lay-up chopped strand mat, woven
fabric, surface mat
suitable for high-speed looms, e.g., air looms.
Fiber/resin spray-up roving For certain applications, e.g., circuit boards for
Intermediate processes printed circuits, the textile finish applied to the
Injection process surface mat, continuous mat
Vacuum injection process surface mat, continuous mat fiber must be removed and replaced by an adhe-
Wet molding surface mat, continuous mat, sive finish (coupling agent) via a special treat-
woven fabric
Industrial processes
ment given to the fabric.
Processing of semi-finished (compression molding, Textile glass fabrics come in different
products injection molding) weaves, depending on the application.
Prepregs woven fabric
SMC ∗ roving Textile glass rovings with untwisted, approx-
Molding compounds chopped strands imately parallel filaments or strands are offered
Rotation process roving, woven fabric
Reinforcement of polyurethane milled fiber, continuous mat
with inside or outside take-off. Textile glass rov-
Filament winding roving, woven fabric, ings are either assembled into a larger strand
chopped strand mat comprising several strands or produced by a di-
Continuous impregnation continuous mat, chopped
strand mat, woven fabric rect process below the bushing. In the second
Pultrusion roving, woven fabric, process roving strands of various tex numbers
continuous mat, chopped
strand mat
are obtained by changing the number of holes in
the bushing or by changing the filament diam-
Glass-reinforced eters. Spun rovings of textile glass are suitable
thermoplastic resins:
Injection molding of glass milled fiber, roving, chopped for the pultrusion process because of their good
fiber-reinforced granulate strands mechanical properties in the transverse direc-
Compression molding of glass
mat-reinforced tion.
thermoplastic plates continuous mat, roving Textile glass mats are made from chopped
∗ SMC = sheet molding compounds
strands (chopped strand mats) or of strands laid
up directly below the bushing (continuous strand
mats). Consolidation in both cases is accom-
plished by chemical binders. Chopped strand
2.1.3.3. Description of Textile Glass Products mats are used primarily for hand lamination;
continuous strand mats for all types of injection
There are separate standards for special prod- molding, compression molding, and continuous
ucts: impregnation (Table 5).
Chopped strands with lengths of 3, 4.5, 6, or
textile glass rovings ISO 2797
textile glass mats ISO 2559 12 mm have been found useful in the production
textile glass fabrics ISO 2113 of molding compounds and as reinforcement of
glass filament yarns ISO 2078 and ISO 3598
glass staple fiber yarns and rovings ISO 2078 and ISO 3598 thermoplastics. As shown in Figure 5, chopped
strands are either cut directly below the bushing
 Fibers, 5. Synthetic Inorganic 19

Figure 23. Textile glass products

Stages 1 – 3 are in the hands of the textile glass producers, while Stage 4 is in the hands of the processors, e.g., weavers

or produced from intermediate products, e.g., textile glass knits, which take the place of plaster
textile glass roving or glass strands. casts.
Milled textile glass fibers with fiber lengths Warp beams are used in the preparation of
of 0.2 mm are suitable as reinforcement of ther- warps for weaving and consist of a multiplic-
moplastics and polyurethane foams. In addition, ity of yarns wound in parallel. Beams of strands
they are used in the production of primers, fire- with plastic sizing are used for unidirectional re-
protection coatings, and the like. inforcement of plastics for the bumper systems
Tissues of glass filaments or glass staple of motor vehicles.
fibers are produced both by dry and wet pro-
cessing. In both cases the fibers are chemically
bonded. 2.1.3.4. Applications
Because of their bulky nature, textured rov- As seen in Table 10 (on next page) there is a
ings or yarns have turned out to be good replace- distinct trend toward the use of GRP in motor
ment products for asbestos, e.g., in the manufac- vehicles, both passenger cars and trucks. Glass
ture of clutch facings. Textured yarns are also fiber reinforced thermosetting resins are used in
used in decorative fabrics. passenger cars primarily for body parts (hoods,
Layersare planar structures of bonded, non- tail gates) and for structural elements (bumpers,
woven textile glass yarns with crisscross or par- bumper supports). Glass fiber reinforced ther-
allel yarns. Layers are primarily used for rein- moplastics are used for operating parts within
forcing paper or bitumen or in the preparation the engine compartment, noise suppressors be-
of prepregs (preimpregnated sheets). low the engine, hub caps, etc.
Textile glass knit goodsare more elastic than Textile glass fabrics for epoxy resin prepregs,
woven fabrics of textile glass. One area of appli- the basic material of circuit boards, is not consid-
cation is medical bandages of pre-impregnated ered to be GRP but rather is considered among
 20 Fibers, 5. Synthetic Inorganic
Table 10. Percentage of textile glass fibers used to reinforce resins by area of application in the Federal Republic of Germany, 1973 and
1985 [32]
Area Thermosetting resins (except circuit boards) Thermoplastic resins

1973 1985 1973 1985

Construction 24 16 0 1
Industry and agriculture 32 24 23 12
Transport 9 25 25 55
Consumer goods 6 4 14 6
Sport and leisure articles 6 3 0 0
Electronic industry 17 25 36 23
Other 6 3 2 3

other applications. However, it is the most im- ceptance standards, which list minimum require-
portant such other application, representing one- ments. In order for the values determined to be
third of the amount used for other applications. comparable and reproducible, standardized test
The following other applications are of im- procedures are used in which all testing condi-
portance: tions are specified precisely.
Processors of textile glass products should
1) Thermal insulation and heat protection (an store the products in dry rooms at temperatures
asbestos replacement) with woven glass fab- below ca. 25 ◦ C at a relative humidity level bet-
rics of glass filament and glass staple fiber ween 55 and 65 %. Exposure to direct sunlight is
yarns for primary insulation jackets, heat to be avoided. Prior to processing, the material
shielding curtains, fire blankets, pipe insu- should be equilibrated under the temperature-
lation, etc. humidity conditions present in processing.
2) Wall coverings of staple fiber yarns
3) Plaster reinforcement of textile glass mesh
fabrics and textile glass nonwovens 2.1.5. Toxicology and Occupational Health
4) Reinforcement of grinding wheels with wo-
ven glass fabrics Textile glass products do not represent a health
5) Filter materials for high-temperature filtra- or environmental hazard, mainly because of the
tion with woven glass fabrics and nonwovens following properties:
6) Bitumen reinforcement with blend fabrics of
glass staple fiber yarns, glass filament yarns, 1) Textile glass fibers do not contain poisonous
and textile glass nonwovens and/or hazardous components.
7) Gaskets with glass cord and glass twine (an 2) Fiber structure, because of the chemical com-
asbestos replacement) position, is affected by body fluids in such a
8) Decorative fabrics of textured glass filament way as to reduce the carcinogenic potential.
yarns and glass staple fiber yarns 3) Textile glass fibers do not split longitudinally,
9) Expansion joints of impregnated woven glass which largely prevents their penetration into
fabrics the alveoli of the lungs.
10) Cable insulation and reinforcement with tex-
tile glass yarns Extensive systematic examinations of many
11) Reinforcement of adhesive tapes with textile thousands of people working for decades in the
glass yarns production and processing of textile glass prod-
ucts have shown that continuing exposure to
textile glass fibers does not produce increased
morbidity or mortality rates. Likewise, innumer-
2.1.4. Product Standards able animal experiments (inhalation and inges-
tion of textile glass fibers as well as skin contact)
The textile glass standards described in Section 4 have revealed no fibrinogenic or carcinogenic
contain supplementary basis sheets with speci- changes in test animals, a contrast to asbestos.
fications. Beyond that, there are customer ac-
 Fibers, 5. Synthetic Inorganic 21

2.1.6. Economic Aspects mechanical or pneumatic processes. For insula-

tion, nontextile fibers are used exclusively. Such
The growth of textile glass fiber production fibers are also called glass wool, slag wool, rock
is illustrated by comparing the total figure of wool, or mineral wool.
1 135 000 for 1985 (Table 11) with that for 1973, While the manufacture of glass filaments
865 000 t. A 56 % increase was achieved. goes back to antiquity, it was not until 1840
Table 11. Production of textile glass fibers by final use and
that the production of nontextile man-made min-
geographic region, 1985 [33] eral fibers (MMMF) was demonstrated in Wales
Area Production, t [34]. This was an effort to utilize blast furnace
slag and at the same time to find a replacement
Uses in glass Other uses, including for natural asbestos. In the United States, rock
fiber reinforced fabrics for circuit
resins boards wool production is documented to have taken
place in 1893 [35]. An early patent for glass
United States,
Mexico, Canada 520 000 80 000 wadding by the centrifugal process was granted
Western Europe 240 000 65 000 in 1912, but industrial exploitation of the pro-
Japan and Korea 165 000 35 000
Eastern Europe,
cess did not occur until 1930 [36]; the blowing
Former States of 155 000 40 000 process for glass wool, still in use today, was
USSR, China patented in 1933 [37].
Others 50 000
Total 1 130 00 220 000 The hope to replace asbestos could not be re-
alized. Instead, these products found their own
areas of application. Synthetic resin binders
were developed around 1950, which made possi-
2.1.7. Producers ble the production of dimensionally stable prod-
ucts and assured a uniform quality for insulation.
The principal producers of textile glass fibers are
listed in Table 12.
2.2.1. Physical Properties
Table 12. Companies producing textile glass fibers and the
location of their plants
Fibrous insulating materials of man-made min-
Company Location of plants
eral fibers are a highly disperse system of finely
Asahi Fiberglass Japan divided fibrous glass with a specific surface of
Certain Teed Corp.
Fiberglass Ltd.
United States
Great Britain
0.1 – 0.2 m2 /g. The fibers are oriented predom-
Glaswerk Schuller ∗ Federal Republic of Germany inantly in the horizontal direction. For this rea-
Manville Corp. United States son, the material is isotropic in two dimensions
Nippon Electric Japan
Nippon Glassfiber Japan but not in the third. It is an open-pore system
Nitto Boseki Japan with little resistance to flow. This is the basis for
Owens Corning Fiberglass United States, Belgium, France
Pittsburgh Plate Glass (PPG) United States
its thermal and acoustic properties.
Scandinavian Glassfiber Sweden The fiber diameters are distributed over a
Silenka The Netherlands broad spectrum. The logarithm of the fiber diam-
Skloplast Former Czechoslovakia
VEB Glasseidenwerk Oschatz Former German Democratic eter approximately follows a normal distribution
Republic (Fig. 24, see next page). The minimum fiber di-
Vetrotex Federal Republic of Germany ∗∗
(Gevetex), France, Italy, Spain
ameter is process dependent and is between 0.18
Vitrofil Italy and 0.30 µm [38]. However, the properties of the
individual fibers are less important than those of
∗ Glaswerk Schuller specializes in staple fibers.
∗∗ The Vetrotex subsidiary Gevetex operates the plant in Germany. the final insulating material, i.e., the fibers and
binder as a whole.
Table 13 (see page after next) lists the limit-
ing temperature in use which is affected by the
2.2. Glass Fibers for Insulation chemical composition, the fiber diameter, the
amount and type of binder as well as the bulk
Glass fibers for insulation are fibers of vitre- density and the actual conditions of installation.
ous structure produced from silicate melts by
22 Fibers, 5. Synthetic Inorganic

Figure 24. Distribution of fiber diameters in glass and rock wools

The most important property of insulation is bles are mineral oils, emulsifiers, silicones, and
the thermal conductivity, which is shown in Fig- low molecular mass components of binders.
ure 25 for 14 mineral wools. The thermal con- Water and aqueous solutions attack the glass
ductivity of a particular fibrous material is de- surface, the attack magnified by the large fiber
termined by its bulk density B and its average surface. Attack by water also loosens the fiber –
fiber diameter D. The mechanical properties are resin bond. Calciferous products (slag wool,
primarily determined by bulk density and binder rock wool) are soluble in acids and are attacked
content; in any case, however, fibrous insulating by acid flue gases.
materials cannot be used as load-bearing struc-
tural units.
2.2.3. Raw Materials and Chemical
Composition
2.2.2. Chemical Properties
Glass wool (wadding, fibers) are produced from
Mineral wool insulation is inert to organic sol- mixtures of minerals and industrial chemicals
vents, even at elevated temperatures. Extracta- that produce the required final composition. In
 Fibers, 5. Synthetic Inorganic 23
Table 13. Chemical composition, fiberization process, and limiting temperature in use of glass fibers for insulation

Glass wool Rock wool Slag wool

1 2 3 4 5 6 7 8 9

Composition, wt %
SiO2 57.4 64.6 53.9 52.7 46.3 47.6 46 46.8 40.2
Al2 O3 3.6 2.9 3.6 8.0 13.3 10.2 15 10.2 15.6
Fe2 O3 0.35 0.35 0.35 1.8 5.6
6.5 ∗ 0.9 ∗
FeO 0.10 0.10 0.09 1.4 6.3 7.3 1.0
MnO 0.05 0.2 0.3 0.3
TiO2 0.1 0.6 2.9 1.9 1.5 0.7
ZrO2 4.0
MgO 4.0 3.1 4.6 4.0 9.7 12.0 12 2.3 4.35
CaO 8.6 6.6 23.4 20.9 10.9 14.8 16 37.7 34.9
BaO 1.8 2.4
Na2 O 11.2 14.0 9.4 10.3 2.6 1.6 2.5 0.9
K2 O 1.7 1.1 1.0 0.6 1.3 1.6 0.6 1.5
B2 O 3 5.0 5.9 3.0 0
F 2.3 0 0 0

Fiberization
process ∗∗ C C A A A B B D D

Limiting temperature
in use, ◦ C 570 550 700 700 750 750 750 730 700

∗ Fe2 O3 and FeO.

∗∗ A) Owens process; B) Rock wool process; C) Rotary process; D) Centrifugal blowing process. These four processes are
illustrated in parts A, B, C, and D, respectively, of Figure 26.

addition to quartz sand, the minerals used in- The glass melting tank furnaces are similar in
clude limestone, dolomite, phonolite, feldspar, construction to those used in other areas of glass
nepheline-syenite, kernite, colemanite, ulexite, manufacture [39]. Preferred are cross-fired recu-
and heavy spar (barite). The industrial chemi- perative furnaces and U-shaped flame furnaces,
cals include sodium carbonate, sodium sulfate, but all-electric melters are also used if energy
and barium carbonate. The use of recycling glass costs are right. Maximum productivity is 300 t/d,
has gained considerable importance. and up to 3.5 tm−2 d−1 can be achieved. Cupola
In contrast, rock wool and slag wool are, as a furnacesare used to produce molten rock. They
rule, prepared from a single mineral raw material require coarse feed and yield a less uniform melt.
of suitable composition, such as basalt, rhyolite, The traditional fuel is coke but oil- or gas-fired
or diabase. To improve meltability, limestone is units are also used. Furnace productivity rarely
added as required. Table 1 shows examples of exceeds 150 t/d.
chemical compositions.
The mineral fiber is the predominant compo- Fiber Production. Numerous processes and
nent of the insulating materials: process variants have been developed for fiber-
izing silicate melt. Of these, only four have with-
90 – 99.8 % vitreous mineral fibers, average fiber diameter 3 – 6 µm
10 % max. phenol – formaldehyde resins, frequently modified stood the test of time (Fig. 26).
with urea or melamine Owens Process. In the Owens blowing pro-
1 % max. aliphatic mineral oil
0.2 % max. emulsifiers, preferably nonionic polyethoxylenes
cess (Fig. 26A), the melt, in the form of a thick
0.5 % max. polymethylsiloxanol primary strand, emerges from holes at the bot-
tom of a platinum crucible (the bushing) and is
subsequently entrained by a downward-directed
2.2.4. Production stream of gas from the blow-jet. The blowing
medium may be steam or compressed air. The
Melting. Two types of melting units are in primary strand is drawn to form fibers with an av-
use for the production of silicate melt: glass erage diameter of 3 – 6 µm (Fig. 27). The length
melting tank furnaces and cupola furnaces.
24 Fibers, 5. Synthetic Inorganic

Figure 25. Thermal conductivity of glass and rock wools as a function of temperature

of the fibers is about 3 – 10 cm. The product con- which distributes the melt evenly on the inside
tains slugs. Glass and rock melts are processed of a rotating spinner. Primary fibers issuing from
in this way. holes in the face of this spinner, are entrained by
Rock Wool Process. This centrifugal cascad- the hot combustion gases of a circular burner and
ing process (Fig. 26B) is also a one-step fiber- drawn to long fibers with diameters of 3 – 6 µm.
izing process. A single stream of melt hits the The product is free of slugs (Fig. 28), but the pro-
face of a horizontal rotor which distributes it to cess can be used only for “soft, long glasses,”
two or three additional rotors; from which it is not for rock melts. The process is highly variable
thrown in the form of fine fibers by centrifugal with respect to process parameters but is easy to
force. The fiber length is in the range 3 – 10 cm. control.
The product contains slugs. Rock melts are used Other Processes. The centrifugal blowing
in this process. process, shown in Figure 26D, is of little signif-
Rotary Process. The rotary process icance in the production of slag wool. The rod
(Fig. 26C) is a two-step process. The melt, in drawing process and a variant of the blowing
the form of a thick stream, passes through the process serve to produce textile glass fibers for
hollow shaft of a rotating centrifuge into a ro- glass mats. Special glass microfibers are made
tating throw-basket of platinum or special steel, by the flameattenuation process. However, these
 Fibers, 5. Synthetic Inorganic 25

Figure 26. Fiberization processes

A) Owens process [40]; B) Rock wool process [41]; C) Rotary process [41]; D) Centrifugal blowing process [41]
a) Melt; b) Bushing; c) Spout; d) Melt stream; e) Primary fiber; f) Jet; g) Centrifugal spinner; h) Burner; i) Fiber stream

Figure 28. SEM photograph of glass wool produced by the

rotary (TEL) process
processes have limited productivity and con-
sume large amounts of energy for fiberization,
Figure 27. Scanning electron microscopy (SEM) photo-
graph of rock wool produced by the Owens process
26 Fibers, 5. Synthetic Inorganic

and therefore they are not used to produce fi- mineral fibers. Emissions from the melting units
brous insulating materials. are similar to those of other glass melting instal-
lations. Electric precipitators have proved useful
Product Forming. The fibers are formed in dust removal but greatly strain the fluegas con-
into a continuous sheet by pneumatic pro- ditioning system. They can be combined with the
cesses, while an aqueous solution of binder is usual wet and semi-wet installations for sorption
sprayed onto the freely falling individual fibers. of fluorine and desulfurization.
The binders are slightly pre-condensed phenol – The binder resins should contain a mini-
formaldehyde resins. They are often modified by mum of monomers. Lubricants, mineral oils, hy-
aminoplastic resins (urea, melamine, melamine drophobic agents, and other organic additives
ether, dicyanodiamide) to suppress the tendency must be selected with an eye to their volatility.
of phenolics to exothermally autoxidize. In the Scrubbing systems with wet electric precipita-
industry these aminoplastic resins are called an- tors or deep-bed aerosol separators are suitable
tipunking agents. for minimizing emissions.
Figure 29 shows schematically the overall Wastewater from the manufacturing plant is
manufacturing process. The binder resins are biodegradable. Treatment with municipal waste-
cured at temperatures around 180 – 250 ◦ C in a water is always preferable. The high water re-
continuous flow dryer heated by circulated air. quirements of the off-gas conditioning system
For shaped articles or pipe insulation, for ex- favors installation of closed circulating systems
ample, special ovens that operate on a similar with the result that manufacturing plants can be
principle are used. On the other hand, presses operated free of wastewater.
with purely convective heat transfer are rarely Local ordinances must be observed in remov-
used since they require long cycle times. ing process waste. The insulating material itself,
Mineral-fiber insulating materials can be cut like other building materials, is inert and does
to any desired dimension with knives, saws, not have the potential for endangering water.
shears, and milling cutters. Both the dust from the filter units and the process
waste is suitable for internal recycling. The fiber-
ization units are serious noise emitters; there-
2.2.5. Environmental Protection fore, the manufacturing plant must be housed in
massive buildings.
Characteristic emissions arise in the various The overall effect of mineral-fiber fibrous in-
stages of producing insulating material from sulating material on the environment is positive.

Figure 29. Mineral-fiber insulation, from raw material to product [42]

The rotary process is used to form fibers.
 Fibers, 5. Synthetic Inorganic 27

There is no other building material that offers the producer. However, analysis of characteris-
a similar potential for minimizing the consump- tic trace elements generally allows identification
tion of primary energy for the same raw material of the producer. Certain finishing specialities of
and energy requirements. Average energy amor- the final product may permit identification.
tization times of 0.3 years and ecological amor- From the ecological point of view, an elu-
tization times of less than 0.1 years have been ate analysis is essential. The eluate is obtained
calculated. by shaking the insulating material at room tem-
perature with a tenfold amount of water for 24
hours.
2.2.6. Quality and Analysis For the determination of formaldehyde, the
perforator method DIN-EN 120 and the gas anal-
Each country has very detailed standards for ysis method of DIN 52693 are suitable. Analo-
fibrous insulating materials. International stan- gous methods are specified in other countries.
dardization is in progress, e.g., in the areas of
thermal insulation in high-rise construction, fire
protection, and industrial acoustics [43]. 2.2.7. Applications
Figure 30 shows a scheme of analysis for
mineral-fiber insulating material. Glass analy- Mineral-fiber insulating materials are finished
sis alone is, as a rule, not sufficient to identify products for use in protection from heat, cold,

Figure 30. Scheme of analysis for mineral-fiber insulating materials

28 Fibers, 5. Synthetic Inorganic

fire, and noise. The major end use area is high- Ordinances pertaining to protection of the
rise construction. Considerable quantities are workplace prescribe a general permissible limit
used in industrial and machine construction for of dust; in most countries, this limit is 5 –
thermal insulation. Fibrous insulating materials 10 mg/m3 . In the Federal Republic of Germany
are also important as noise absorbers in build- the limit is 6 mg/m3 . Epidemiological investiga-
ings and elsewhere. tions suggest that there is no health risk associ-
ated with the handling of mineral-fiber insulat-
Economic Significance. World production ing material if these limits are observed.
of mineral-fiber insulating material reached a Suspicions of a carcinogenic potential were
maximum of ca. 6×106 t in 1980 and has stag- derived from animal experiments with ex-
nated since (Table 14). About 75 % of the total tremely fine glass fibers carried out in 1972 –
is produced in the industrialized countries with 1978. Up to now these suspicions have not been
temperate and subarctic climate. Consumption confirmed with fibers from insulating materials.
is closely tied to investment and building activ- Animal experiments involving dust inhalation
ity. About 60 % of the demand for insulation in gave no indication of carcinogenicity. Exten-
industrialized countries is met by mineral-fiber sive epidemiological investigations could nei-
insulating material. ther confirm nor deny these suspicions. Further
Table 14. Production of mineral-fiber insulating materials in
research is needed.
various geographic areas, 1973 and 1983. Fibrous insulation materials are free of
Area Production
preservatives, fungicides, or biocides. They do
not contain asbestos or silicogenic material.
1973 1983 Increase, Formaldehyde is usually absent or present only
%
in trace amounts (<10 mg/kg).
t % t %

North America
Western Europe
1 600 000 43
1 200 000 32
2 350 000 42 46.9
1 750 000 31 45.8
3. Refractory Fibers
Eastern Europe and 600 000 16 800 000 14 33.3
the Former States of Refractory fibers are used at temperatures in ex-
USSR
Japan 200 000 5 400 000 7 100
cess of 1000 ◦ C. They are distinguishable from
Australia 50 000 1 mineral and synthetic aluminosilicate fibers by
} 120 000 } 3 } 150 their greater durability at high temperature and
Other 250 000 5
World total 3 750 000 100 5 600 000 100 49.3 by the fact that they have polycrystalline mi-
crostructures rather than being amorphous. They
are relatively new products, having only been de-
veloped during the last 20 years, and additional
2.2.8. Toxicology and Occupational Health varieties continue to be announced at a signif-
icant rate. The majority of fibers of this type
Synthetic mineral fibers are hard, abrasive mate- have been developed for thermal insulation at
rials. Constant handling can damage the epider- high temperatures or for advanced composites
mis, especially the finger tips and other exposed having the special physical properties required
areas of the body. Therefore, work gloves should in aerospace applications. These materials are
be worn, and the skin should be kept smooth by expensive since they are still manufactured on a
applying oily, protective skin lotions. small scale.
The fibrous dust formed during mechanical Historical Background.Until the 1960s, re-
loading, cutting, sawing, or rubbing may irritate fractory fibers were either naturally occurring
the skin or the mucous membranes. Especially fibrous minerals of the asbestos type or melt-
the coarse fibers, with diameters greater than spun glass fibers such as E glass, rockwool, or
about 12 µm, and the nonfibrous components are kaolin-derived fibers. Their maximum use tem-
able to penetrate the epidermis, thus causing in- peratures were limited by their melting points,
juries and facilitating the entry of germs. The kaolin fibers having the highest use temperature
irritations are slight and rapidly heal with nor- of 1250 ◦ C. Since then more refractory grades
mal body hygiene.
 Fibers, 5. Synthetic Inorganic 29

of melt-spun kaolin fibers, capable of use up to fibers and silicon carbide variants represent the
1400 ◦ C, have appeared. two main categories of refractory fibers.
The development of several types of novel The chief materials of interest are boron
oxide fibers since 1970 has had several moti- [7440-42-8], silicon carbide [409-21-2], high-
vations. At the time, an awareness was devel- alumina [1344-28-1] (0 – 30 % SiO2 /Al2 O3 ),
oping that a safe, noncarcinogenic, cheap as- and zirconia-based [1314-23-4] products. For
bestos replacement might be possible. Asbestos each of these materials there is a choice of sev-
was widely used in medium-temperature insu- eral grades from a range of suppliers. Fibers are
lation, in textiles, and in friction materials so available in a variety of primary forms such as
that replacement in these uses appeared to be continuous multifiber yarn, short staple random
an attractive technical target. About the same fibers, or as whiskers (→Whiskers). Typically,
time the worldwide rise in oil prices increased products have diameters within the range 1 –
the demand for energy-saving insulation, espe- 150 µm. Some of these primary products may be
cially in high-temperature furnaces operating converted easily to secondary forms such as wo-
above 1250 ◦ C. Consequently the need for im- ven cloths, ropes, papers, boards, prepregs, etc.
proved fiber refractoriness and freedom from All products on the market have complex com-
nonfibrous impurities (combined with an aware- positions and microstructure so that each can
ness that very fine fibers like asbestos might be only be referred to uniquely by its trade name.
carcinogenic) lead to the development of new These are listed in Table 15.
high-alumina and zirconia staple fibers. Simulta- Other materials that are or have been avail-
neously, continuous textile-grade multifilament able in fiber form are boron carbide (B4 C), sili-
fibers have also been developed to satisfy the con nitride [12033-89-5] (Si3 N4 , whiskers), and
need for high-temperature resistant textile appli- boron nitride (BN). For these materials the sup-
cations such as furnace curtains, fire barriers, hot ply situation varies since their applications tend
gas filters, electrical insulation, and protective to be highly speculative.
fire-fighting suits. In the 1980s renewed interest
in the potential of metal-matrix composites is
also sustaining the further development of novel 3.1. Properties and Raw Materials
high-alumina fibers.
During the 1960s the needs of the U.S. 3.1.1. Physical Properties
aerospace program for high-modulus, low-
density reinforcing fibers led to the develop- The behavior of fibrous materials is strongly de-
ment of entirely new non-oxide fibers; initially pendent on the shape and diameter of the fibers.
to CVD boron fiber and later to carbon fibers. To Typically the finer fibers are in diameter, the
a large extent the development of cheap, high- more flexible they become and the more diffi-
quality, carbon fibers in the 1970s has overtaken cult it is to pack them into high volume frac-
that of boron fiber since the price of the latter tions. Fine random staple and whisker fibers
has not been reduced significantly. A major dis- are usually low bulk density materials, while
advantage of carbon and boron fibers is their thick monofilament or multifilament continuous
ready oxidation at moderate temperatures, and fibers, which are both more rigid and less flexi-
so during the late 1960s and 1970s various kinds ble, are easily packed into high volume fractions
of oxidation-resistant silicon carbide fibers have (60 % for example).
been evolved. For example, the makers of CVD These characteristics determine utility and
boron have turned to CVD silicon carbide as the methods of handling. Fine staple fibers are
a potentially cheaper and better product. An- easily used as low density thermal insulation
other driving force in the development of con- and for the manufacture of low volume fraction
tinuous textile-grade silicon carbide fibers (such composites, but may present dust problems in
as Nicalon) has been the desire to have good handling. Large diameter continuous fibers are
high-temperature properties combined with re- more readily woven into textile forms for high-
sistance to oxidation and to attack by molten temperature use and are also more readily made
metals. At present, therefore, advanced oxide into unidirectional high-volume fraction com-
posites. On the other hand, the main handling
Table 15. Fiber properties ∗

30
Manu- Fiber name Chemical Type (fiber Dimensions Mechanical properties Compress- Fiber Thermal properties Crystal
facturer type count) ive strength, density Phases
MPa kg/m3 ,

Parti- Diameter, Length Modulus, Tensile Coeffi- Melting Maximum

culate µm GPa strength, cient of point or use temper-
◦
MPa thermal liquidus, C ature,
◦
expansion, C
106 K−1

Avco Boron boron filament 140 continuous 390 3000 – 5000 6600 2400 4.7 – 7.0 2200 500 Amorphous
(tungsten)
Avco SCS2 silicon filament 140 continuous 420 3400 – 4500 4000 3000 2830 1600 β-SiC
carbide
Nippon Nicalon silicon yarn (500) 15 continuous 176 – 196 2450 – 2950 >3000 2600 3.1 ca. 1400 β-
Carbon SiC/graphite

carbide
Ube Tyranno silicon− yarn 10 – 13 continuous 220 2800 – 3000 2300 – 2500 3.1 >1300 Amorphous
Industries
Fibers, 5. Synthetic Inorganic

Ti−C−O
Arco Silar SCS9 silicon whisker 10 – 20 % 0.6 10 – 80 µm 700 7000 3200 2700 α-SiC
Metals-
Silag carbide
Tokai Tokomax silicon whisker <1 % 0.1 – 0.5 50 – 200 µm 400 – 700 3000 – 3190 2700 1600 β-SiC
Carbon 14 000
carbide
Tateho SCW#1 silicon whisker 0.1 – 0.5 10 – 40 µm 480 20 700 3210 β-SiC
Chemical carbide
Los silicon whisker 3 – 10 10 – 25 mm 520 – 650 2000 – β-SiC
Alamos 20 000
carbide
Tateho SNW#1 silicon whisker 0.5 – 2 50 – 300 µm 380 14 000 3180 1900
nitride
Chemical
3M Nextel 312 24 % Silica/ yarn (600, 11 continuous 152 1720 2700 3.5 1800 1200 “inverse
mullite”
14 % 900, 1200)
Boria/
Alumina
3M Nextel 440 28 % Silica/ yarn (600, 11 continuous 207 – 240 1720 3100 5.0 1890 1430 η- or
γ-Al2 O3
Table 15. (Continued)

Manu- Fiber name Chemical Type (fiber Dimensions Mechanical properties Compress- Fiber Thermal properties Crystal
facturer type count) ive strength, density Phases
MPa kg/m3 ,

Parti- Diameter, Length Modulus, Tensile Coeffi- Melting Maximum

culate µm GPa strength, cient of point or use temper-
◦
MPa thermal liquidus, C ature,
◦
expansion, C
106 K−1

2 % Boria/ 900, 1200)

Alumina
Carbo- Fibermax 27 % Silica/ staple 2 – 3.5 150 850 1890 1650
rundum
Alumina
Denka Alcen 20 % Silica/ staple; yarn 2 – 3; 10 170 1700 3300 1890 1600 mullite/α-
Al2 O3

Alumina
Sumitomo 15 % Silica/ yarn (1000) 17 continuous 200 1500 2800 – 4400 3200 8.8 1890 1250 γ-Al2 O3
Alumina
ICI Catalytic 5 % Silica/ staple <1 % 1–5 5 cm 100 1000 1800 1980 η-Al2 O3
Saffil Alumina
ICI Saffil RF 5 % Silica/ staple <1 % 1–5 5 cm 300 2000 3300 1980 δ/θ-Al2 O3
Alumina
ICI Saffil HA 5 % Silica/ staple <1 % 1–5 5 cm >300 1500 3400 1980 1600 α-
Al2 O3 /mullite

Alumina
Du Pont Fiber FP >99 % yarn (200) 20 continuous 380 >1400 6900 3900 2040 1320 α-Al2 O3
Alumina
3M Nextel Z11 32 % Silica/ yarn 14 continuous 76 1310 3700 2000 1000 tetragonal
ZrO2
Zirconia
Zircar ZYBF-2 8 % Yttria/ yarn/staple 3 – 10 continuous/ 6000 2580 2200 tetragonal
Products ZrO2
Zirconia 1.6 mm

∗ In air, fiber strength severely affected.

Fibers, 5. Synthetic Inorganic
31
32 Fibers, 5. Synthetic Inorganic

risk is skin irritation caused by penetration of 3.1.2. Chemical Properties

the rigid fibers.
The physical properties of most importance Refractory fibers as a class of materials are of
are fiber diameter, length, shape, density, mod- low reactivity. The chief area of concern is their
ulus, tensile and compressive strength, expan- resistance to oxidation at high temperatures and,
sion coefficient, thermal conductivity, and max- if used in metal – matrix composites, their inert-
imum working temperature. These are summa- ness to corrosion by metals during fabrication
rized from available manufacturers brochures in and use. Reported thermal data are also given in
Table 15. Table 1, including claimed maximum use tem-
Only data on fibers with diameters greater peratures. Boron fibers are the most reactive to-
than 1 µm are reliable. Data for finer whiskers wards oxidative and metallic attack. Several at-
are implicit from data on composites. Neverthe- tempts have been made to coat boron fibers with
less, single crystal whiskers of silicon carbide inert layers, which has led to the BorSic product
have the best mechanical properties (modulus (SiC-coated boron). The chemical vapor deposi-
around 600 GPa, strengths up to 20 000 MPa). tion process for making boron fibers lends itself
Polycrystalline Avco silicon carbide and boron to laying down additional coatings. In France
and Du Pont α-alumina are of comparable stiff- boron carbide-coated boron has also been tested
ness, but Du Pont alumina is weaker than the [44].
others (modulus about 400 GPa and strengths The properties of silicon carbide fibers and
1500 – 5000 MPa). Finally polycrystalline tran- whiskers in composites have been thoroughly
sition aluminas, mullites, and Nicalon have reviewed by Andersson and Warren [45, 46].
moduli around 200 GPa and strengths around Their resistance to metal attack exceeds that of
2000 MPa. In composite applications specific boron by 200 – 300 ◦ C. High alumina fibers are
modulus and strength are more important, and inert in air and light alloys, but are slowly at-
here boron possesses the greatest advantage tacked by hot strong acids or alkalis. Zirconia
since its density is the lowest. Silicon carbide and fibers have exceptional thermal stability and are
transition aluminas follow at ca. 3000 kg/m3 , also resistant to hot alkali.
while α-alumina and zirconia-based fibers fol-
low with densities of ca. 4000 kg/m3 . Figure 31
shows SEM microphotographs of three different 3.1.3. Resources, Raw Materials
refractory fibers.
The raw materials for refractory fibers are usu-
ally specially selected intermediates. Since the
elements needed are among the most abundant,

Figure 31. SEM microphotographs of several refractory fibers; scale: —−→—10 µm

A) Silicon carbide whiskers; B) Aluminum oxide staple fiber (Saffil, ICI); C) Titanium-modified silicon carbide fiber (Tyranno,
Ube Industries)
 Fibers, 5. Synthetic Inorganic 33

there is no shortage of primary sources. The in-

termediates, however, are only readily available
in industrialized countries. In the case of silicon
carbide whiskers, a process has been commer-
cialized which uses rice hulls as raw material
[47].

3.2. Production

Because of their relative novelty, the processes

for making refractory fibers are almost all pro-
prietory, and full details have never been pub-
lished. A summary of the patent literature [48]
since 1970, relating to both the production of
refractory fibers and their uses in composites,
has appeared. There is a special section on re-
fractory fibers in Bela von Falkai’s book [49].
For further useful information refer to [50, 51].

3.2.1. Boron Monofilament

Carlsson [52] has reviewed general methods

of making boron fibers. In the 1960s, Avco
(USA) developed a chemical vapor deposition
(CVD) process to make 140-µm boron monofil-
aments having an 8-µm tungsten core [52, 53] on
a scale of 15 t/a. According to the company’s lat-
est brochure, the present capacity is only slightly
greater. More recently, a cheaper variant was
made available, in which the core is a 30-µm
carbon fiber, but this has now been withdrawn.
This development was initially financed by the Figure 32. Apparatus with mercury seals for the prepara-
tion of boron fibers by two-stage chemical vapor deposition
U.S. Government to develop advanced compos- [76].
ites for use in the space shuttle and in aerospace a) Apertures (25 – 254 µm diameter); b) hydrogen feed tube;
applications [53]. c) BCl3 feed tube; d) Mercury pool; e) Tungsten wire sub-
The process deposits amorphous boron with strate; f ) Gas effluent; g) Power supply (d.c.)
a nodular morphology from a BCl3 – H2 mixture
onto the electrically heated tungsten core at ca. and output. A range of products with various
1300 ◦ C. diameters has been produced. Initially, the tung-
sten core made up a large proportion of raw
BCl3 + 3/2 H2 → B + 3 HCl materials costs, but later the price of tungsten
The operation is carried out in single-stage dropped, and larger diameter fibers were devel-
or two-stage tube reactors (Fig. 32), the filament oped so that this cost factor decreased in impor-
passing at 3 – 4 m/min through mercury seals, tance. The introduction of carbon-cored B fila-
which also act as electrical contacts. Control of ment has lead to further cost reduction [53]. Var-
deposition temperature is critical because too ious surface treatments, such as acid polishing,
high values lead to crystallization of the boron, have been investigated to increase the strength
which reduces the strength of the filaments. Aux- from 2 GPa to 5 – 7 GPa. Also surface coatings
iliary heating techniquescan increase quality such as silicon or boron carbide are applied by
34 Fibers, 5. Synthetic Inorganic

the CVD technique [54] to reduce the reactivity

with aluminum alloys and oxidation at temper-
atures above 300 ◦ C.
In the commercial plant, hundreds of reactors
are fed in parallel with the gaseous reactants.
Since the conversion of gas per pass is low, the
unconverted gases are recovered and recycled,
while the byproduct HCl is sold.
More recently, more rapid boron deposi-
tion methods have been reported: these meth-
ods operate at high temperature and high pres-
sure and do not require resistive heating of the
substrate. Pulse discharges have been used for
boron coating of filaments [55]. The excited
gas species are formed by inductive or capac-
itive coupling of pulsed high electric power to
a boron-containing gas mixture at a pressure of
0.1 – 0.3 MPa (Fig. 33). The gases admitted to
the deposition zone are hydrogen, mixed with
boron halides, boranes, or alkyl borates. The
deposition process is performed at 20 – 350 ◦ C
on filaments suspended in the deposition zone:
tungsten filaments, graphite yarn, and polyacry-
lonitrile yarns were coated with boron to a thick-
ness of about 50 µm. The residence time of the
substrate within the deposition zone was about Figure 33. Apparatus for the production of boron fibers
5 min. by capacitive coupling of pulsed high electric power [55].
a) Power supply (pulsed high electric power); b) Oil-cooled
reaction tube; c) Let-off spool; d) Seal; e) Take-up spool; f )
Oil reservoir; g) Pump
3.2.2. Silicon Carbide Fibers
Because of the highly attractive physical prop-
since been commercialized by Nippon Carbon
erties of fully crystalline silicon carbide and the
Co. as Nicalon [58]. A second generation car-
low cost of raw materials, more effort has been
bide fiber, namely Tyranno fiber from Ube In-
devoted to generating silicon carbide in fibrous
dustries, contains titanium in addition to silicon
forms than for any other material [45, 46, 56].
and is reported to have superior strength and
Silicon Carbide Monofilament. This mate- chemical resistance.
rial is available in composites from Avco and The Nicalon fiber process begins with the
is probably made by a CVD process [57] simi- conversion of dimethyldichlorosilane (an inter-
lar to that used for boron filament. The reagents mediate in silicone manufacture) to poly(di-
are an alkylchlorosilane or a mixture of alkane methylsilane) by dechlorination with sodium.
and chlorosilane condensed onto a tungsten or The poly(dimethylsilane) is heated under Ar in
carbon core. The product has a columnar grain an autoclave at 470 ◦ C for 8 – 14 h to convert
structure with the growth direction normal to the it to a poly(carbosilane) of complex structure
fiber axis. In order to increase the strength of the (see [58]). After vacuum distillation to 280 ◦ C
fiber it is usually coated with a thin carbon layer to remove low molecular mass fractions, the
(CVD process), which fills in any grain bound- poly (carbosilane) (M r 1500) is then melt-spun
ary faults at the filament surface. at 350 ◦ C as a multifilament tow. The raw fibers
are then cross-linked by oxidation in air for
Silicon Carbide Continuous Yarn. Sili- 30 min up to 190 ◦ C and heat-treated to 1200 ◦ C
con carbide continuous yarn was invented by in inert atmosphere to convert them to the fin-
S.Yajima in the 1970 – 1975 period and has
 Fibers, 5. Synthetic Inorganic 35

ished fiber having maximum strength. The fibers spinnerets. The gel fibers are converted to refrac-
have a complex constitution consisting of a tory fibers by heat treatment, usually in multi-
fine-grained mixture of graphite, β-SiC, and stage furnace treatments. Major features of these
glassy silica. The fiber stability is limited above processes are the ability to make any composi-
1200 ◦ C, and the modulus (which is a function tion and the large shrinkage experienced during
of fiber diameter) is only 50 % of the value of calcination.
CVD polycrystalline silicon carbide. According to patents [62, 63], Du Pont’s
FP fibers may be made from colloidal α-
Silicon Carbide Whiskers (→Whiskers, alumina (e.g., Alcoa XA16 fractionated to 90 %
Chap. 4.1.). These have traditionally been made <0.5 µm diameter) dispersed by HCl treat-
by high-temperature synthesis between SiO2 ment and blended with an aluminum salt,
and a carbon source under reducing conditions. such as the chlorohydrate (commercially avail-
A more recent development uses as raw material able basic aluminum chloride [1327-41-9],
rice hulls, which contain Si and are processed at Al2 (OH)5 Cl · 2 – 3 H2 O), acetate, or nitrate. The
1500 – 1660 ◦ C [47, 59]. They are usually single viscous mixture is extruded into air to give gel
crystals, although there is some confusion in the fibers, which are then subjected to two- or three-
literature as to the direction of the growth axis. stage calcination to give the final fiber (either
Very high strength β-silicon carbide whiskers flame-polished in an oxypropane flame or at
(6 µm diameter) are grown by a vapor – liquid – 1400 – 1500 ◦ C in a furnace). The fibers have
solid (VLS) method at 1400 ◦ C from methane a diameter of 20 µm and are polycrystalline
and silicon monoxide using powdered iron cat- α-alumina with a grain size <0.5 µm. Their
alyst [60, 61]. Properties are given in Table 1. strength can be improved by a surface coating
ca. 5 nm thick of silica derived from a silicone
[64].
According to a patent [65] 3 M’s Nex-
3.2.3. High Alumina Fibers
tel fibers are made from a silica hydrosol
blended with aluminum formoacetate and boric
High alumina fibers containing less than 30 wt % acid together with organic improvers such as
SiO2 cannot be readily spun from melts be- polyvinylpyrollidone (PVP), poly(vinyl alco-
cause the temperatures are too high. Fibers in hol) (PVA), lactic acid, or glucose. After concen-
this class are either made from water-soluble tration to a viscosity between 45 and 500 Pa · s,
or dispersible precursors (sol – gel products) or the solution is extruded through a multi-hole
from an organometallic precursor (only Sumit- spinneret into air to give gel fibers. These gel
omo’s alumina). Fibers that are available range fibers are calcined in air to at least 1000 ◦ C (poly-
from fine diameter (3 µm) random staple (ICI crystalline η- or γ-alumina <60 nm grain size)
Saffil alumina fiber) through to relatively coarse or to 1400 ◦ C (polycrystalline mullite >50 nm
(20 µm) continuous fibers (Du Pont FP alumina). grain size) if they are to be used up to 1400 ◦ C.
This class includes mullite [1302-93-8] fibers The finished fibers have an oval cross section
(27 % SiO2 ) and 3 M Nextel alumina – boria – with a mean diameter of 11 µm and are suitable
silica fibers. Single-crystal whisker products are for weaving cloths.
also available (→Whiskers, Chap. 4.3.). Sumitomo has described their process [66,
67]: first triethylaluminum or triethoxyalu-
Continuous Yarn Fibers. Du Pont, 3 M, minum is hydrolyzed with a controlled amount
and Sumitomo have supplied products of this of water to a polyalkyl(oxy)aluminoxane (de-
type for several years. ICI, Denka Kagaku, and gree of polymerization of 10 – 200), which is
Mitsui mining announced new alumina-based then dissolved in an organic solvent. An alkyl sil-
continuous or semicontinuous fibers. icate is added (to give 15 wt % SiO2 in the final
In each case a different precursor is used, product) to prepare the viscous solution (0.1 –
but the processes are otherwise broadly similar 500 Pa · s) for spinning. The fibers are dry-spun
(Fig. 34, see next page). First a viscous precursor into air. These gel fibers are then calcined in air to
solution is prepared and then converted to green 700 ◦ C to decompose them to oxide and further
(or gel) fibers by extrusion through multi-hole fired at 1000 ◦ C to crystallize them to a dense
36 Fibers, 5. Synthetic Inorganic

Figure 34. Flow chart of continuous refractory oxide fiber production [77].
a) Precursor solution; b) Metering pump; c) Multi-hole spinneret; d) Fiber bundle; e) Hot air distributor; f ) Draw rolls;
g) Transfer conveyor; h) Pre-fire resistance furnace; i) High-temperature tube furnace; j) Transfer rolls; k) Multi-filament fiber
tow

polycrystalline fiber having a γ-alumina and/or lected as a random mat on a conveyor belt. They
a mullite structure with a grain size of several are decomposed at 200 – 500 ◦ C and calcined
nanometers). Production fibers are made with a in one or two stages to recrystallize and sinter
diameter of 17 µm. the initially amorphous material. Various prod-
So far no details are available for methods of ucts are available, with different finishing tem-
producing the newest continuous fibers. peratures and containing different crystalline-
transition alumina phases (Table 1). Centrifu-
Staple Fibers. Staple fiber products include gally spun products contain more nonfibrous
ICI Saffil alumina, Carborundum’s Fibermax material than blow-spun products.
(and the equivalent Toshiba Monofrax), and
several products available from Japan such as
Denka’s Alcen. 3.2.4. Zirconia Fibers
In sol – gel processes [68], an aqueous
Zircar fibers (yttria stabilized) are made by the
spinning solution is formulated from basic
relic process, where a continuous cellulose fiber
aluminum chloride (aluminum chlorohydrate,
is impregnated with suitable salts and then cal-
Al2 (OH)5 Cl · x H2 O), a water-dispersible silox-
cined in air to decompose the salts to oxides and
ane, or a silica sol, and a viscosity modifier such
burn away the cellulose. Yttria is added to main-
as PVP, PVA, or poly(ethylene oxide). Fibers are
tain the zirconia in the tetragonal phase, pre-
either blow-spun through multi-hole spinnerets
venting the destructive conversion to monoclinic
or centrifugally spun into warm dry air and col-
phase on cooling. Alternative phase stabilizers
 Fibers, 5. Synthetic Inorganic 37

that have been investigated are calcium oxide of blanket are glued to a rigid backing (stack-
and magnesia. An alternative process, which has bonding) to give a surface with high gas ero-
been used by ICI to make staple fibers, is the sion resistance. This technique can be applied to
sol – gel route. This is described by others in existing brick-lined gas-fired furnaces (veneer-
the literature [69] and generally uses zirconyl ing) to give substantial energy savings. Staple
acetate as the raw material. Other details are fibers can also be converted by wet-lay vacuum-
similar to those used for alumina fibers. Nextel forming processes to rigid forms. For such prod-
Z-11 continuous zirconia – silica [14940-68-2] ucts the refractory fibers are often blended with
fibers from 3 M are made much like the alu- amorphous alumino-silicate fibers so as to uprate
mina – silica – boria products [70]. the maximum working temperature of the amor-
phous fibers, e.g., from 1250 to 1400 or 1500 ◦ C.
In these forms, sacrificial organic binders, such
3.3. Environmental Protection as starch, are often combined with a refractory
binder such as a silica sol. It is also possible to
Since these products have only been made in make papers by blending small proportions of
small quantities so far and are physically and fine glass fibers into the slurry.
chemically inert under ambient conditions, they Thermal insulation for nuclear reactors
pose no significant threat to the environment. presents a requirement of high resilience under
Ultimate disposal is likely to be by burial. high acoustic vibration loadings at modest tem-
The byproducts of fiber manufacture are either peratures. Very low shot level staple fibers are
acids, which are scrubbed and sold or neutral- superior for this application.
ized before disposal, or carbon oxides and small The yarn and monofilament materials are best
amounts of volatile organic compounds. used as woven cloths [71], which can be em-
ployed as flame barriers and radiation shields or
as bag filters for hot-gas filtration. Where den-
3.4. Uses sity is not a prime consideration, Nextel Z11 is
claimed to have superior firewall properties. The
The principal uses of refractory fibers are in long fiber products can be converted to string,
high-temperature insulation and composites. woven cloths, ropes, tapes, thread, braiding for
electrical wiring, etc. Such yarns, ropes, etc. can
be employed as expansion joint packings, door
3.4.1. High-Temperature Insulation and seals, and the like. Both staple and continuous
Filtration fibers can be used for space vehicle insulation
systems, e.g., tiles as on the space shuttle.
By reason of their refractoriness, those fibers Both short and long fiber products can be used
which are not attacked by oxygen or which form in advanced composites. Large volumes of data
passive oxide layers (oxides, SiC) can be used are available for composite properties using ei-
in furnaces as high-temperature insulation or ther resin matrices, metal matrices, or ceramic
structural elements. High-alumina fibers dom- matrices. These present a range of opportunities.
inate these applications. In general, the staple The refractory properties of the fibers are
and whisker materials that have diameters be- most effectively exploited in metal – matrix
low 6 µm are best for low-density insulation hav- or ceramic – matrix composites because good
ing a low thermal conductivity. Conductivities at properties are then available above 200 ◦ C in
1400 ◦ C as low as 0.3 – 0.4 Wm−1 K−1 can be many such systems. Both types of material are
reached. Use of such low thermal mass insula- presently undergoing intensive development to
tion allows faster cycle times in batch furnaces, evaluate their potential for replacement of con-
giving energy savings of 20 – 40 %. ventional metal alloys.
In furnace applications, the short fiber prod-
Resin-Matrix Composites. In resins, re-
ucts can be used in a variety of forms. When re-
fractory fibers are in competition with carbon
silience is required, blanket or loose wool can be
fibers and Kevlar fibers. In situations where the
employed in several ways. In one method, strips
composite is required to have high compressive
38 Fibers, 5. Synthetic Inorganic

strength, the use of boron, silicon carbide, or alu- maximum operating temperature of this alloy,
mina fibers is preferable. This has found utility but this matrix is generally too aggressive to be
in parts of sporting goods such as golf clubs, ten- compatible with other types of fibers.
nis rackets, and fishing rods. Aerospace applica-
tions have also been explored [53]. The U.S. F14 Ceramic – Matrix Composites. When ma-
fighter had boron – epoxy horizontal-stabilizer terials are required to exceed the maximum
skins. Where electrical insulating properties as working temperature of nickel-based superal-
well as mechanical properties are important, loys, ceramic – matrix composites are forecast
then alumina or silicon carbide fibers can be to fill the gap. If the more severe processing
more effective than glass or Kevlar fibers. and property requirements can be met, they will
be utilized in advanced gas-turbine blades and
Metal – Matrix Composites. Metal – in advanced internal combustion engine compo-
matrix composites (MMCs) where the matrix nents such as pistons and exhaust turbo-charger
is an aluminum, magnesium, titanium, or nickel rotors.
alloy, should be able to replace parts currently Currently much effort is devoted to improv-
made of steel, titanium, or nickel alloys. Fabrica- ing the fracture toughness of monolithic engi-
tion and shaping of MMCs presents formidable neering ceramics such as glasses, glass ceram-
problems. Corrosion of fibers by the metal dur- ics, silicon carbide, silicon nitride, alumina, and
ing fabrication and use is the chief problem. partially-stabilized zirconia by the incorporation
Aluminas are superior in this respect to silicon of fiber reinforcement. This is the most severe
carbide and boron, which, for example, is only application of refractory fibers since they are re-
stable to 200 ◦ C in 2024 aluminum alloy. How- quired to resist corrosion by the matrix during
ever, boron fibers are usable when SiC-coated. fabrication of the composite at temperatures of-
Because of high costs, nearnet-shape forming ten exceeding 1200 ◦ C. Some encouraging re-
methods such as squeeze-casting, extrusion, and sults have been reported in the literature [57],
forging are preferred. Aluminum-based MMCs but a real application has not yet been success-
have reached commercialization in a few appli- ful.
cations. Boron filament – aluminum composites
have been utilized for cargo bay spars in the
space shuttle. In the future, other fibers, such as 3.5. Miscellaneous Uses
silicon carbide (continuous and whiskers) [72,
73] and alumina [74], will find uses in aerospace Miscellaneous applications of refractory fibers
and automotive engineering applications where have developed, such as the use in nuclear tech-
low density must be combined with rigidity, nology. Here, boron fibers find uses in fabricat-
strength, heat, and/or wear resistance. ing flexible neutron shields.
The use of small amounts (<30 vol %) of Zirconia fibers find utility because of their
short alumina fibers in diesel engine pistons has great resistance to alkali attack and are recom-
been commercialized by Toyota. Here the effect mended for use as battery separators. Nextel Z-
of fibers is to increase the wear resistance of the 11 has outstanding flame resistance and is pre-
piston alloy in the region of the ring grooves so ferred for fire-wall uses.
that high nickel alloy inserts are not required. In Porous fibers, such as ICI catalytic grade Saf-
more advanced applications such fibers in piston fil alumina, have been found to be effective as
crowns can increase resistance to fatigue crack- catalyst supports in domestic flameless heaters.
ing so that more efficient engines become pos-
sible. High volume fractions of unidirectional
long alumina fibers are currently being evalu- 3.6. Economic Aspects
ated in connecting rods for internal combustion
engines to decrease the mass of moving parts, Refractory fibers are specialities made on a rel-
which should lead to increased engine efficiency. atively small scale where raw materials costs
BorSic and silicon carbide monofilaments make little contribution to the selling price. The
have been successfully incorporated into Ti-6Al- major costs are related to processing and capital
4V alloy [44] with the aim of increasing the costs.
 Fibers, 5. Synthetic Inorganic 39

Of all the fibers considered, short staple alu- to that of asbestos has been recommended until
mina fibers are the product available in the great- more definitive information is available.
est quantity and at lowest price. World capac-
ity probably exceeds several hundred tonnes per
year. Prices range from $ 30 to $ 60 per kg (ca. 4. Metal Fibers
30 – 60 ¤/kg).
Prices for continuous fibers or whiskers vary The definition for a metal fiber is not straight-
from $ 80 – 900 per kg. The cheapest is Nextel forward, especially when metal fibers are classi-
312 at $ 80 per kg with Nextel 440 at $ 260 per fied according to nature, structure, properties, or
kg. SiC whiskers, Nicalon, Sumitomo alumina, manufacturing processes. What cannot be con-
and DuPont FP fibers all cost ca. $ 450 – 550 per sidered a metal fiber is easier to state:
kg, while Avco boron fiber (tungsten core) is A single drawn wire used separately; any-
$ 825 – 900 per kg. These products are all prob- thing much thicker than 100 µm; and steel wool.
ably made on a 10 – 20-t/a scale. Du Pont has Metal fibers can usually be handled in the same
projected that at 500 t/a FP alumina fiber would way as textiles, paper, or polymers, and have
cost $ 88 per kg. small, equivalent diameters.
Secondary forms of the above materials–such In this chapter, emphasis is placed upon
as vacuum-formed shapes for staple fiber or wo- bundle-drawn and melt-spun fibers. For metal
ven cloths for continuous fibers–can cost double whiskers see →Whiskers. Other methods of
the basic fiber cost. Some products are available manufacturing fibers are mentioned briefly.
as epoxy prepregs, and there is an appropriate
markup in price for such intermediates.
4.1. Production
3.7. Toxicology and Occupational 4.1.1. Bundle Drawing
Health
Fibers with diameters exceeding 3 µm are not Very fine wires can be produced by wire draw-
respirable and, like glass fibers, are difficult to ing. Production costs are extremely high, how-
handle only because of skin irritation. For such ever, and increase exponentially as the diame-
materials, operators handling the fibers are rec- ter decreases. To overcome this problem bun-
ommended to wear loose-fitting clothing. dle drawing was developed as early as 1936
Fine fibers with diameters below 3 µm are [78]. Instead of drawing wires singly, a num-
respirable. Because of the known ability of ber (in some cases several thousand) are bundled
asbestos dust to cause both asbestosis and and drawn simultaneously [79] (Fig. 35, see next
mesothelioma, considerable effort has been de- page). The sole difficulty remaining is to sepa-
voted to assessing other fibrous mineral and ce- rate the individual fibers with a suitable material
ramic dusts for similar effects. In general, sus- prior to bundling so that the final fibers can be
picion has now focussed on those materials that individualized again. Quite often used is another
are durable in the body and have diameters be- metal that has sufficiently similar properties to
low 0.5 µm and lengths greater than 8 µm [75]. the wire metal to be made into fibers, to with-
Products that have diameters significantly above stand the drawing and annealing operations, but
this limit have been found to be inert biologi- a lower chemical resistance to allow the fibers to
cally. According to a proposal, such materials be freed from this matrix in a leaching operation.
should be classified as nuisance dusts, for which Whereas this method greatly reduces drawing
an MAK of 6 mg/m3 is appropriate. In the UK and annealing costs, it only produces bundles of
and the United States the MAK is 10 mg/m3 . The fibers and not reels of single wires such as is
finer materials, especially whiskers, remain un- needed to produce fine tungsten wire to serve as
der suspicion. Similar products have been with- core material for boron fiber manufacturing.
drawn from the market because animal tests have
proved them to have positive carcinogenic po-
tential. For such materials an MAK equivalent
40 Fibers, 5. Synthetic Inorganic

4.1.2. Melt Spinning [80–82] Melt Extrusion. Melt extrusion (melt spin-
ning) involves the solidification of a liquid jet of
The basic idea behind all the from-the-melt metal extruded through an orifice (Fig. 36). The
production methods is the possible economic stream of molten metal is inherently unstable,
advantage of single-step processes over con- mainly due either to its high surface tension and
ventional time- and energy-consuming, labor- low viscosity or to a violent drop in its viscosity
intensive fiber-drawing processes. These from- at its spinning temperature.
themelt processes can be roughly divided into
two classes: melt extrusion and melt extraction.
Dating back to the 1930s, from-the-melt fibers
developed rapidly in the 1960s after Duwez de-
veloped the splat cooling technique: a revolution
in metallurgy, resulting in what are now gen-
erally known as the RST (Rapid Solidification
Techniques), sparked intense interest in glassy
or amorphous metals. The Battelle Development
Corporation has pioneered all these processes in
one way or another, and is still doing so.

Figure 36. Melt spinning of metal fibers.

a) Crucible; b) Nozzle

The stream must be stabilized. There are a

number of variants, which can be grouped in
four divisions:
1) Jet stabilization in a controlled atmosphere,
triggering off a surface reaction and oxide
film formation (e.g., Monsanto, Michelin,
Bekaert, Brunswick).
2) Jet stabilization by sheathing in glass and
spinning the resulting composite. This so-
called Taylor process (Fig. 37) has been suc-
cessful on a semi-industrial scale (Glass De-
velopment, U.K.), but has virtually been
abandoned in spite of the excellent fiber qual-
Figure 35. Manufacturing alternatives of bundle-drawn ity, mainly because of low production capac-
metal fibers
 Fibers, 5. Synthetic Inorganic 41

ity, hence high cost. Fibers down to 1 µm are multi-hole process), raw-material prices (up to
possible. 10 % boron), and some vital mechanical prop-
3) Stabilization by heat transfer to a liquid (in- erties, especially torsion characteristics and fa-
rotating-liquid spinning) (e.g., Allied Signal, tigue behavior.
Michelin, Unitika).
4) Solidification by direct contact with a Melt Extraction. The melt extraction pro-
moving-solid, heat-extracting surface. Al- cesses avoid the need for orifices because the
though round fibers cannot be made by this molten metal is extracted from a melt by a
technique, it was and still is the only one that wedge-shaped edge of a rotating disk: CME
has developed into a full-blown industrial (crucible melt extraction) or PDME (pendant
process (Allied Signal, 1976). In this respect, drop melt extraction), see Figure 38. The pro-
it is the process responsible for the commer- cess was invented and developed by Battelle and
cialization of amorphous metals (ribbons and exploited on an industrial scale by Fiber Tech-
sheets). nologies (U.K.).

Figure 38. Crucible melt extraction (CME) for the produc-

tion of metal fibers.
a) V-edged wheel; b) Wiping wheel

4.1.3. Other Processes

Metal fibers have also been made by chemical

vapor deposition, mechanical methods, and elec-
trolytic procedures. Other less important meth-
ods include slurry drying, decomposition, and
reduction; in-situ decomposition of inorganic
and organic compounds; and physical vapor de-
position.

Chemical Vapor Deposition (Whiskers).

Figure 37. Taylor process for the production of metal fibers Metallic whiskers are generally made from the
gas phase by decomposing a compound of the
Most of the processes failed to become fully metal (e.g., pentacarbonyl iron). Whiskers of
industrial because they could not be upgraded iron, copper, and tin have been manufactured.
from workable single-fiber processes to multi-
fiber operations. The most promising method Mechanical Methods. Mechanical shaving
is the in-rotating liquid spinning, established in methods, similar to those for steelwool produc-
1981 and the only method that enables fibers tion can be used, starting from either wire or
with circular cross sections to be manufactured stacked thin foils. The fibers so produced have ir-
in continuous lengths. regular cross sections, either triangular or rectan-
Improvements remain to be realized with re- gular with a surface roughness and poor mechan-
spect to production costs (development of the ical properties. The shaving methods were im-
42 Fibers, 5. Synthetic Inorganic

proved by the introduction of superimposed vi-

brations, which result in more homogeneous
cross sections and properties.

Electrolytical Procedures. After car-

bonization, organic fibers can be coated by elec-
trolysis to produce metal sheaths. The organic
and carbon residues can also be decomposed to
leave hollow fibers. Metal fibers of Ni, Cr, or Cu
as well as their alloys, can be formed. Another
process consists of depositing continuous fibers
on a suitably grooved mandrel.

4.2. Bundle-Drawn Fibers

4.2.1. Form and Dimensions

Bundle-drawn fibers can be produced in the

form of continuous bundles, broken bundles
(slivers), cut fibers, spun yarns, threads, cables,
web, sintered web, needle felt, filter media, etc.
All these morphologies are obtained by tex- Figure 39. Microphotographs of bundle-drawn metal fibers
tile industry-like operations combined with met- A) Scanning electron microscope (×1250) B) Optical mi-
allurgical techniques, processes, and methods. croscope (×1100)
a) 22 µm; b) 12 µm; c) 8 µm; d) 4 µm
The fiber diameters depend to a large extent
on the metallurgical and structural purity of the
starting material (wire rod), itself a function of
the alloying elements and the manufacturing and
purification procedures during wire-rod produc-
tion.
Figure 40. Very thin bundle-drawn metal fibers, diameter
2 µm (×625)
4.2.2. Composition

The following are typical alloys lending them-

selves to the bundle-drawn fiber manufacturing: 4.3. Uses
Stainless AISI 316L
Stainless AISI 302 Anti-Static Applications. Since metal
Carpenter 20Cb3 fibers are good electrical conductors, they were
Inconel 601 first used in anti-static carpeting to dissipate
FeCrAlloy the static charges. Very soon the same principle
Hastelloy X was applied to clothing for medical use as well
Nichrome as for work with explosives or sensitive elec-
titanium tronic components of instruments, followed by
anti-static filterbags for use with explosive dusts
Standard diameters are 4, 8, 12, and 22 µm [83]. Cast floors, e.g., as in operation rooms,
(Fig. 39). Of course, larger diameters are possi- are made sufficiently conductive to eliminate
ble, such as 40, 50, and even 100 µm. For some the possibility of sparks and electric discharges.
alloys 12 µm is the lower limit. For very pure The same also applies to bed linen for use with
alloys, fibers 2 µm and even finer are possible oxygen tents, etc.
(Fig. 40).
 Fibers, 5. Synthetic Inorganic 43

Filter Media [84]. Filters are one of the most of the space shuttle thrust rockets. These sin-
promising areas for the use of metal fibers, since tered metal fiber structures also make highly
the existing products, such as woven wire mesh permeable, extremely efficient, versatile flame
and sintered metal powders, no longer fulfill all arrestors.
criteria:
Medical Applications. Titanium fibers are
1) Fine pore size from 20 µm to a few microm- bio-compatible and can consequently be applied
eters as porous ingrowth materials for implants to
2) Large permeability (4 – 10 times higher than evoke bone development in the pores, guarantee-
at present) ing perfect fixing and load transmission. Stain-
3) High dirt holding capacity, therefore longer less steel fibers can be used to reinforce dental
operational life (fourfold or more than at bioglass.
present)
4) Acceptable and competitive price in the ap- Electromagnetic Interference (EMI) [86].
plication niches With the proliferation of electronic appliances
Only sintered metal fiber filter media can sat- and instruments in our daily life, electromag-
isfy these requirements successfully. The princi- netic interference must be controlled. More and
pal areas of metal fiber filter media applications more appliances are shielded against outside
include the following: interference, as well as against creating inter-
ference themselves. Present-day housings for
polymer fiber and foil manufacturing
electronic devices are made from composite
hot gas filtration
materials of polymer matrix and metal fibers.
aircraft fuel de-icing and filtration
The presence of a low concentration of conduc-
filtration in the fields of hydraulics and robotics
tive metal fibers of the correct alloy, structure,
fine chemicals and pharmaceuticals
diameter, and length give these casings a total
crossflow filtration
attenuation of more than 80 dB, this without
generation of nuclear energy: gas cooled reac-
altering the other properties of the polymer ma-
tors, cooling
trix.
water condensate, elimination of radioactive
aerosols from waste gas flows during emer- Radar Camouflage. As a special case of
gencies EMI, an amount of the correct metal fiber in
radar camouflage netting that matches as closely
Sound Absorption. Sintered metal fiber as possible the absorption and reflection char-
sheets can be deployed as highly effective sound acteristics of radar waves for the environment
barriers under circumstances where other ab- has the effect of concealing an object. Structures
sorbers are inefficient, e.g., in high-temperature containing metal fiber can be adjusted to vary
environments and at high-energy sound levels. from zero to almost 100 % reflection or absorp-
This is particularly the case for aircraft and tion.
turbine noise reduction.
Microwave Detection. Every metallic fiber
Gas Burner Panels and Tubes [85]. structure has a unique microwave signature, or
Highly porous sintered FeCrAlloy sheets and fingerprint, that can be detected, registered, per-
tubes produce an efficient radiant surface for sonalized, stored, and recognized. This feature
burning natural gas. The advantages over the can serve for the identification and verification
usual ceramic burners are improved life cycle, of valuables, security papers, passports, credit
lower NOx , better malleability, and sturdiness. cards, identification cards, etc.
Thermal Insulation and Flame Arresting. High-Voltage Protection. The effect of the
The heat conductivity of porous metal fiber strong electromagnetic field on persons work-
structures is comparable to that of an aver- ing on live high-tension lines can be harmful to
age quality glass fiber mat, and such products their health. A protective suit made from cloth
have solved high-temperature insulation prob- containing up to 25 % metal fibers acts as an ef-
lems such as those involving the exhaust gases ficient shield.
44 Fibers, 5. Synthetic Inorganic

Capillary Uses. Since bundle-drawn metal

fibers are finely grooved on their surfaces and
form very fine tubes in between themselves, a
fiber wick exhibits large capillary action. This
effect is used in heat pipes, space technology,
etc.

Other Uses. Many other uses are under con-

sideration or are being developed. A few impor-
tant ones should be mentioned: catalysts and cat-
alyst carriers, heat-exchanger media, diffusion
barriers, coalescing and demisting media, gas –
liquid separator media, high-temperature seals,
and the heating of textiles (e.g., curtains).

4.4. Manufacturers Figure 41. Surface of melt-extruded metal fiber, diameter

ca. 0.36 µm (magnification ×250)
There are presently three major metal fiber pro-
ducers: Brunswick Corporation (U.S.A.), Nip-
pon Seisen (Japan), and N.V. Bekaert (Belgium).
Not all of them produce all the various quali- 4.6. Uses
ties and shapes available; some are integrated Melt Extrusion Fibers. If amorphous or mi-
into the endproducts. N.V. Bekaert S.A. makes crocrystalline fibers with circular cross section
the largest variety of alloys, diameters, half- become commercially available, there would be
products, and shapes, as company policy is not an opening in those areas that already are served
to be integrated. by amorphous ribbons: transformers and other
electromagnetic equipment, shielding, sensors,
etc. However, by far the biggest market would
4.5. Melt Spun Fibers be for structural uses, especially in tire reinforce-
ment, with a potential of 0.5 – 1.0×106 t/a.
4.5.1. Properties
Melt Extraction Fibers. Melt extraction
The quality and the properties of fibers produced fibers are mainly used for the reinforcement
by most melt extrusion processes are quite sat- of concrete and, in particular, of refractory ce-
isfactory, and this is particularly the case for the ments where they compete with conventionally
amorphous or microcrystalline fibers (Fig. 41). drawn carbon and stainless steel wires. The
In addition to the somewhat unusual magnetic smaller flakes also have some potential as fillers
and physical properties of the fibers, tensile in polymers for electromagnetic interference
strengths up to 7000 N/mm2 have been obtained. applications, where they must compete with the
However, poor dynamic behavior (e.g., fatigue) bundle-drawn metal fibers.
is still a weakness. Equivalent diameters (gen-
erally the fibers are not round) range from 25 to Economic Aspects. Metal fiber prices are
300 µm, depending on the process and the melt tending downwards as more and more high vol-
composition. ume applications are being implemented.
Producing continuous lengths by melt extrac-
tion has proved to be extremely difficult, but by
notching the edge, short fibers and flakes with an 5. Carbon Fibers
equivalent diameter of 20 – 200 µm can be pro- Carbon fibers are black fibers used as yarns,
duced. Filaments with circular cross sections are felt, or powderlike short monofilaments with di-
not available commercially. ameters smaller than 10 µm. They are mainly
 Fibers, 5. Synthetic Inorganic 45

applied to reinforce polymers, much like glass

fibers have been used for decades in fiber glass,
with the principal difference that composites
with carbon fibers are so-called advanced com-
posites or high-performance composite materi-
als. The progress achieved with carbon fibers,
as compared with glass reinforcement fibers, is
based on the superior stiffness of carbon fibers,
combined with high strength and low density.
As can be seen from Figure 42, the density of
polyaramide fibers, introduced into the market
nearly simultaneously with carbon fibers, is even
lower, but strength and stiffness of these organic
fibers do not reach near the top values for carbon
fibers.

Figure 43. Specific tensile modulus (Young’s modulus di-

vided by density) of the various carbon fiber types (PAN and
MPP) in comparison to other structural materials
∗ = single crystal (a-direction)

Nomenclature.Terms for description of new

materials should be based on scientific char-
acterization. Trivial terms, introduced locally,
and still used, should be avoided. In UK and
France the term carbon fiber is used correctly.
In USA, however, the scientifically unjustified
term “graphite fiber” is preferred in industry,
and in German, as well as in Eastern Euro-
pean languages, the tradition of describing car-
bon materials as coal has been carried over to
Figure 42. Comparison of the reinforcing fibers for ad- the new material carbon fiber (German: Kohle-
vanced composites with polymer matrix: glass, polyarami-
des, and carbon faser). The IUPAC has therefore established a
sub-committee for description and characteriza-
Figure 43 shows the superior specific stiff- tion of carbon and graphite materials in general
ness (Young’s modulus measured in fiber direc- and of carbon fibers in specific. Some tentative
tion divided by the density) of various types recommendations for the terminology [87], part-
of carbon fibers in comparison with those of ly still under discussion, are the following:
polyaramide and glass fibers. The extremely Carbon fibers are fibers (filaments, yarns,
low values for isotropic conventional metals rowings) consisting of at least 92 wt % carbon,
and the theoretical maximum for the anisotropic regularly in the nongraphitic stage, that is, with
graphite single crystal are also included. This two-dimensional long-range order of the carbon
figure demonstrates not only the superiority of atoms in planar hexagonal networks, but with-
carbon fibers but also the variability of stiffness out any measurable crystallographic order in the
among the various carbon fiber types. In the best third direction (c direction) apart from more or
case, up to 80 % of the theoretical modules of a less parallel stacking.
graphite layer can be realized in a commercial HM-type carbon fibers are carbon fibers with
material. a value of the modulus of elasticity in the fiber
direction larger than 30 % of the elastic number
c11 of a graphite single crystal, but with a ratio
of tensile strength to tensile modulus below 1 %.
46 Fibers, 5. Synthetic Inorganic

HT-type carbon fibers are carbon fibers with strength: stiffness ratio strictly controls the frac-
a value of the tensile strength above 3000 MPa ture elongation (strain to failure) of the fibers.
and a ratio of strength to stiffness of ca. 1.5 – In Figure 44 these relationships are demon-
2.0 %. strated graphically in three coordinates. The val-
IM-type carbon fibers belong to the HT type ues of all commercially available carbon fibers
carbon fibers because of comparable values of are grouped around two areas, which describe
tensile strength but are characterized by im- opposing combinations of properties: the high
proved stiffness (Young’s modulus up to 30 % modulus domains (HM-type fiber) and the high-
of the theoretical c11 value with remaining val- strength, high-tenacity domains (HT-type fiber).
ues of the ratio strength to modulus above 1 %).
In addition, the precursor material of the car-
bon fibers is important because the combination
of various fiber properties and the behavior of
the carbon fiber mechanically, physically, and
chemically depend strongly on the raw material.
PAN-based carbon fibers are carbon fibers
obtained from polyacrylonitrile (PAN) precur-
sor fibers by stabilization treatment, carboniza-
tion, and possibly final heat treatment at even
higher temperature.
Isotropic pitch-based carbon fibers are car-
bon fibers obtained from isotropic pitch fibers
by stabilization treatment and carbonization.
Anisotropic pitch-based carbon fibers (MPP-
based carbon fibers) are carbon fibers obtained
from mesogenic pitch after this has been trans-
formed into mesophase pitch (MPP) during the Figure 44. Characterization of the various commercial car-
process of spinning, by stabilization of the spun bon fiber types by tensile strength and Young’s modulus
mesophase pitch fibers, carbonization, and final HT = high tensile; IM = intermediate modulus; HM = high
modulus; MPP = mesophase pitch-based high-modulus
heat treatment at even higher temperature. fibers
Rayon-based carbon fibers are carbon fibers
obtained from rayon precursor fibers by chem-
ical pretreatment and carbonization. They are Nearly all carbon fibers available commer-
isotropic carbon fibers and can be transformed cially have a near-circular cross section. As
into anisotropic carbon fibers with high strength shown in Figure 45 (see next page) the cross
and stiffness by hot stretching above 2800 K. section of the carbon fibers mirrors the fiber pre-
Gas-phase grown carbon fibers are carbon cursor. Currently (1986) wetspun PAN is usually
fibers grown in a hydrocarbon atmosphere with the raw material. Gasphase-grown carbon fibers
the aid of fine particulated solid catalysts such as exhibit the best graphitic order and preferred ori-
iron or another transition metals. They consist of entation, but have no importance for reinforce-
graphitizable carbon and can be transformed into ment.
graphite fibers by heat treatment above 2800 K.

5.1.2. Chemical Composition

5.1. Properties
Carbon fibers consist of elemental carbon. As all
5.1.1. Mechanical Properties synthetic carbon materials, they are fabricated
from carbon compounds by thermal degrada-
The strength values differ dramatically among tion (pyrolysis), and the final (i.e., maximum)
the various carbon fiber types. Because car- heat-treatment temperature controls the nature
bon fibers exhibit brittle fracture behavior, the and amount of remaining ligand atoms in the
residual carbon. The HM-type fibers consist
 Fibers, 5. Synthetic Inorganic 47

Figure 45. Fracture surface of the precursor fibers (rayon, wetspun PAN, mesophase pitch) and of the resulting carbon fibers
(REM)
Carbon yield given in wt %

of nearly pure carbon; however, the HT-types carbons belongs to the graphitic modification
contain some nitrogen (<4 wt %) and oxygen mainly with sp2 hybridization and thus a ten-
(<1 wt %). Hydrogen contents can be neglected dency to form planar polyaromatic molecules
[88,89]. but with only two-dimensional order and no
Surface-treated carbon fibers contain, in ad- hexagonal ABAB-shaped arrangement of these
dition, solid oxygen complexes on the surface polyaromatics in the third dimension. In this
and organic coatings (sizing), which protect the sense carbon fibers can be described as disor-
carbon fibers during handling and transport. dered carbon with more or less ordered polyaro-
matic layers and a hypermolecular anisotropic
arrangement of these polyaromatics parallel to
5.1.3. Structure the fiber axis. Perfectness, size, and arrange-
Solid elemental carbon has two equilibrium ment of these polyaromatics control the physical
modifications: diamond with isotropic homopo- and especially the mechanical properties of the
lar bonds between the carbon atoms and sp3 fibers. Partial sp3 hybridization was confirmed
hybridization of the electron levels and the in all artificial carbon, and especially in carbon
hexagonal graphite with sp2 hybridization, thus fibers, and is explained by the carbon atoms on
anisotropic structure. Rhombohedral graphite the edges and in disclinations of the polyaromat-
is a result of mechanical deformation of the ics [90, 91].
hexagonal form. The broad variety of disordered
48 Fibers, 5. Synthetic Inorganic

Figure 46. TEM bright field images (cut perpendicular to the fiber axis) [90, 92]
A) Typical commercial HT type (T 300) B) HM type (SIGRAFIL HM) carbon fiber

Transmission electron microscopy (TEM)

produces bright field images of thin-layer cut-
tings of HT- and HM-type carbon and reveals
the different degree of defect structure (Fig. 46)
[90,92].
The preferred orientation in the direction of
the fiber axis as indicated by the Ruland param-
eter q (0 corresponds to a statistic arrangement
and −1.0 means completely preferred orienta-
tion) is shown in Figure 47 [93]. Some exper-
imental fiber types based on mesophase pitch
reach nearly 100 % of the theoretical Young’s
modulus, i.e., that of a single crystal. Such a
Figure 47. Young’s modulus of the various types of car-
preferred orientation is combined, however, with bon fibers correlated with the degree of preferred orientation
the disadvantage of low shear resistivity. measured by X-ray diffraction and expressed by the Ruland
The layer distance, which is easily measured, parameter [93]
is a good indication of the degree of defect struc- 0 = statistical distribution, 1.0 = orientation of graphite sin-
gle crystal
ture of a carbon fiber. Figure 48 shows the values
for commercial fibers as received and the reduc-
tion of the c/2 value by further heat treatment,
which heals structural defects [94].
 Fibers, 5. Synthetic Inorganic 49

cape of the remaining ligands, which causes

severe structural disturbance. Only minor im-
provement takes place during further annealing.
The variety of curves for PAN-based fibers is
caused by differing oxidative pretreatment dur-
ing the stabilization before carbonization [96,
137].
Figure 50 (see next page) shows the effects on
the ultrastructure of heat treatment. The ordering
process at the highest temperatures is easy to rec-
ognize for a commercial HT fiber by the enlarge-
ment of domains with parallel layer stacking
(Figs. A and B). Such improvement of strength
by annealing is not found in the case of pitch-
based fibers with superior preferred orientation
Figure 48. Main interlayer distances c/2 of various com- because of increased shear sensibility by anneal-
mercial carbon fibers and their decrease due to subsequent
heat treatment. The c/2 values of graphitizable petroleum ing (Figs. 50 C and D). The much higher ten-
coke are included for comparison [92, 94, 95] dency of mesophase pitch-based fiber towards
a) Ideal graphite; b) Petroleum coke; c) P55, MPP-based; structural rearrangement can also be seen in Fig-
d) AS4, PAN-based; e) T300, PAN-based; f ) T800, PAN- ure 50.
based
Based on electron microscopic studies, sev-
This healing process results in higher density eral models for structure in carbon fibers have
and increased Young’s modulus, which is shown been proposed. Four of these are shown in Fig-
in Figure 49B. The strength passes a maximum ure 51 [97–99]. In all cases, parallel stack-
at heat-treatment temperatures around 1500 ◦ C ings of polyaromatic layers are arranged in
(Fig. 49A). The reduction of strength, with the the fiber direction in forms such as ribbons,
minimum around 1800 ◦ C, is caused by the es-

Figure 49. The effects of heat posttreatment of carbon fibers [96, 137]
A) Tensile strength
SAF, stabilization treatment a) 230 – 260 ◦ C/40 min; b) 230 – 270 ◦ C/40 min; c) 230 – 290 ◦ C/40 min; d) MPP
B) Young’s modulusSAF, stabilization treatment a) 230 – 260 ◦ C/40 min; b) 230 – 270 ◦ C/40 min; c) 230 – 290 ◦ C/40 min;
d) MPP
The effect of varied heat pretreatment during stabilization is included. For all PAN-based fibers, SAF precursor was used
[137]. For comparison [96], the behavior of MPP carbon fibers is included.
50 Fibers, 5. Synthetic Inorganic
Table 16. Physical properties of typical commercial PAN-based carbon fibers.

Density, g/cm3 Electrical TEP, µV/K Susceptibility χ ∗, Specific Thermal

resistance, 10−6 emu/g heat Cp, J/gK conduct. λ,
10−3 Ω m W/mK

⊥ 

PAN-based HT 1.76 – 1.81 1.5 – 2.4 −1.6 to −2.4 −0.3 −0.05 0.71 8 – 20
PAN-based HM 1.82 – 2.00 0.6 – 1.0 17.2 −6.6 −0.63 0.71 60 – 100
Anisotropic 2.00 – 2.15 0.4 – 1.1 22.6 −9 to −10.4 −0.70 0.93 110 – 375
pitch-based
Isotropic 1.60 5 – 10 −0.74 to −5.32 −0.64 to −4.26 15
pitch-based

∗ Perpendicular (⊥) or parallel () to fiber axis

plates, hoses, tubes, or combinations of the var-

ious structural elements.

5.1.4. Physical Properties

Table 16 shows the densities, electrical resistivi-

ties, thermoelectric powers (TEP), magnetic sus-
ceptibilities, heat capacities, and thermal con-
ductivities of the various carbon fiber types.
The reversible thermal expansion is highly
anisotropic (Table 17). In PAN-based HT-type
carbon fibers high anisotropy is also found, as is
the case for graphite single crystals. In contrast,
the reported anisotropy in a mesophase pitch-
based HM-type fiber is much smaller [100]. Ex-
perimental measurement for the direction per-
pendicular to the fiber axis, however, is very
difficult, and a comprehensive study is still not
available.

Table 17. Reversible thermal expansion of some commercially

available carbon fibers.
CTE α , CTE α⊥ , — α⊥ /α —
10−6 K−1 10−6 K−1

Graphite, single crystal 0.5 – 1.0 29 29 – 58

PAN-based HT 0.6 5 – 30 8.3 – 50
PAN-based HM 1.0 15 15
Anisotropic, pitch-based 0.9 – 1.4 6 4.3 – 6.7
Isotropic, pitch-based 3 3 1

Typical mechanical properties of carbon

fibers are listed as a part of Figure 44.
Figure 50. Effect of high-temperature heat treatment on the
ultra structure and especially on the enlargement of the do-
mains with parallel stacking of layers (TEM bright field of 5.1.5. Chemical Properties
cuts parallel to the fiber axis)
A) PAN-based HT fibers (AS4W) as received; B) The same The chemical resistivity of carbon and graphite
after-treatment at 2400 ◦ C; C) MPP-based fiber (P55) as re- materials against aqueous solutions and most
ceived; D) The same after treatment at 2440 ◦ C
 Fibers, 5. Synthetic Inorganic 51

Figure 51. Structural models of carbon fibers

A) Two-dimensional model proposed by Ruland [97] (ribbon model); stretched graphitized rayon-based fibers B) Three-
dimensional model proposed by Johnson [98] (plate/sheet model); PAN-based fibers C) Ring/tube model proposed by Ober-
lin [98] for all carbons resulting from thermal degradation of carbonizable solids [99] D) Hose-shaped layer stacking model
proposed for highly heat-treated carbon fibers [99]

chemicals at ambient temperatures is well-

known and has been utilized in chemical appa-
ratus. The behavior of carbon fibers is similar.
Only fluorine acids as well as strong oxidants
attack carbon fibers strongly. The tendency of
graphite to form intercalation compounds with
halogens, salts, oxidizing acids, and some other
substances is also well-known. The majority of
carbon fibers, which consist of nongraphitizable
carbon is less susceptible to intercalation attack.
Only gasphase grown fibers can be intercalated
easily.
Most destructive for carbon fibers are their
reactivity with metals, above all aluminum at
temperatures below 1000 K, and their reactivity
with solid oxides at temperatures above 1000 K.
This reactivity limits the use of uncoated carbon
fibers for reinforcement of metals and oxides.
However, if reaction and diffusion barriers are
built in – silicon carbide, titanium nitride, and
similar coatings have proved to be successful
barriers (Fig. 52) –carbon fibers can be used to
reinforce metals and oxides [101, 102]. Figure 52. SiC-coated carbon fibers in a SiO2 glass matrix
(parallel to the fibers) [101]
52 Fibers, 5. Synthetic Inorganic

Figure 53. Oxide complexes on surface-treated carbon fibers and their affinity to polar groups in epoxy resins and curing
agents [103]

Solid surface oxides form as an intermediate [103] shows the various types of surface oxides
stage before formation of volatile carbon oxides. and their affinity to polar groups in the resins,
Such solid surface oxide complexes improve the which initiates at least chemisorptive adhesion
adhesion of carbon fibers in polymers and matrix and perhaps even formation of extensive chem-
in a composite [105,106]. The thermal stabil- ical bonding between fiber and resin.
ity of surface oxides is limited to temperatures The degree of adhesion is measured by inter-
below 800 K for carboxylic groups and below laminar shear strength (Ilss). Figure 54 shows
1000 K for nonacidic surface oxides. Figure 53 the effect of stepwise desorption of the surface

Figure 54. Gases (CO2 , CO) liberated during thermal desorption of surface-treated carbon fibers [89]
A) HM type, Sigrafil HM12S (Sign), 120 h oxidized in 68 % HNO3
B) HT type, showing loss of nitrogen, content of PAN-based carbon fibers above 1000 ◦ C
a) T300S; b) T300U; S: surface treated; U: untreatedIlss = interlaminar shear strength
 Fibers, 5. Synthetic Inorganic 53

oxides in surface-treated carbon fibers by heat bon fibers in air [104]. The HT-type fiber, which
treatment in argon and the resulting effects of is given a maximum heat treatment at 1450 ◦ C
such stepwise desorption on the remaining ad- during fabrication, is much more sensitive to to-
hesion in an expoxy matrix. The strong improve- tal oxidation than the HM-type fibers, which are
ment of adhesion in surface-treated HM fibers is heat treated above 2500 ◦ C during fabrication.
associated with the carboxylic groups. The im- Total oxidation can be catalyzed even by alkali-
provement of adhesion in HT-type fibers by sur- metal compounds, as is the case for carbon and
face treatment is much smaller, a maximum of graphite materials. Heavy metal oxides are ef-
30 % of the total adhesion. The remaining ad- fective catalysts. Experimental results on the ef-
hesion in HT-type fibers is strongly correlated fect of copper oxide and vanadium oxide on the
with the nitrogen content in the fiber. The ad- relatively resistant HM-type fibers are included
hesion of the fibers decreases abruptly if they in Figure 56. As a consequence, metallic impu-
are heat-treated above 1200 ◦ C, which drives off rities in carbon fibers have to be strictly avoided
the nitrogen remaining from the PAN precursor during industrial production.
[88].
The controlled formation of surface oxides
can be attained by three routes:
1) Thermal oxidation at temperatures above
700 K
2) Wet oxidation in boiling nitric acid or in a
similar oxidative liquid
3) Anodic oxidation in aqueous solution
Anodic oxidation is the only method used in-
dustrially for surface oxidation of carbon fibers.
This process is the easiest to control and forms
the greatest amount of surface oxides (Fig. 55).
Figure 56. Thermal oxidation rates of HM- and HT-type
carbon fibers (Arrhenius plots), also showing the catalytic
effects of heavy metal oxides on the oxidation of HM fibers
[104]; r = rate constant
a) HM (Sigrafil); b) HT (Toho); c) HM + CuO;
d) HM + V2 O5

5.2. History
Public disclosures of practical processes for con-
verting textile fibers into useful carbon fibers
have been confined largely to the patent liter-
ature.
Figure 55. Amount of surface oxides formed by thermal,
wet, and anodic surface treatment of HM fibers as measured
by weight loss during thermal desorption in argon [104] 5.2.1. Rayon-Based Carbon Fibers
a) Thermal oxidation; b) in HNO3 oxidized; c) anodic oxi-
dation For rayon as the precursor material, a com-
prehensive survey was published by R. Bacon
Thermal oxidation, although simple to do, is [107]. One hundred years ago, Edison [108]
dangerous because of the rapid reaction rate and described an incandescent-lamp filament made
the danger of fiber damage due to total oxida- by carbonizing a filament of natural and re-
tion. Figure 56 shows in an Arrhenius plot the generated cellulose material. In the 1950s Ab-
experimental weight loss on oxidation of car- bott [109] developed a process for converting
54 Fibers, 5. Synthetic Inorganic

rayon into a fibrous carbon material for insu- 5.2.2. PAN-Based Carbon Fibers
lation, filtration, and absorption. This material
was carbonized at temperatures up to 1000 ◦ C The history of PAN-based carbon fibers starts in
and possessed tensile strengths of only 280 MPa. 1950 with the observation of R. C. Houtz [119]
In 1959, Union Carbide [110–112] started com- that polyacrylonitrile fibers are converted into
mercial production of similar fibers, and other black, flameproof materials by heat treatment at
companies in the U.S.A. followed. 300 ◦ C in air. However, products produced by
Various fiber types heat-treated at final tem- this method were not used before 1959 [120].
peratures around 1200, 1800, and even above At that time the discovery was made that flex-
2500 ◦ C have become commercially available, ible, flameproof textiles with the original fiber
e.g., the carbonized VIB type and the WYB type structure can be obtained only if the exother-
heat-treated at graphitization temperatures, both mic reaction between 150 and 300 ◦ C is strictly
from UCC (Union Carbide). The tensile strength controlled and if the high shrinkage during this
of such fibers ranged from 300 to 700 MPa, thermal treatment is minimized by mechanical
while their moduli were between 30 and 50 GPa. means. In 1960 the process to produce a flame-
The most important application was the rein- proof fiber, starting with Dupont’s AF Orlon
forcement of phenolic resins to form ablative fiber and commercialized as Black Orlon, was
materials for rocket and missile components. described in detail by Vosburgh [121]. Heat
This early period of carbon fiber production treatment up to 15 h at 220 ◦ C was needed to
and application is reviewed by Schmidt and produce a well stabilized fiber with a strength
Hawkins [113]. of 40 % of the value of the original PAN fiber.
In these first years of the carbon fiber indus- The oxygen content of the final product was 10 –
try, several companies introduced a pretreatment 20 wt %.
process for the precursor fibers to increase car- Surprisingly, this oxidizing-blackening treat-
bon yields and speed up the processing rates, ment of the PAN fibers was not complemented
especially in the early heat treatment stage. The by carbonization. Such a combination was first
Pluton fiber of 3 M [114] was introduced in claimed by Shindo [120] in 1959. A maxi-
1961. A decisive improvement of the mechani- mum tensile strength of 100 MPa was obtained.
cal properties of the carbon fibers was the plastic In 1965, Johnson, Philip, Watts [122] added
deformation of the fibers at temperatures above to this combined process the need to restrain
2500 ◦ C. This UCC process [115] led to the com- shrinkage or alternatively to stretch the PAN
mercial production of the Thornell type, which fiber during stabilization treatment. They ob-
had in 1965 a tensile strength of 1260 MPa and tained carbon fibers with Young’s moduli up
a modulus of 175 GPa (Thornell 25). to 420 GPa. This process is now the standard
This was the period when the US Air Force process for fabrication of PAN-based carbon
Material Laboratory in Dayton, Ohio, strongly fibers, although patent protection turned out to
supported further development in the field of be limited and is completely gone today. A more
high-modulus carbon fibers [116, 117]. The goal detailed history is given by Watts [123], and
was to replace boron fibers as soon as it proved a complete literature survey is given by D. J.
possible to fabricate high-performance carbon Mueller [124].
fibers with a minimum modulus of 350 GPa.
In 1970, UCC reached the goal with the com- 5.2.3. Pitch-Based Carbon Fibers
mercially available Thornell 75 HM-type car-
bon fiber, which also had a Young’s modulus The processes for carbon fibers from pitches are
of 500 GPa, a value corresponding to 50 % of based on the observation of Otani [125] in 1963
the theoretical c11 value. Hitco [118] entered the that some pitches are spinnable to pitch fibers,
market with yarns produced by similar methods. which can be converted into carbon fibers. Pitch
Although these carbon fibers were satisfactory in from poly(vinyl chloride) turned out to be the
applications, the final decision of the market was best, but a variety of other pitches can be used af-
to restrict use to the PAN-based carbon fibers. ter specified pretreatment as summarized by Su-
gio Otani and Asao Oya [126]. The mechani-
cal properties of the resulting carbon fibers were
 Fibers, 5. Synthetic Inorganic 55

in the range 800 – 1800 MPa for tensile strength ported by Endo [134] in 1974 when he rec-
and 20 – 50 GPa for Young’s modulus. These ognized that the whisker growth follows a cat-
pitch-based carbon fibers were commercialized alytic mechanism starting from fine, dispersed
in 1970 by Kureha Chemical Industries and are solid metal particles in the substrate. Whisker
still the only ones commercially available in the lengths up to 250 mm and tensile strength val-
form of continuous yarns [127]. In 1985, Free- ues up to 26 000 MPa have been reported so far
man [128] reported that the Ashland Company by Endo [134]. Commercialization has not been
started production of a variety of carbon fiber announced, however, probably because of the
types using petroleum pitch as the raw material. completely different structure of vapor-grown
Coal tar pitch is recommended as an alternative carbon fibers. These consist of soft carbon,
precursor material by Rommey [129]. All these that is, the graphitizable less-disordered variety.
pitch-based carbon fibers belong to the isotropic, Therefore, high mechanical properties cannot be
low-modulus type. expected. They are most suitable for intercala-
Fabrication of anisotropic pitch-based carbon tion (high electrical conductivity).
fibers with greatly improved mechanical prop-
erties was achieved by Lewis and Singer et
al. [130] in 1976. This process is based on the 5.3. Production
mesophase, a liquid crystal formed within the
pitch before spinning that enables the forma- All commercial production processes for car-
tion of a preferred orientation in the pitch fiber, bon fibers are based on carbonization of poly-
thus also in the final carbon fiber. Values of ten- mer fiber precursors. The preconditions for use-
sile strength up to 3000 MPa and an extremely ful fiber formation compiled in Table 18 must
high Young’s modulus, up to 600 GPa, can be be fulfilled. Thus, the number of suitable poly-
achieved. mer fibers is limited. The fiber form is always
Laboratory developments have continued in preserved during carbonization in the case of
many countries of the Western World. Commer- nonmeltable polymers, such as thermosetting
cial products are available from AMOCO (pre- resins, which can be thermally degradated di-
viously Union Carbide) [131]. rectly. Thermoplastic precursor fibers have to be
converted into a nonmeltable form before car-
bonization. This is called stabilization treatment
5.2.4. Vapor-Grown Carbon Fibers and occurs on conversion of the linear polymers
into ladder polymers and on formation of addi-
Whiskers and needles of carbon deposited from tional cross-linkages. In the case of pitch precur-
the gas phase were described in 1966 by Fitzer sor fibers, the melting of the mixture of polyaro-
and Schlesinger [132]. Fitzer and Rhee matic compounds must be hindered by oxida-
[133] continued these studies and reported in tion. Three precursor materials are satisfactory:
1970 growth rates and mechanical properties of (1) rayon fibers, (2) PAN fibers, and (3) pitch
the whiskers and needles. Tensile strengths up fibers. Rayon fibers do not require stabilization,
to 1500 MPa and stiffness values up to 300 GPa only preimpregnation is necessary to improve
were reported. The decisive progress was re- the carbon yield. PAN and pitch fibers need sta-

Table 18. Restrictions on the precursor fiber for carbon fiber fabrication

Preconditions for carbon fiber manufacture Parameters

Precursor Process

Preservation of the fiber form of the thermosetting or thermoplast fibers direct thermal degradation or stabilization treatment of
polymer meltable precursor before thermal degradation
High carbon yield selection of the polymers optimization of the stabilization and carbonization
parameters
Preferred orientation of the polycarbon highly cross-linked, unmeltable stretching of the precursor before or during stabilization
layers with highest degree of defects in the polymers and/or hot-stretching of the carbon fiber
ultra structure
56 Fibers, 5. Synthetic Inorganic

bilizing pretreatment. The carbon yield is lowest This hot stretching process is difficult to carry
for rayon fibers and highest for stabilized pitch out on an industrial scale. Therefore, carbon
fibers: fibers are no longer produced from rayon.
Rayon fibers 25 %
In PAN- and pitch-based anisotropic carbon
Oxidized pitch fibers 80 % fibers, the preferred orientation is introduced
Polyacrylonitrile 50 % into the precursor before carbonization. Poly-
Oxidized pitch up to 80 %
Phenolic and furan resins up to 85 % acrylonitrile is the most important precursor ma-
terial. More than 90 % of all commercially pro-
The most important parameter in producing duced carbon fibers that are used for reinforce-
high-quality carbon fibers is the preferred orien- ment of polymer material are based on this poly-
tation of the polyaromatic layers parallel to the mer. Only a minor part is produced from pitch.
carbon fiber axis. Only then can the high strength
of the bonds in the molecular structure of the
graphite lattice (c11 = 1060 GPa, c33 = 33 GPa) be 5.3.1. PAN Precursor Fiber
transferred into stiffness and strength of the car-
bon fiber. The low shear modulus in the graphite Textile PAN fibers usually consist of ternary
crystal structure (c44 = 4.6 GPa) must be avoided mixtures of copolymers with 89 – 95 wt % acry-
by having the highest degree of defects in the lonitrile (AN), 4 – 10 wt % of a non-ionogenic
ultrastructure of the carbon fiber. In the case of comonomer plasticizer, and 1 wt % of additive
rayon precursor fibers the needed high degree of to chemically bond dyes [135]. For the pre-
structural imperfectness can be realized, how- cursors for carbon fibers, a lower content of
ever the preferred orientation is realizable only comonomers, usually below 3 wt %, is used.
by hot working of the carbon fiber at 3000 K.

Figure 57. The chemistry of stabilization and carbonization: fabrication from homopolymer PAN and stabilized PAN [137,
138, 147]
 Fibers, 5. Synthetic Inorganic 57

Polymer fibers can be spun by melt, wet, and jugated double bonds. The resulting aromatic
dry spinning processes. In the case of polyacry- polymer has ladder units of about five, corre-
lonitrile as a carbon fiber precursor, the wet spin- sponding to the average number of isotactic se-
ning process is the most important. In 1986 a quences in the nitrile polymer. Cyclization can
new melt spinning process was presented which occur with or without simultaneous dehydrogen-
would offer economic advantages [136]. ation as shown in Figure 58 [137]. In both cases
The solvents dimethylformamide (DMF) and strong exothermic reactions are observed. In in-
dimethylacetamide (DMA) are usually preferred dustrial processes, cyclization is always carried
for wet spinning today. For carbon fiber precur- out in an oxidizing atmosphere because of the
sors, however, the inorganic solvents nitric acid, much higher carbon yield during the subsequent
stannum chloride and thiocyanate are also used. carbonization [139].
In any case, copolymer composition of the pre-
cursor, the spinning technology, and especially
the solvent are almost always strict commercial
secrets. Only Courtaulds (United Kingdom) de-
scribes the use of dimethyl sulfoxide for fiber
precursor fabrication.
The main difference between textile PAN
fibers and PAN precursor fibers is the different
degree of stretching: the stretching ratio for tex-
tile fibers is 1 : 2 to 1 : 10, that for PAN precur-
sor fiber 1 : 12 or more. There is the danger of
overstretching, which introduces defects into the
polymer fiber that initiate defects in the carbon
fibers, thus causing low strength.
The extremely high-strength and high-
tenacity carbon fibers are mainly produced from
precursors more carefully spun and stretched to
a higher degree. Dry-jet wet spinning would be
a good method for this.

5.3.2. Stabilization

Polyacrylonitrile is a thermoplastic polymer that

decomposes above 370 ◦ C. A suitable stabiliza-
tion process is needed before carbonization to
obtain an infusible intermediate that preserves
the orginal fiber structure. This intermediate is
known as inflammable textile (e.g., PAN-Ox).
The stabilization step is the most important
Figure 58. The exothermic stabilization in nitrogen (cy-
one from the viewpoint of carbon fiber qual- clization) and in air (cyclization and dehydrogenation) as
ity and process economy. The reaction is dif- revealed by DSC (differential scanning calorimetry) [137]
fusion controlled, and a residence time of ca.
1 h at temperatures between 200 and 280 ◦ C There is a direct correlation between the
is needed. Fiber shrinkage during stabilization amount of oxygen absorbed and the density of
must be avoided (see Section5.2.2). the stabilized fiber. The best mechanical prop-
The chemistry of the stabilization process is erties result for a precursor density of 1.4 –
illustrated schematically in Figure 57 (see pre- 1.42 g/cm3 , which corresponds to oxygen con-
vious page). The thermoplastic chain is cyclized tents of 10 – 14 wt % (Fig. 59).
to a naphthyridine ring system and simultane- The stabilization causes the color to change
ously dehydrated in the backbone to form con- from the white of polyacrylonitrile to yellow
58 Fibers, 5. Synthetic Inorganic

and brown and finally to the black of the in- ity of the final carbon fiber product is controlled
termediate, the oxidized, inflammable polyacry- by the precursor fiber, the stabilization treatment
lonitrile. The stabilization chemistry has been and the oxygen content, and finally by the car-
treated comprehensively in numerous papers, bonization schedule.
e.g., [137, 138, 140–147]. An example of a continuous stabilization and
carbonization for fabrication of carbon cloth
from PAN from patent literature is shown in Fig-
ure 60 [152].

5.4. The Pitch Fiber Process

5.4.1. Isotropic and Anisotropic Pitch Fiber

Precursors

Carbon fibers made from pitch precursor are

available with isotropic or anisotropic structure,
the former made from isotropic pitch, the later
from mesophase pitch. The isotropic pitch-based
carbon fibers have low mechanical properties.
They have been produced industrially from coal
Figure 59. The effect of oxygen uptake during stabilization tar pitch by Kureha (Japan), for more than 15
on the strength of the final carbon fiber
a) 230 ◦ C isotherm/air; b) 230 ◦ C isotherm, 1st stage N2 , years. The petroleum pitch producer Ashland
2nd stage air; c) 230 → 270 ◦ C nonisotherm/air (United States) manufactures isotropic carbon
fibers, which are used mostly for thermal and
mechanical insulation but also as fillers.
5.3.3. Process Parameters Anisotropic carbon fibers, which can be used
for reinforcement because of their excellent
The carbonization step can be carried out much mechanical properties, are produced in a process
faster than the stabilization step; however, the that takes advantage of the larger planar polyaro-
evolution of the volatile byproducts, mostly matic molecules in pitch and their tendency to
H2 O, HCN, CO2 , and N2 , must be taken into form liquid crystals with parallel polyaromatic
account [148]. layers. The mesophase pitch is melt spun and
Practical temperature – time profiles have stretched in the plastic deformable stage to pro-
been published [137, 142, 149–151]. The qual- duce pitch fibers with preferred orientation.

Figure 60. Hitco process for production of carbon cloth from PAN cloth showing temperature and tension profiles [152]
 Fibers, 5. Synthetic Inorganic 59

Figure 61. The coalescence of discotic liquid crystals in pitch

All pitch fibers must be stabilized before car- ics with aliphatic side chains and a molecular
bonization, but pitch fibers with preferred orien- mass around 1000 (petroleum pitches) are able
tation consisting to a large extent of mesophase to form nuclei for discotic liquid crystals [153].
not only hinder melting during carbonization but The liquid crystals in pitch are spherical with
also cross-link the polyaromatics upon oxidation the molecular orientation shown in Figure 61.
thus hindering formation of graphitized carbon The coalescence of these liquid crystals with
fibers. disklike molecules is similar to that of the liquid
crystals with rodlike molecules.
From the viewpoint of the phenomenology,
5.4.2. The Mesophase Formation the formation of liquid crystals is similar to that
of crystallization, starting from observable nu-
Pitch is the residue from distillation of coal tar clei with diameters larger than 1 µm. The growth
or crude oil or from cracking hydrocarbons. All and coalescence proceed until all isotropic pitch
pitches consist of thousands of aromatic hydro- matrix is consumed. Insoluble impurities in the
carbons along with more or less cyclic aliphatics molten pitch matrix (primarily quinoline insol-
and aliphatic side chains. The molecular mass ubles, i.e., the pitch residue) inhibit coalescence
of the polyaromatic compounds ranges between and therefore also the formation of large vol-
200 and 800. All the compounds in a single pitch umes of anisotropy.
have never been identified. Pitches are char-
acterized by fractionation: their solubility in a
sequence of standard solvents (Table 19). The 5.4.3. Process Steps
model molecules shown in the table are sug-
gested by comprehensive analytical investiga- The viscosity of pitch, a precondition for sat-
tions [153]. The melting points of the various isfactory melt-spinning behavior, is determined
pure compounds cover a range of hundreds of by pitch composition. Figure 62 shows the ap-
degrees. Pitches, however, form multi-eutectic parent viscosities of a typical petroleum pitch
systems with softening temperatures between 50 and a typical coal tar pitch as functions of heat
and 300 ◦ C, much lower than the melting tem- treatment [154]. The behavior of toluene-soluble
peratures of the pure aromatic components. (TS) and toluene-insoluble (TI) fractions of the
The mesophase is formed during thermal coal tar pitch and of two mixtures of TS and TI
degradation in the temperature range 400 – fractions are included. Softening of the pitches
450 ◦ C and is controlled by the hydrogen con- upon heating is indicated by viscosity decrease;
tent remaining in the aromatics during this heat solidification due to mesophase formation, by
treatment. Aromatics with an average molecular viscosity increase. Spinning is difficult for
mass around 800 (coal tar pitches) and aromat-
Table 19. Characterization of typical coal tar and petroleum pitches by solvent fraction and model molecular structures for the fractions [153]

60
Fibers, 5. Synthetic Inorganic
 Fibers, 5. Synthetic Inorganic 61

high mesophase contents (which produce the

HM fibers), however carbon yield increases with
viscosity (Fig. 63) [154]. These contradicting
conditions cause technological problems.

Figure 62. Apparent viscosity (rotation viscosimeter) of the

petroleum pitch A240, the purified coal tar pitch SP80, frac-
tions resulting from toluene extraction of SP80 (TS = toluene
soluble, TI = toluene insoluble), as well as two mixtures of
TS and TI [154]

Figure 63. Carbonization residues from the pitch samples

described in Figure 62 [154]
a) Toluene soluble; b) SP80 and 4 : 1 mixture; c) 1 : 1 mix-
ture; d) 1 : 4 mixture; e) 1 : 9 mixture; f ) toluene insoluble

Stabilization is carried out between 200 and

300 ◦ C [155], much like in the PAN process.
The stabilization times are dramatically shorter,
however, between 10 and 30 min. The patent lit-
erature indicates that commercial pitch-based
carbon fibers are given a final heat treatment
Table 19. Continued.

around 1800 ◦ C (P55 type). Fiber types with a

relatively high Young’s modulus, in the area of
400 GPa, can be achieved (cf. Fig. 44). A flow
sheet for the entire fabrication process is given
in Figure 64 [156].
62 Fibers, 5. Synthetic Inorganic

available, of the intermediate modulus fibers in

development, and of isotropic and anisotropic
pitch-based fibers.

Figure 65. Stress – strain behavior of commercially avail-

able PAN- and pitch-based carbon fibers

The pitch process for carbon fibers poten-

tially offers the capacity to produce carbon fibers
covering the whole mechanical property range
of the carbon fiber family. However, these ex-
pectations for pitch-based fibers have not yet
been realized in spite of worldwide, intensive
research.
The overwhelming part of commercial car-
bon fibers is the PAN-based HT type. High
strain-to-failure of the fibers is seen as one of the
key properties for the fracture toughness needed
for broader application of advanced compos-
ites. The best strain values, between 1.5 and
2 %, are possible on industrial scale only with
PAN-based HT-type fibers. Further, manufac-
turing problems are reduced if fabrication starts
from a fully synthetic precursor material, with
strictly controlled quality, instead of from a
semi-natural raw material, such as petroleum or
coal tar pitches, with strongly varying compo-
sitions depending on crude or coal type and the
Figure 64. Flow sheet for manufacture of carbon fibers from
thermal history.
pitch (Union Carbide Corp. (UCC) process) [156] The applications of ultrahigh modulus carbon
fibers from anisotropic pitch will most likely re-
main restricted to space structures and to carbon
fiber-reinforced carbon fiber material (carbon –
5.5. Comparison of the Carbon carbon composites). The challenge to increase
FibersBased on PAN and on Pitch the applications of anisotropic pitchbased car-
bon fibers can be satisfied only if production of
Figure 65 shows the stress – strain behavior medium-quality fiber types can be coupled with
of PAN-based carbon fibers, as commercially further drastic price reductions.
 Fibers, 5. Synthetic Inorganic 63

5.6. Commercial Availability and Sumitomo, another Japanese PAN-precursor

Economic Aspects producer. Courtaulds fabricates precursors and
is thus independent from Japanese imports. It is
5.6.1. Companies and Trade Names also the only company that sells PAN-precursor
fibers suitable for a carbon fiber manufacture the
In the 1960s, the industrial production of car- world over without the limitations of licenses
bon fibers started in UK, Germany, Japan, and or joint ventures. In Germany, Sigri is inde-
USA with a total volume below 1000 t/a. Very pendent, but fabricates no precursors. The pro-
soon, however, Japan had the advantage because ducers, their production, their trade names, and
of the availability of PAN-fiber plants using the some commercially available carbon fiber types
wet process, whereas in USA and Germany PAN from PAN precursors are compiled in Table 20.
was produced mostly by the older dry process.
Two Japanese companies specializing in the pro-
duction of synthetic fibers, namely Toray and 5.6.2. World Capacity
Toho Beslon, have succeeded in greatly expand-
ing carbon fiber production. Today, these two The world capacity to produce carbon fibers is
companies dominate the world’s carbon fiber estimated to exceed 5000 t/a, and is increasing
production by licenses and joint ventures. rapidly. The development of world production
Hercules (USA) is independent from the two capacity during the last 15 years is shown in Fig-
Japanese companies, but works jointly with ure 66. The small quantities of anisotropic and

Table 20. Carbon fiber producing companies, trade names, and commercial availability in the world market.

Producer (country) Production Trade name Types Licensed by

capacity, t/a state
1988

HT IM HM

Toho (Japan) 1380 Besfight HTA IM 400 HM 35

ST 3 IM 500 HM 40
HM 45
Toray (Japan) 1500 Torayca T 300 T 800 M 30 Asahi Nippon
T 700 T 1000 M 40 (Japan) 300
M 50
Amoco (USA) 360 Torayca T 300 T 800 M 30 Toray
T 700 T 1000 M 40
M 50
Hercules (USA) 1360 Magnamite As 4 IM-6 HMS Toray
As 6 IM-7 HMU
IM-8
BASF (USA) 450 Celion G 30 – 400 G 40 – 600 G 50 – 300 Toho
G 30 – 500 G 40 – 700 Gy 70
G 30 – 600 Gy 80
Hysol (UK + USA) 700 Grafil XA-S IM-S HM-S
Sigri (FRG) 100 Sigrafil C − +
(PANOX 400)
AKZO (FRG + USA) 860 Tenax HTH Toho
ST 3
Soficar (F) 300 Filkar T 300 T 800 M 30 Toray
T 400 M 40
M 50
Amoco (USA) 230 ∗ Thornel P 55 P 75
P 100
P 125
Mitsubishi Chem. Ind. 500 ∗ Dialead
Ashland (USA) 140 ∗ Carboflex isotropic types
Kureha (Japan) 900 ∗ isotropic types

∗ pitch-based carbon fiber types

64 Fibers, 5. Synthetic Inorganic

isotropic pitch-based carbon fibers are included. for cutting into chopped fibers. However, mul-
There is disequilibrium between capacity, pro- tifilament tows with only 40 000 monofilaments
duction, and real consumption, but more exact have been introduced. The technological gap
information is not available. It is estimated that between the low filament tows (12 K and in-
capacity will grow up to 10 000 t/a and increase creasing) and the multifilament tows (40 K and
between 30 and 50 % per year. decreasing) is diminishing. This should result in
lower prices.
The price situation for anisotropic pitch-
based carbon fibers is complicated. Around 1981
Union Carbide started to produce high-quality
carbon fibers and sell them at $ 20 per kg, much
below the price of PAN-based fibers at that time.
As shown in Figure 67, the market situation and
production difficulties forced the producer in
1983 to more than double the price. Anisotropic
pitch-based high-modulus fibers are now much
more expensive than PAN-based HT fibers.
The price situation is stable for isotropic
pitch-based carbon fibers as delivered by Kureha
for decades. Ashland, the Major petroleum pitch
Figure 66. World production capacity for carbon fibers producer, has entered the market.

Average prices of carbon fibers are shown

in Figure 67. The price for PAN-based carbon 5.7. Future Importance
fibers strongly depends on the number of fila-
ments in one tow. The so-called low-filament As has become evident over the last decade,
tows, with 3000 monofilaments, have been used polymers reinforced with carbon fibers present
for years. Currently (mid-1980s) most prepregs the opportunity not only to replace but also to
use tows with 6000 monofilaments. The ten- displace structural metals [157]. The advanced
dency is to try to increase the filament number composites (carbon fiber-reinforced plastics,
up to 12 000. CFRPs) are superior to conventional metals in
respect to strength, stiffness, lightness, ther-
mal expansion, fatigue, and corrosion resistance
(Fig. 68).

Comparable Costs. The comparable costs

of strength and stiffness of a unit volume of
an advanced composite reinforced with PAN-
based HT or HM carbon fibers, polyaramide
fibers, glass fibers, former boron, or silicon car-
bide fibers have been estimated and compiled in
Table 21.
From the viewpoint of strength, the glass
fiber reinforcement is cheapest, followed by pol-
yaramide and PAN-based HT fibers. PAN-based
Figure 67. The development of carbon fiber prices
HM fibers are much more expensive. The CVD
PAN-multifilament tows are the cheapest boron and silicon carbide fibers cannot be con-
form of PAN-based carbon fibers: continuous sidered on an economical basis. From the view-
320 000 monofilament tows as used in tex- point of stiffness, the carbon fiber-reinforced
tile application are difficult to handle in high- composites, although attractive on a price basis,
performance composites. They are mainly used are limited to the low modulus range.
 Fibers, 5. Synthetic Inorganic 65

Figure 68. The technical advantages of CFRPs over conventional metals

Table 21. The price related to specific tensile strength and specific
stiffness.
carbon-reinforced resins instead of light metals
like aluminum. Commercial aircrafts are follow-
Fiber type Price, Density, Price divided by
DM/kg 103 kg/m3 specific
ing step by step to replace aluminum by carbon
fiber-reinforced composites.
Tensile Young’s The cost-benefit schedule of typical compos-
strength, modulus,
DM/ DM/ ite applications is:
104 kgm 104 kgm
space market 5 000 ¤/kg
E glass 10 2.50 1.5 0.07 air craft 500 ¤/kg
Kevlar 40 1.45 2 0.05 racing car 50 ¤/kg
CPAN (HT) 70 1.75 3 0.05 automotives up to 5 ¤/kg
CMPP 200 1.99 17.5 0.19
CPHN (HM) 450 1.85 27 0.30 The present calculation gives load savings of
B/c 1000 2.50 67 0.50
SiC/c 4000 3.50 400 3 15 – 30 % in aircraft and component costs of 77 –
150 ¤/kg. In automotives, load savings of 20 –
50 % but component costs up to 2.6 ¤/kg. Al-
Technological Fields. The aerospace field though the cost-benefit ratio is lowest in automo-
can expect the highest technical and economic tive applications, this field is the most promis-
benefit from application of these new materials. ing for the future. To produce large cars with
In the past such risky innovations were the only extremely light weight using the design rules of
chance to realize some ambitious projects. The the aerospace industry presents a real challenge
U.S. space shuttle is the best example. Although to the auto industry. The question becomes more
NASA designed this shuttle in the early 1970s and more a question of economy of scale for the
essentially in conventional materials, it was not fiber production on the one hand, and of rational-
realizable without carbon fiber-reinforced doors ized processing for final products on the other.
for the loading room. In this way, carbon fiber- Plans for future production lines have already
reinforced epoxies were tested in practice and been published [158].
accepted as performing structural materials for Another argument supporting a shift from
primary structures in manned flying vehicles. metals to carbon fiber-reinforced composites
Today, military aircraft contain up to 50 wt % is the energy requirements shown in Table 22
66 Fibers, 5. Synthetic Inorganic

[159]. The numbers in the table include both the wet slurries of raw fibers and a refractory binder
energy needed to process the materials and to (usually a silica sol). Products can be designed
process the raw material. The composites ap- to be dimensionally-stable and to have excellent
pear advantageous in terms of volumes and even low thermal conductivity up to 1500 ◦ C when
more so in terms of mechanical properties per combined with high-alumina products such as
unit volume. ICI “Saffil” alumina (see Section 3.4.1) Rigid
Table 22. Energy requirement in kWh for the production of Al, Fe,
boards lend themselves to modular furnace de-
CFRP’s and PVC [159]. signs with rapid heating and cooling cycles or
Material Density, Energy requirement for
where high gas velocities would lead to erosion
g
cm3
production of blankets. In all cases, the use of low-density
kWh kWh kWh N
fiber aggregates leads to significant energy sav-
/ mm 2
kg L L ings in batch firing regimes compared to furnace
Al 2.8 37.3 104.5 232.2 designs employing dense refractories.
Fe 7.9 6.8 53.6 26.8
CFRP (UD) 1.5 3.7 5.6 3.5
CFRP (2D) 1.5 3.7 5.6 6.9
PVC 1.4 7.9 11.1 1110.0 7. References
1. ASTM D3878.
2. Tonen, 1988, Data sheet.
6. Refractory Ceramic Fibers 3. A. A. Griffith, Philos. Trans. R. Soc. London
221 A (1920) 163.
High-purity aluminosilicate wool fibers, essen- 4. F. Pott Staub.-Reinhalt. Luft 38 (1978) 181.
tially free from group 1 and group 2 oxides, are 5. ASTM D3379.
melt-spun from calcined kaolin or pure alumina 6. H. Böder, D. Gölden, G. Popp, J. Vogelsang,
and silica mixtures in a fashion similar to that SAMPE (1983), paper 12.
for glass wool, rock wool, and mineral wool 7. ASTM D4018-81.
8. S. W. Tsai, NASA Tech. Rep. CR-224 (1965).
fibers (see Chap. 2). Five compositions are in
9. E. Fitzer, W. Hüttner, Bericht über das 93.
common use: 50/50 wt % alumina/silica (maxi- Wehrtechn. Symp., Verbundwerkstoffe in der
mum use temperature of 1250 ◦ C), 60/40 wt % Wehrtechn. part I, Bundesakademie für
alumina/silica (maximum use temperature of Wehrverwaltung und Wehrtechnik, p 93.04.01.
1400 ◦ C), and chromia-, boria-, or zirconia- 22 – 24 May 1978, Mannheim.
modified 50/50 wt % alumina/silica (also for use 10. E. Fitzer, M. Heym, Chemistry and Industry,
at 1400 ◦ C). The physical properties of the fibers 21 August 1976, 663 – 676.
are mainly determined by their diameters. most 11. A. K. Dhingra, Philos. Trans. R. Soc. London
products have a weight mean diameter in the A 294 (1980) 411 – 417.
range of 2 – 3 µm. 12. R. W. Lang, H. Stutz, M. Heym, D. Nissen,
Further details concerning production tech- Lecture held on the symposium organized by
nology and composition can be found in [160]. the Fachgruppe “Makromolekulare Chemie”
The principle use of such fibers is for hot-face in- der Gesellschaft Deutscher Chemiker on
sulation of pottery kilns and metal-working fur- “Neue Polymere – Spezielle Eigenschaften –
naces. Production in Europe is of the order of Moderne Technologien,” Bad Nauheim
16 000 t/a. Correspondingly large amounts are 14. – 15. April 1986.
manufactured in the USA and in Japan. World- 13. R. Weiss, Ph. D. Dissertation University of
Karlsruhe 1984.
wide, the major manufacturers are the Morganite
14. J. B. Donnet, P. Ehrburger, Carbon 15 (1977)
Group (USA, Japan, UK, FRG), the Carborun- 143.
dum Group (USA and FRG), and the Société 15. E. Fitzer: Fibre Reinforcement for Composite
Européenne des Produits Réfractaires (SEPR) Materials, A. R. Bunsell, Amsterdam.
in France [161]. 16. E. Fitzer, J. Schlichting, 18. Int.
The fibers are manufactured as a low density Chemiefasertagung Dornbirn (1979), in:
blanket (64 –96 kg/m3 ), which is flexible and Anorganische Fasern – Herstellung,
can be used as such. Alternatively, rigid boards Eigenschaften, Verwendung – 2.
and shapes can be created by vacuum-forming Werkstofftechnik, 11 (1980) 330 – 341.
 Fibers, 5. Synthetic Inorganic 67

17. G. Jacobsen, “Influence of the Interface on 36. G. von Pazciczky, DE 272 441, 1912. F.
Transverse Strength, Creep Behaviour and Rosengarth, DE 539 738, 1930.
Impact Behaviour of Boron- and Silicon 37. Owens Illinois Glass, US 2 133 236, 1933 (G.
Carbide-Fibre Reinforced Aluminum,” Slayter, J. H. Thomas).
ICCM-IV, Tokyo, 25. – 28. 10. 1982, Prog. Sci. 38. E. Poeschel, R. König, R. Haag, U. Roth et al.:
Eng. Compos., 1323 – 1330. Umweltrelevanz künstlicher Fasern als
18. E. Fitzer, Carbon 25 (1987) 163 – 190. Substitut für Asbest, Erich Schmidt Verlag,
19. E. Fitzer, Pure Appl. Chem. 60 (1988) no. 3, Berlin 1978.
287 – 302. 39. W. Trier: Glasschmelzöfen, Springer Verlag,
20. E. Fitzer, P. Schubert, Rev. Int. Hautes Temp. Berlin-Heidelberg-New York-Tokyo 1984.
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Springer Verlag, Berlin-Göttingen-Heidelberg
General References 1964.
21. Tagungshandbücher SPI, Conference reports, 41. J. A. Škol’nikov, B. M. Polik, E. P. Kočarov,
(Society of the Plastic Industry) (SPI), New E. R. Nigin: Steklannoe štapel’noe volokno,
York. Isd. Khimija, Moscova 1969.
22. Tagungshandbücher AVK (conference reports), 42. F. V. Tooley: The Handbook of Glass
Arbeitsgemeinschaft Verstärkte Kunststoffe, Manufacture, 3rd ed., vol. 2, Ashlee
Frankfurt. Publishing, New York 1984.
23. K. A. F. Schmidt: Textilglas für die 43. ISO/DIS 8142, ISO/DIS 8144, ISO/DIS 8145.
Kunststoffverstärkung, Zechner und Hüthig, 44. J. Thebault, R. Pailler, G. Bontemps-Moley,
Speyer 1972. M. Bourdeau et al., J. Less Common Met. 47
24. K. L. Loewenstein: The Manufacturing (1976) 221 – 223.
Technology of Continuous Glass Fibers, 45. C.-H. Andersson, R. Warren, Composites 15
Elsevier, Amsterdam-Oxford-New York 1983. (1984) 16 – 24.
25. H. S. Katz, J. V. Milewski: Handbook of Filers 46. C.-H. Andersson, R. Warren, Composites 15
and Reinforcements for Plastics, van Nostrand (1984) 101 – 111.
Reinhold, New York 1978. 47. J. G. Lee, I. B. Cutler, Am. Ceram. Soc. Bull.
26. W. Bobeth, W. Böhme, J. Techel: 54 (1975) 195 – 198.
Anorganische Textilfaserstoffe, VEB Verlag 48. P. Bracke, H. Schurmans, J. Verhoest:
Technik, Berlin 1955. Inorganic Fibres and Composite Materials,
27. J. G. Mohr, W. P. Rowe: Fiber Glass, Van 1st ed., Pergamon Press, Oxford 1984.
Nostrand Reinhold Co., New York 1978. 49. B. von Falkai (ed.): Synthesefasern,
Section 6.2.4, Verlag Chemie, Weinheim 1981,
Specific References pp. 268 – 274.
28. R. Kleinholz, J. Molinier: 50. W. C. Miller, Kirk-Othmer, 20 (1982) 65 – 77.
“Verstärkungswerkstoffe nach Maß,” 51. G. Winter, Angew. Chem. (1972); Angew.
AVK-Tagung, 1985. Chem. Int. Ed. Engl. 11 (1972) 751 – 760.
29. R. Kleinholz: “Neue Erkenntnisse bei 52. J.-O. Carlsson, J. Mater. Sci. 14 (1979)
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Chemiefasertagung 22. Dornbirn, Austria, (eds.): Handbook of Fillers and
1983. Reinforcements for Plastics, Chap. 28, Van
30. J. Eule: “Glasstapelfaser-Vorgarne für die Nostrand, New York 1978, pp. 545 – 561.
Herstellung textiler Erzeugnisse,” Textilbetrieb 54. A. M. Tsirlin in W. Watt, B. V. Perov (eds.):
Würzburg, 100 (1982). Handbook of Composites, “Strong Fibres,”
31. J. Bijen: “Durability of Some Glass Fiber vol 1, Chap. 5, Elsevier, Amsterdam 1985,
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Concr. Inst. 80 (1983) no. 7, 8. 55. K. C. Hou, US 3 677 799, 1972.
32. Vetrotex report 2/86, Gevetex, Aachen 1986. 56. J. Schlichting, Ber. Dtsch. Keram. Ges. 57
33. Gevetex Textilglas GmbH, Aachen 1986. (1980) 289 – 298.
34. C. Z. Carroll-Porczinski: Inorganic Fibers, 57. T. F. Foltz, Ceram. Eng. Sci. Proc. 6 (1985)
National Trade Press, London 1958. 1206 – 1220.
35. P. A. Koch, Glastech. Ber. 23 (1950)
204 – 212.
68 Fibers, 5. Synthetic Inorganic

58. S. Yajima in W. Watt, B. V. Perov (eds.): 81. H. Jones: “Experimental Methods in Rapid
Handbook of Composites, “Strong Fibres,” Quenching from the Melt,” Treatise Mater. Sci.
vol 1, Chap. 6, Elsevier, Amsterdam 1985, Technol. 20 (1981).
pp. 201 – 237. 82. E. A. Feest: “Rapid Solidification for the Wire
59. Tokai Carbon Co., GB 2 129 025, 1983 Industry,” Wire Ind. June 1985.
(Akiyama, Yamada, Takashata). 83. P. Vansteenkiste: “Prevention of Static Charges
60. J. V. Milewski, F. D. Gac, J. J. Petrovic, S. R. in Dust Filter Fabrics with Stainless Steel
Skaggs, J. Mater. Sci. 20 (1985) 1160 – 1166. Fibres,” Filtr. Sep. 18 (1981) March-April.
61. J. J. Petrovic, J. V. Milewski, D. L. Rohr, F. D. 84. R. De Bruyne: “Multipass Test Performance of
Gac, J. Mater. Sci. 20 (1985) 1167 – 1177. Metal Fibre Filter Media,” Proceedings World
62. Du Pont, US 3 808 015, 1968; GB 1 264 973, Filtration Congress III, vol. 2, Downingtown,
1969 (L. E. Seufert). 1982, pp. 400 – 408.
63. A. K. Dinghra, Philos. Trans. R. Soc. London. 85. L. C. Shirvill, I. Lefever: “Metallic Fibre
Ser. A 294 (1980) 411 – 417. Surface Combustion Radiant Gas Burners,”
64. Du Pont, GB 1 417 791, 1973 (J. R. Green, Proceedings 1986 International Gas Research
R. F. Tietz). Conference, Toronto, Canada, 1986.
65. 3 M, US 4 047 965, 1976 (K. A. Karst, H. G. 86. J. Samyn: “Bekiscan, a Fast Nondestructive
Sowman). Method to Evaluate Emi-Shielding Properties
66. Y. Abe, S. Horikiwi, K. Fujimura, E. Ichiki in of Metal Fibre-Filled Poylmers,” Antec ’86
T. Hayashi, K. Kawata, S. Umekawa (eds.): Proceedings, Boston 1986.Chapter 5
87. J. B. Donnet, E. Fitzer, K.-H. Köchling,
Prog. Sci. Eng. Compos., ICCM-IV, Tokyo
Proceedings of 4th International Carbon
1982, pp. 1427 – 1434.
Conference (Carbon ’86), Baden-Baden
67. Sumitomo, GB 1 457 801, 1973; US 4 495 121,
30. 6. – 4. 7. 1986, pp. 701 – 705.
1982.
88. J. Simitzis, Ph. D. Thesis, University of
68. J. D. Birchall, J. A. A. Bradbury, J. Dinwoodie
Karlsruhe, FRG, 1975.
in W. Watt, B. V. Perov (eds.): Handbook of 89. H. Jäger, Ph. D. Thesis, University of
Composites, “Strong Fibres,” vol 1, Chap. 4, Karlsruhe, FRG, 1986.
Elsevier, Amsterdam 1985, pp. 115 – 154. 90. E. Fitzer, F. Rozploch, High Temp. – High
69. E. Leroy, C. Robin-Brosse, J. P. Torre in L. L. Pressures, 1988 in print.
Hench, D. R. Ulrich, (eds.): Ultrastructure 91. E. Fitzer, E. Gantner, F. Rozploch, D. Steiner,
Processing of Ceramics, Glasses and High Temp. – High Pressures, 1988, in print.
Composites, Wiley-Interscience, New York 92. E. Fitzer, W. Frohs, M. Heine, F. Rozploch,
1984, pp. 219 – 231. Proceedings of 4th International Carbon
70. 3 M, US 3 793 041, 1971, (H. G. Sowman). Conference (Carbon ’86), Baden-Baden
71. H. G. Sowman, D. D. Johnson, Ceram. Eng. 30. 6. – 4. 7. 1986, pp. 850 – 852.
Sci. Proc. 6 (1985) 1221 – 1230. 93. W. Ruland: J. Polym. Sci. Part C 28 (1969) 5.
72. H. Teranishi, H. Ichikawa, T. Ishikawa, New 94. E. Fitzer, W. Frohs, F. Rozploch, High Temp. –
Mater. New Processes 2 (1983) 379 – 385. High Pressures 19 (1987) 311 – 322.
73. S. V. Nair, J. K. Tien, R. C. Bates, Int. Met. 95. E. Fitzer, P. Laudenklos, G. Schwarz, Ber.
Rev. 30 (1985) 275 – 290. Dtsch. Keram. Ges. 53 (1976) no. 6, 169 – 174.
74. A. K. Dinghra, CHEMTECH 1981, 600 – 608. 96. A. A. Bright, L. S. Singer, Carbon 17 (1979)
75. F. Pott, Staub Reinhalt. Luft 38 (1978) 59 – 69.
486 – 490. 97. W. Ruland, J. Appl. Phys. 38 (1967) 3585.
76. United Aircraft Corporation, BE 1 177 854 98. S. C. Bennet, D. J. Johnson: Proc. London Int.
(1967); US 3 549 424, 1971, 3 574 649, 1971. Carbon Graphite Conf. 5th 1 (1978) 337.
77. US 3 760 049, 1973. 99. M. Guigon, A. Oberlin, G. Desarmot, Fibre
78. S. J. Everett, US 2 050 298, 1936. Sci. Technol. 20 (1984) 117 – 198.
100. W. Marciniak, F. Rozploch, High Temp. –
79. J. A. Roberts in H. S. Katz, J. V. Milewski
High Pressures 11 (1979) 709 – 710.
(eds.): Handbook of Fillers and
101. P. Schubert, Ph. D. Thesis, Univ. of Karlsruhe,
Reinforcements for Plastics, “Metal
FRG, 1977.
Filaments,” Chapter 31, Van Nostrand 102. K. Brennfleck, E. Fitzer, G. Schoch, 1984 in
Reinhold, New York, 1978, pp. 597 – 616. Extended Abstracts, Carbone 84, Bordeaux,
80. S. Kavesh: Spinning Wire from Molten Metal, France (Talence: Centre de Recherche Paul
vol. 74, AIChE no. 180, 1978. Pascal) pp. 162 – 163.
 Fibers, 5. Synthetic Inorganic 69

103. H.-P. Boehm, Catalysis 16 (1966) 176. 129. I. Romey, “Preprint,” 2. Int.
104. J. Cziollek, Ph. D. Thesis, University of Kohlenstofftagung, Baden-Baden 1976, p. 470.
Karlsruhe, FRG, 1983. 130. J. B. Barr, S. Chwastiak, R. Didchenko, R. T.
105. E. Fitzer, Carbon Fibres and Their Lewis, J. C. Lewis, L. Singer, Appl. Polym.
Composites, Springer Verlag 1985. Symp. 29 (1976) 261.
106. E. Fitzer, R. Weiss, Carbon 25 (1987) no. 4, 131. Union Carbide, US 4 005 183, 1977.
455 – 467. 132. E. Fitzer, H. Schlesinger, Ber. Dtsch. Keram.
107. R. Bacon, in P. J. Walker, jr. (ed.): Chemistry Ges. 43 (1966) no. 3, 209 – 218.
and Physics of Carbon, vol. 9, Marcel Dekker, 133. E. Fitzer, W. Fritz, B. Rhee, High Temp. –
New York 1973, p. 7. High Pressures 4 (1972) 219 – 224.
108. T. A. Edison, US 223 898/470 925, 1879/1892. 134. T. Koyama, M. Endo, Y. Hishiyama, Jpn. J.
109. W. F. Abbott, US 3 053 775, 1962. Appl. Phys. 13 (1974) no. 12, 1933 – 1939.
110. J. Electrochem. Soc. 106 (1959) 147 C.
135. A. Nogaj, in B. von Falkai (ed.):
111. G. E. Cranch: in Proceedings of the Fifth
Synthesefasern, Verlag Chemie, Weinheim
Conference on Carbon, vol. 1, Pergamon
1981, pp. 197 ff.
Press, New York 1962, p. 589.
136. G. P. Daumit, Y. S. Ko, in K. Brunsch et al.
112. C. E. Ford, C. V. Mitchel, US 3 107 152, 1963.
113. D. L. Schmidt, H. T. Hawkins, in Reinforced (eds.): in High Tech – the Way into the Nineties,
Plastics ’65, Society of Plastics Engineers Elsevier, Amsterdam, 1986, pp. 201 – 213.
Regional Conference, Seattle, 1965, p. 111. 137. E. Fitzer, W. Frohs, M. Heine, Carbon 24
114. E. M. Peters, US 3 235 353, 1966. (1986) 387 – 395.
115. R. Bacon, G. E. Cranch, R. O. Moyer, jr., W. H. 138. K. Morita et al., Ext. Abstracts Int. Symp. on
Watts, US 3 305 315, 1967. Carbon, Toyohashi 1982, p. 321.
116. R. Bacon, W. A. Schalamon, Eighth Biennial 139. E. Fitzer, M. Heine, G. Jacobsen, Int. Symp. on
Conference on Carbon, Buffalo, N. Y., June Carbon, Toyohashi, Japan 1982.
1967, Paper MI-58. 140. E. Fitzer, D. Müller, A. K. Fiedler, Int.
117. W. J. Spry, GB 1 093 084, 1967; US 3 454 362, Conference on Carbon Fibres, Their
1969. Composites and Application, no. 2, London
118. D. W. Gibson, G. B. Langlois, ACS Polymer 1971.
Preprints 9 (1968) 1376. 141. E. Fitzer, A. K. Fiedler, D. J. Müller, Circ. Inf.
119. R. C. Houtz, Tex. Res. J. 20 (1950) 786. Tech. Cent. Doc. Sider. 43 (1971) 923 ff,
120. A. Shindo, JP 28 287, 1959. 1022 ff.
121. W. G. Vosburgh, Tex. Res. J. 30 (1960) 142. E. Fitzer, A. K. Fiedler, Preprints Carbon 72,
882 – 896. Baden-Baden, Juni 1972, paper 21.
122. W. Johnson, H. Phillips, W. Watt, 143. E. Fitzer, D. J. Müller, Chem. Z. 96 (1972)
GB 1 110 791, 1965. 20 – 26.
123. W. Watt, in A. Kelly et al. (eds.): Handbook of 144. E. Fitzer, M. Heym, Chem. Ind. 16 (1976)
Composites, “Strong fibres,” vol. 1, Elsevier, 663–676.
Amsterdam 1985. 145. E. Fitzer, T. Müller, Proc. of Carbon ’82 Ext.
124. D. J. Müller, Ph. D. Thesis, University of Abstracts, London 1982, pp. 249 – 252.
Karlsruhe, “Zur Herstellung von 146. N. Grassie, R. McGuchan, Eur. Polym. J. 7
Kohlenstoffaser aus Polyacrylnitril über die (1971) 1357.
katalytische Cyclisierung des Polymeren,” 147. E. Fitzer, D. J. Müller, Carbon 13 (1975) 63.
1973. 148. E. Fitzer, M. Heine, W. Metzler, Proc. of
125. S. Otani, Mol. Cryst. Liq. Cryst. 63 (1981) Carbon ’86, Baden-Baden, DKG 1986,
249. pp. 853 – 855.
126. S. Otani, A. Oya, Kogyo Kagahu Zasshi 73
149. Toho, Beslon Co., Ltd. DE-OS 31 32 784,
(1970) 493.
1981.
127. S. Otani, A. Oya, in Petroleum Derived
150. Toray Industries, JP 48 228, 1975.
Carbon, Am. Chem. Soc. Symp. Ser. 303,
151. E. Fitzer, A. Gkogkidis, G. Jacobsen, Extended
Washington, D.C., 1986, p. 323.
128. W. P. Hettinger, J. W. Newmann, R. P. Krook, Abstracts Int. Symp. on Carbon, Toyohashi
D. C. Boyer, Earth Moving Industry 1982, p. 284, Carbon Society of Japan, Tokyo.
Conference, Peoria, Illinois, USA, April 152. D. W. McGuffin, R. J. Larsen, R. W. Mitchell,
8 – 10, 1986 in SAE (Society of Automotive B. E. Caruso, US 3 803 672, 1974 assigned to
Engineers) Technical Paper series 860 767. HITCO.
70 Fibers, 5. Synthetic Inorganic

153. T. Trendelenburg, Ph. D. Thesis, University of 158. H. Böder, SIGRI GmbH Meitingen/Augsburg,
Karlsruhe, FRG, 1984. Vortrag anläßlich Carbon ’86 in Baden-Baden.
154. D. Kompalik, Ph. D. Thesis, University of 159. H. Fleckenstein, VDI-Z. 125 (1983) nr. 4,
Karlsruhe, FRG, 1986. 123 – 131.
155. E. Fitzer, D. Kompalik, Sprechsaal 119 160. W. C. Miller, Kirk-Othmer 20 (1982) 65 – 77.
(1986) no. 10, 911 – 916. 161. J. Griffiths, “Synthetic Mineral Fibres,” Ind.
156. Union Carbide, US 4 005 183, 1977. Miner. (London), Sept. (1986) 20 – 43.
157. Engineering, Sept. 1982, p. 611.
 Fibers, 6. Testing and Analysis 1

Fibers, 6. Testing and Analysis

Ernst Kleinhansl, Institut für Textil- und Verfahrenstechnik, Denkendorf, Federal Republic of Germany
Mary C. Sawyer, E. I. Du Pont de Nemours and Company, Wilmington, DE 19898, United States

1. Introduction . . . . . . . . . . . . . . 2 2.10. Identification of Wool and Hair . . 13

1.1. History and Current State of the 2.11. Analysis of Fiber Impurities and
Art . . . . . . . . . . . . . . . . . . . . . 2 Extractable Matter . . . . . . . . . . 13
1.2. Definitions and Basic Terms . . . . 2 2.11.1. Trash and Dust Content of Cotton
1.3. Test Procedures, Rules, Standards 3 (Nonlint Content) . . . . . . . . . . . . 13
1.4. Climate . . . . . . . . . . . . . . . . . . 3 2.11.2. Honeydew on Cotton . . . . . . . . . . 13
1.5. Sampling . . . . . . . . . . . . . . . . . 3 2.11.3. Grease Content of Wool – Extractable
2. Tests of Form and Mass . . . . . . . 4 Matter Content . . . . . . . . . . . . . 14
2.1. Length . . . . . . . . . . . . . . . . . . 4 2.11.4. Preparation and Finishing Agents for
2.1.1. Single-Fiber Length . . . . . . . . . . 4 Man-Made Fiber . . . . . . . . . . . . 14
2.1.2. Comb Sorter Method . . . . . . . . . . 4 2.12. Maturity of Cotton . . . . . . . . . . 14
2.1.3. Electronic Method – Capacitive
3. Tensile Properties . . . . . . . . . . . 15
Scanning . . . . . . . . . . . . . . . . . 5
3.1. Tensile Test . . . . . . . . . . . . . . . 15
2.1.4. Electronic Method – Optical Scan-
3.2. Elastic Behavior . . . . . . . . . . . . 16
ning . . . . . . . . . . . . . . . . . . . . 6
2.2. Width, Thickness . . . . . . . . . . . 7 3.3. Modulus . . . . . . . . . . . . . . . . . 16
2.3. Fineness . . . . . . . . . . . . . . . . . 7 3.4. Loop Tensile Test . . . . . . . . . . . 16
2.3.1. Gravimetric Method . . . . . . . . . . 7 3.5. Bundle Stress Test . . . . . . . . . . . 16
2.3.2. Projection Microscope Method 4. Behavior toward Water . . . . . . . 17
(Fiber Diameter) . . . . . . . . . . . . 7 4.1. Moisture Adsorption . . . . . . . . . 17
2.3.3. Diameter Measurement with Laser 4.1.1. Oven Drying Test . . . . . . . . . . . . 17
Beam . . . . . . . . . . . . . . . . . . . 8 4.1.2. Other Tests for Moisture Content of
2.3.4. Projection Microscope Method with Fibers . . . . . . . . . . . . . . . . . . . 17
Image Analysis Techniques . . . . . . 8 4.2. Water Absorption . . . . . . . . . . . 18
2.3.5. Vibration Method . . . . . . . . . . . . 8 5. Thermal Behavior . . . . . . . . . . . 18
2.3.6. Airflow Method . . . . . . . . . . . . . 9 5.1. Melting Point . . . . . . . . . . . . . . 18
2.3.7. Microscopic Area Measurement . . . 9 5.2. Burning Test . . . . . . . . . . . . . . 18
2.4. Microscopic Investigation of Cross 6. Dyeing Properties . . . . . . . . . . . 18
Section . . . . . . . . . . . . . . . . . . 9 6.1. Laboratory Dyeing . . . . . . . . . . 18
2.5. Microscopic Investigation of Fiber 6.2. Identification of Fiber Type by Dye-
Surface . . . . . . . . . . . . . . . . . . 10 ing (Neocarmine) . . . . . . . . . . . 19
2.6. Crimp . . . . . . . . . . . . . . . . . . . 11
7. Processing . . . . . . . . . . . . . . . . 19
2.6.1. Crimp Frequency . . . . . . . . . . . . 11
7.1. General . . . . . . . . . . . . . . . . . . 19
2.6.2. Crimp Ratio, Crimp Retention . . . . 11
7.2. Spinning Devices for Trials . . . . . 19
2.7. Density . . . . . . . . . . . . . . . . . . 12
2.7.1. Pycnometer Method . . . . . . . . . . 12 7.3. Electrostatic Charging . . . . . . . . 19
2.7.2. Density Balance (Archimedes’ Prin- 7.4. Rotor Ring Method . . . . . . . . . . 19
ciple) . . . . . . . . . . . . . . . . . . . 12 7.5. Combination of Micro Dust and
2.7.3. Gradient Method . . . . . . . . . . . . 12 Trash Analyzer with the Rotor
2.8. Chemical Identification of Fibers Ring Method and a Spinning De-
by Solubility . . . . . . . . . . . . . . 12 vice for Trials . . . . . . . . . . . . . . 20
2.9. Other Identification Methods for 8. Automated Test Units . . . . . . . . 20
Fibers . . . . . . . . . . . . . . . . . . . 12 9. References . . . . . . . . . . . . . . . . 20

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11 067
2 Fibers, 6. Testing and Analysis

1. Introduction Depending on their form, fibers are desig-

nated as
1.1. History and Current State of the Art
1) Staple fibers (fibers of limited length)
For as long as textile fibers have been used, 2) Filaments (fibers of practically unlimited
people have tested them in one way or another length)
usually aided by nothing more than their eyes, Test methods can sometimes be used with
their fingers, and occasionally, their noses. Vi- all kinds of fibers and sometimes only with cer-
sual methods, in refined form, are still in use tain kinds. In addition, methods are available for
today, generally because objective methods of measuring characteristics specific to fiber type.
measurement are lacking or are very expensive.
Visual test methods are subjective and require
great experience on the part of the person mak-
1.3. Test Procedures, Rules, Standards
ing the test.
Over the past decades, various methods of
To assure comparable and reproducible re-
measurement and appropriate test apparatus
sults, various organizations issue test proce-
have been developed for measurement of indi-
dures, rules, and standards. The following are
vidual fibers. Such measurements presume great
some of the most important ones.
care, intuition, and skill on the part of the in-
dividual; nevertheless, the tester usually influ- International standards and rules:
ences the results. Many individual values must ISO International Organization for Standard-
be obtained because of the relatively high dis- ization
persion of fiber characteristics and properties; EN European Standards
hence, measurements are tedious and costly. BISFA International Bureau for the Standard-
Current developments tend toward so-called ization of Man-Made
collective testing procedures which, together Fibers
with automation and the use of computers, pro- IWTO International Wool Textile Organiza-
vide information on fiber properties very rapidly tion
and minimize the influence of the individual
tester. Frequently, the required properties them- Some national standards:
selves are not measured, but others that correlate ASTM United States
with them. By coupling several testing devices, AATCC United States
so-called test beds (high-volume testing, high- DIN Germany
volume instruments) are created. This technol- BS United Kingdom
ogy is still evolving. NF France
Standards or rules do not exist for all test
methods. In that case, measurements are carried
1.2. Definitions and Basic Terms out according to methods developed by com-
panies, institutes, associations, or instrument
Fibers are linear products that can be processed manufacturers.
on textile machinery. Their common character- Any existing standards or rules promulgated
istic is a relatively high ratio of length to cross by ISO, CEN, ASTM, BISFA, IWTO, and DIN
section, sufficient strength, and flexibility. De- are listed with each of the test methods described
pending on their origin or composition, they are below.
divided into the following groups:
1) Natural fibers (vegetable, animal, and min-
eral) 1.4. Climate
2) Man-made fibers from natural or synthetic
polymers Fiber properties, especially those of natural
3) Industrially produced fibers based on inor- fibers and of man-made fibers from natural poly-
ganic substances mers, depend on the testing climate. The relative
 Fibers, 6. Testing and Analysis 3

humidity is of primary importance here. In addi- cess as well as the quality of the textile end prod-
tion, fibers exhibit hysteresis when water is ab- uct. The lengths of natural fibers vary widely;
sorbed. Fibers take up different amounts of wa- therefore, many individual measurements are
ter, depending on whether they have been con- needed. The large number of fibers in a test lot
ditioned by adsorption or desorption. Therefore, and the inhomogeneities (e.g., from bale to bale
fibers are tested in a standard climate: or from batch to batch) also necessitate many in-
dividual measurements. Man-made fibers, with
Temperature ( 20 ± 2) ◦ C
few exceptions, are cut to a certain length; sub-
Relative humidity (65 ± 2) %
stantially less variation occurs, but the length
Samples must always be conditioned to the can be reduced by stresses on the fiber while it
standard climate in the adsorptive phase. When is being processed into yarn. This increases the
necessary, they must be dried first if, prior to deviation.
testing, they have been exposed to a climate with
more than 65 % R.H. Conditioning of samples
is prescribed by standards ISO 139; ASTM D 2.1.1. Single-Fiber Length
1776; and DIN 53 802.
Currently, the European standardization With the aid of two pairs of tweezers, a fiber is
commitees are striving for a change in the stan- picked up at both ends, the crimp is pulled out by
dard climate, with the aim of harmonization with applying a slight tension, and the length is read
testing laboratories in other fields such as plas- off on a ruler. Crimp can also be removed by
tics, paper, leather, and biology. The standard using a pair of tweezers to draw the fiber over a
climate would then be: glass plate covered with paraffin oil or vaseline.
Temperature ( 23 ± 2) ◦ C The length is then measured with a ruler.
Relative humidity (50 ± 5) % The measuring process can be simplified by
mechanical devices. One of them is shown in
Figure 1. With a pair of tweezers, the fiber is
drawn under a loading weight and the crimp is
1.5. Sampling thus removed. The results are presented in the
form of a cumulative frequency diagram (Fig. 2);
Fiber samples must be tested so that from the average fiber length and coefficient of variation
values obtained for a given property, the value are calculated.
of that property for the source material can be
deduced. The sample must, therefore, be repre-
sentative of the source material. Details of sam-
pling are governed by the following standards
and rules: ISO 1130; BISFA Rules; ASTM D
1060, D 1441, D 1771, D 2525, D 3333; DIN
53 803 (ASTM D 1771 has been discontinued
without replacement, although copies are avail-
able from ASTM headquarters). A new standard
is in preparation, prEN 12751:1997, which re-
places all European national standards for sam-
pling and later later the international standard
ISO 1130.

2. Tests of Form and Mass

2.1. Length Figure 1. Length measurement of single fibers
a) Loading weight; b) Velvet strips
Staple fiber length is an important fiber charac-
teristic which greatly affects the spinning pro-
4 Fibers, 6. Testing and Analysis

10 mm for longer wool fibers. This distance is

also the class interval for length classes. Once
ordered, fibers of individual length classes are
drawn from the bank and weighed. The weight
is used to calculate the number of fibers of each
class and, thus, to determine the average fiber
length and the coefficient of variation. The re-
sult is presented as shown in Figure 2.
Mechanized devices that perform the order-
ing operation have been developed to test wool.
Manual preparation, particularly end alignment,
is difficult, time-consuming, and dependent on
the care and skill of the tester. The procedure
Figure 2. Cumulative distribution of fiber length is applicable to fibers from flock (raw material),
L = average fiber length
slivers, and rovings.
Specific standards for length measurement Standards for comb sorting are ISO 920;
are ISO 6989; ASTM D 3661; IWTO-5-60; DIN IWTO-1-66; ASTM D 519, D 1440, D 1575,
53 808 T 1. For future reference, ASTM is de- D 3660; DIN 53 806.
veloping another method (57-507) which is as-
signed “D”.
2.1.3. Electronic Method – Capacitive
Scanning
2.1.2. Comb Sorter Method
Two steps have been taken to simplify mea-
A prepared fiber sample containing at least surement of fiber length. (1) Parallelizing has
10 000 fibers is first end-aligned with the aid of been automated. This is more readily accom-
two banks of combs and special forceps (Fig. 3). plished with sliver than with flock. Long fibers
The distance between pins depends on the type such as wool or long staple man-made fibers can
of fiber being tested: e.g., 3 mm for cotton, be ordered more easily and accurately. (2) The

Figure 3. Comb sorting principle

 Fibers, 6. Testing and Analysis 5

frequency of individual length classes is deter- Almeter. Fibers are end-aligned by a fully
mined by means other than drawing and weigh- automatic sample preparation machine; the sam-
ing. ple is then measured in the electric field of a
condenser (Figs. 4 and 5).
This method is suitable for all fibers in flock
or sliver form; the standards are ISO 2648 and
IWTO-17-85.

2.1.4. Electronic Method – Optical Scanning

Optical Scanning of a Beard. The Fibro-

graph was developed specifically for measuring
the length of cotton fibers. A beard is formed in
a special comb by using the Fibrosampler. The
beard is not end-aligned. In the measuring zone,
the optical density of the beard is measured as a
function of fiber length (Fig. 6).
Figure 4. End-aligned beard with capacitive measuring prin-
ciple
a) Clamp; b) Measuring condenser

WIRA Fiber Diagram Machine. The end-

aligned beard is prepared by mechanical means.
The ends are thermally bonded with plastic film.
The fiber beard, which is now easy to handle, is
drawn through the electrodes of a condenser, and
the fiber mass for each length zone is measured.
Standards are ISO 2646 and IWTO-16-67.
In the latest version of this machine, all char-
acteristics of fiber length measurement, includ-
ing the fiber length diagram, are printed out. The Figure 6. Beard, not end-aligned, with optical scanning
procedure is suitable for wool and long staple a) Clamp; b) Optical sensor
man-made fibers in sliver form. Results are given in terms of so-called span
length, defined as a function of cumulative fre-
quency. The frequency diagram is called a fibro-
gram (Fig. 7). It has become customary to report
the span length at 2.5 and 50 % frequency, ab-
breviated as the 2.5 % SL value and the 50 %
SL value. In addition, the uniformity index is
given, which correlates with the deviation of
fiber length.
The Fibrograph was developed by SpinLab
(Knoxville, USA) and is now available from
Zellweger (Uster, Switzerland) under the trade
name Uster Fibrograph 730. Many measure-
Figure 5. Sketch showing principle of Almeter ments can be made in a short time with this ma-
a) End-aligned fiber sample; b) Measuring sled; c) Spindle; chine, which is especially important in testing
d) Measuring condenser; e) Detector; f) Stepping motor raw cotton. Standards are ISO 4913; ASTM D
1447.
6 Fibers, 6. Testing and Analysis

nonround fibers). The fiber diameter or width is a

measure of the fineness. Other modules measure
fiber neps (Module N) and impurities (Module
T).

2.2. Width, Thickness

Further geometric characterization of a fiber
should include width or thickness and, for cir-
cular cross section, the diameter. Because of
the multiplicity of fiber cross sections (see Sec-
tion 2.4), a precise definition of one or more
width measurements is not possible. Such mea-
surements are, therefore, made only in excep-
tional cases. Fiber diameter is used as a char-
acteristic of fineness only for wool (see Sec-
tions 2.3.2, 2.3.3, 2.3.4).

2.3. Fineness
Figure 7. Fiber length measurement with Fibrograph
Fibrogram shows 2.5 % and 50 % span lengths Fiber fineness is defined as mass referred to a
length (length-related mass). In the internation-
ally accepted tex system (ISO 1144), the mass
in grams is referred to 1 km:
1 tex = 1 g/km
From this, the decitex unit (dtex), frequently
used for fibers, is derived:
1 dtex = 1 dg/km = 1 g/10 km
In certain countries, the millitex unit (mtex)
is preferred:
1 mtex = 1 mg/km

2.3.1. Gravimetric Method

In gravimetric determination of fineness, the

length and weight of the fibers are measured.
Figure 8. Schematic of the AFIS system The following practical method is used: a care-
fully parallelized, combed fiber bundle is cut
at both ends when as much crimp as possible
Optical Scanning of Single Fibers. In the
has been pulled out by suitable tensioning. The
AFIS tester (AFIS = advanced fiber information
length should be as great as possible. Groups of
system; Figure 8) flocks or slivers of fibers are in-
50 fibers – generally ten groups – are taken from
dividualized by a special device. The individual
this bundle. The total length is calculated from
fibers are aligned longitudinally and stretched in
the cut length and the number of fibers. The mass
an air stream. They then pass through a tapered
of the individual groups of fibers is determined
channel into an optical measuring system. The
by weighing, and the fineness is calculated from
data are evaluated by various modules, the most
the mass and the length. Standards are ISO 1973,
important of which is the L & D module, which
EN 21 973; BISFA Rules; ASTM D 1577; DIN
measures fiber length and diameter (or width for
53 812 T 1.
 Fibers, 6. Testing and Analysis 7

2.3.2. Projection Microscope Method (Fiber beam and an electronic optical measuring de-
Diameter) vice. About 30 – 50 fibers per second can be
measured. The measurements are analyzed by
Because the fineness of individual wool fibers computer, and the results are printed out.
varies widely, the fineness distribution of indi- This instrument is still used in many labo-
vidual fibers, in addition to the average fineness, ratories, but has since been replaced by a bet-
must be determined. As a rule, at least 300 fibers ter and more effective measurement system (see
must be measured. Figure 9 shows the results of Section 2.3.4) and is therefore no longer manu-
a wool fineness measurement. factured.

2.3.4. Projection Microscope Method with

Image Analysis Techniques

With the aid of an electronic image analyzer,

microscopic pictures of wool fibers can be suit-
ably analyzed; thickness measurements can also
be carried out. A more detailed description of
this measuring procedure is contained in ASTM
standard D 3510 (discontinued without replace-
ment, copies are available from ASTM head-
quarters).
A new method for rapid and automatic mea-
Figure 9. Example of wool fineness measurement surement of fiber diameter has been developed
x̄ = average fiber diameter by Australian Wool Testing Authority (AWTA)
Ltd., Kensington, Victoria, Australia. It is based
To calculate the fineness in decitex, the fol- upon image analysis techniques and is called FI-
lowing formula is used: DAM (Fiber Image Display and Measurement).
The measurement section consists essentially of
πd2 ·
Td = a high-quality CCD (Capacitive Coupled Diode)
400
television camera attached to a low-power mi-
where T d = fineness, decitex; d = diameter, mi- croscope. The camera output feeds signals to a
crometers;
= density, grams per cubic centime- flash analog-to-digital converter (ADC) and then
ter. to a desktop personal computer which is the heart
Appropriate standards are ISO 137; IWTO- of the system. Sample preparation is also largely
8-89; ASTM D 2130; DIN 53 811. automatic; it involves microcoring the sample
and spreading the resulting snippets, which are
air-mounted, onto a large microscope slide. The
2.3.3. Diameter Measurement with Laser calibration, which is linear, is based on the In-
Beam terwoollabs’ Calibration Tops and is very stable
[6].
Because measuring the fiber diameter of wool A further development is the OFDA (optical
is very costly and time-consuming, simpler test fiber diameter analyzer) instrument, marketed
methods are being sought. The Commonwealth by Zellweger, Uster, Switzerland, in which com-
Scientific and Industrial Research Organisation puter image processing is performed through a
(CSIRO) of Ryde, New South Wales, Australia, projection microscope. In 50 s, 2000 – 5000 fiber
has developed the so-called fiber distribution an- sections can be measured (standard: IWTO-22-
alyzer (FDA) [5]. Wool fibers are first cut to a 92).
length of ca. 2 mm and then finely dispersed in
a nonswelling liquid. The liquid with the pieces
of fiber then flows through a measuring cham-
ber where it is measured by means of a laser
8 Fibers, 6. Testing and Analysis

2.3.5. Vibration Method 1282, D 1448; IWTO-6-90, IWTO-28-89; DIN

53 941.
The vibroscope is based on the vibrating string
principle. Linear density, or mass per unit length,
can be calculated from the fundamental reso- 2.3.7. Microscopic Area Measurement
nant frequency of transverse vibration of a fiber
measured under known conditions of length and The area can be measured microscopically when
tension. This device is often combined with a few fibers are available for measurement and
fiber tensile tester. The measured fiber fineness when these fibers are not circular in cross sec-
is combined directly with the breaking force, and tion. In this case, the above-mentioned meth-
the breaking tenacity is calculated from it. The ods cannot be used. Fiber cross sections for mi-
applicable standards are ISO 1973; EN 21 973; croscopic examination are prepared with a mi-
ASTM D 1577; DIN 53 812 T 2. crotome, and drawings or photographs of these
cross sections are made. The cross-sectional area
can be determined by planimetry or by electronic
2.3.6. Airflow Method analysis of the pictures; fineness is calculated
from the area.
The resistance of a plug of fibers to airflow de-
pends on fiber fineness. For cotton, a character-
istic called “Micronaire value” has been defined 2.4. Microscopic Investigation of Cross
which can be read off the Micronaire instru- Section
ment, designed for this purpose, as a function
of resistance to airflow (“Micronaire reading”). An investigation of fiber cross section may be
The instrument is calibrated with fixed cotton necessary for several reasons:
standards. Resistance to airflow also depends on 1) Identification of fibers
maturity. For wool, the scale is calibrated in mi- 2) Estimation of blend ratios
crometers. Figure 10 shows a sketch of the prin- 3) Determination of fineness (see Section 2.3.7)
ciple of this device. This instrument is now avail- 4) Determination of maturity of cotton (Sec-
able from Zellweger (Uster, Switzerland) under tion 2.12)
the trade name Uster Micronaire 775. 5) Determination of depth of penetration of
dyes or optical brighteners, sheath – core
zones of fibers
6) Measurement of cross-sectional parameters,
e.g., modification ratio (the “deviation” from
a circle) and angle of lobes
Modification ratio is the ratio of the diameter
of an inscribed circle, touching all the valleys in
a lobed cross section, to the diameter of a cir-
cumscribed circle touching all the peaks in that
cross section.
In addition, Special Instrument Laboratory
(SpinLab) (Knoxville, TN 37901) has developed
the “Fibrofine” Specific Surface Tester Model
820, used for measuring fiber fineness of cot-
Figure 10. Micronaire tester Sheffield 60 600 ton, to correlate with modification ratio mea-
a) Pressure regulator; b) Scale; c) Rotameter plummet; surements from cross-sections.
d) Sample holder with fiber plug; e) Fiber compression The identification of specific fiber types
plunger is possible by viewing their cross sections
Further details can be found in the follow- (Fig. 11). Man-made fibers, which are normally
ing standards: ISO 1136, ISO 2403; ASTM D extruded from spinneret holes with circular cross
section, can also be produced with cross sections
 Fibers, 6. Testing and Analysis 9

of different shapes (Fig. 12). Test Method 20 titative,” has sections on microscopic analysis
(AATCC) shows photographs of common tex- and procedures which cover this subject.
tile fibers. Dye Penetration. The distribution of dyes
across the fiber cross section can be determined
if the colorants are still recognizable in the
relatively thin cross sections. The distribution
of optical brighteners is determined easily un-
der the microscope in UV light. Fibers with
sheath – core structure can be made visible by
using special dyes, e.g., Solophenyl Blue-Green
BL (Ciba-Geigy). Some so-called bicomponent
fibers can also be detected microscopically.

Figure 12. Some special cross sections in man-made fiber

production

2.5. Microscopic Investigation of Fiber

Surface
Figure 11. Cross sections of various fiber types In certain cases, the fiber type can be identi-
a) Cotton; b) Flax; c) Silk; d) Viscose rayon (normal); e) Most
acrylic fibers (including modacrylic); f) Wool, cupram- fied by microscopic examination of a longitu-
monium rayon, polyester, polyamide, polypropylene, some dinal view, i.e., of the fiber surface (Fig. 13).
acrylic fibers Thus, for example, wool can be recognized by
its scale structure. When an unknown fiber must
Mixing Ratios. When the components of a
be identified, microscopic examination begins
fiber blend have different cross sections, an ap-
with the surface, because preparation of a spec-
proximate blend ratio can be established through
imen for longitudinal viewing is considerably
counting, by using photomicrographs of the
faster and simpler than preparing one for cross-
cross sections. Mixtures of fiber of the same type
sectional viewing. Wool, cotton, flax, and vis-
but with different fiber fineness can also be ex-
cose fibers can be identified unmistakably in this
amined in this way provided the difference in
way. Test Method 20 (AATCC), also has infor-
fineness is large enough (e.g., 3 – 6 dtex). Test
mation on longitudinal characteristics of natural
Method 20 A (AATCC) “Fiber Analysis: Quan-
fibers which is important to their identification.
10 Fibers, 6. Testing and Analysis

from them. The crimp of wool is relatively uni-

form and characterized by true waves. Man-
made fibers, on the other hand, may exhibit ir-
regular crimp, and the shapes of the waves can
differ widely (Fig. 14).

Figure 14. Different forms of crimped fibers

a) Wool; b) Synthetic fiber with stuffer box crimping

Several characteristics can be used to de-

scribe crimp; two of these are discussed in detail
below.
Figure 13. Longitudinal view of some fiber types
a) Wool (characteristic: scales); b) Cotton (characteristic:
longitudinal torsion); c) Flax (characteristic: lumen, trans- 2.6.1. Crimp Frequency
verse cracks); d) Viscose rayon (characteristic: longitudinal
stripes) The number of crimp waves per centimeter is de-
termined. The waves are counted either directly
For man-made fibers, the longitudinal view
on the fiber or on enlargements, for example,
also indicates if the fiber contains delusterants
with the aid of a projector. Care must be taken
or if it is of the bright type.
to count either the peaks or the valleys, not both
Microscopic examination of the longitudinal
(Fig. 15).
view can also serve many other purposes, such
as
1) Determination of the surface structure of
fibers, pores, vacuoles, cracks
2) Detection of foreign matter on the fiber
3) Inspection of crack formation at the fiber
ends, an indication of overload
4) Investigation of thermal damage due to ex- Figure 15. Definitions of crimping
cessive friction
5) Checking wool fiber ends for hair roots, and In addition, the depth and width of the crimp
differentiating between shorn wool and lime waves can be measured with the aid of enlarge-
wool ments (ASTM D 2491; discontinued without re-
6) Detection of insect damage placement but available from headquarters).
These investigations are best carried out with
scanning electron microscopes (SEM) which 2.6.2. Crimp Ratio, Crimp Retention
provide high magnification and good depth of
field. The crimp ratio E is defined by two parameters,
the crimped length and the extended length of a
fiber (Fig. 16).
2.6. Crimp Fibers should be straightened so that the
crimp is removed but the material is not
Crimp is very important for the processibility stretched. Crimp retention B is another charac-
of fibers and the properties of textiles made teristic that can be measured along with crimp.
 Fibers, 6. Testing and Analysis 11

The fiber which has been straightened to mea- suring liquid, the density of the fiber can be cal-
sure the crimp remains under this load for 5 min. culated.
After unloading, the fiber recovers partially; the
extent depends on crimp retention. The length
of this partially crimped fiber is then measured. 2.7.2. Density Balance (Archimedes’
The testing device used is the so-called crimp Principle)
balance (Fa. Zweigle, Reutlingen, Federal Re-
public of Germany) which greatly facilitates the A small specimen is weighed in air and then im-
entire operation. mersed in a liquid of lower density than the fiber.
The change in length from the crimped to The difference in weight is equal to the weight of
the straightened fiber can also be measured on a the liquid displaced, i.e., the volume of the fiber
tensile testing machine. The Vibrotex machine specimen times the density of the fiber specimen
(Lenzing AG, Lenzing, Austria) works by this times the density of the liquid.
principle. Displacement liquids used are n-heptane (
=
0.648 g/cm3 ) or methanol (
= 0.791 g/cm3 ).
The standard applied is ASTM D 276.

2.7.3. Gradient Method

A liquid column with a density gradient is pre-

pared by stacking layers of two liquids of dif-
ferent densities (e.g., xylene with
= 0.9 g/cm3
and pentachloroethane with
= 1.7 g/cm3 ), one
above the other. The fiber sample to be mea-
sured remains suspended at the height at which
the densities of liquid and fiber coincide.

2.8. Chemical Identification of Fibers by

Figure 16. Definition of crimp ratio and crimp retention Solubility
Crimp ratio:


E = l−l
l Specific fiber types are also identified by a com-


or E (in%) = l−l l
·100% bination of microscopic and solubility tests. To
Crimp retention:



save space, a complete solubility test scheme is
B (in%) = l−ll−l

·100% not presented here (see ASTM 276). Some sol-
vents for fibers are
Wool: potassium hydroxide
2.7. Density Polyamide: hydrochloric acid (6 mol/L)
Polyacrylonitrile: dimethylformamide
2.7.1. Pycnometer Method Polyester: 1,2-dichlorobenzene
Cellulose acetate: acetone
The pycnometer is a container of known vol-
ume, usually 50 cm3 . The mass P of the empty
pycnometer is known. It is filled with a mea- 2.9. Other Identification Methods for
suring liquid, preferably toluene, and weighed Fibers
(P + F 0 ). The container is then emptied, filled
with the fiber whose mass is to be measured Other characteristics can be used to identify
(P + G), and filled to the mark with measuring fibers, provided suitable measuring devices are
liquid (P + G + F). From these four weight de- available:
terminations and the known density of the mea-
Fiber density (see Section 2.7)
12 Fibers, 6. Testing and Analysis

Melting point (see Section 5.1) dust. Slivers from carding and drawing may also
Infrared spectroscopy be more or less contaminated, depending on the
Refractive index and birefringence intensity of cleaning. The various testing ma-
chines for determining trash and dust operate
The methods, including all necessary spec-
on the mechanical – pneumatic principle. Two
ifications and characteristic IR spectra, are de-
of these are mentioned below.
scribed in ASTM D 276.
Shirley Analyzer. A known weight of raw
cotton, partially processed cotton, or waste is
2.10. Identification of Wool and Hair fed into the machine. The machine separates the
foreign matter from the cotton and discharges
The wool and hair of different animals consist of the non-lint cotton into a separate chamber. The
the same basic substance; to differentiate among amounts of lint and nonlint recovered are calcu-
them under a standard microscope is often dif- lated as a percentage of the original specimen
ficult or impossible. Other characteristics, such mass (ASTM D 2812).
as fineness, fiber length, and crimp, are not suffi-
ciently different to assure unambiguous identifi- Micro Dust and Trash Tester. The Institute
cation. The scanning electron microscope has of Textile Technology and Process Engineering
proved suitable for identifying various wools Denkendorf (Germany) has developed a testing
and hairs. Good information is available in Test machine based on the opening device of a ro-
Method 20 of AATCC. tor spinning machine, which separates trash and
Distinguishing characteristics are the scales dust from the fiber material. Trash and micro
of the fibers and their thickness. Institutes that dust are picked up separately by separation and
have a scanning electron microscope and a staff suction, respectively, and weighed [9]. This in-
experienced with animal fibers are capable of strument has been adopted by Zellweger (Uster,
carrying out such investigations [7], [8]. Switzerland), modified, and sold under the trade
name MDTA 3 (micro dust and trash analyzer).
2.11. Analysis of Fiber Impurities and
Extractable Matter 2.11.2. Honeydew on Cotton

Natural fibers contain various impurities. In cot- The secretion of the white fly, a sticky sugar-con-
ton, these impurities originate predominantly taining substance called honeydew, is deposited
from the cotton plant. During ginning, cotton on the cotton shrub. Honeydew is very disrup-
fiber is contaminated further with seed-coat frag- tive during spinning. Various procedures have
ments. Scoured wool also contains vegetable im- been developed in recent years for determining
purities which cannot be removed by scouring. honeydew, none of which are satisfactory. The
In addition, the surface is covered with wax, highly nonuniform distribution of honeydew de-
grease, or oil, either of natural origin or ap- posit creates difficulties. Some procedures uti-
plied subsequently. Those substances which are lize chemical test solutions which discolor ap-
applied later are called preparations or finish propriately in the presence of sugar [10–12],
agents and, collectively, extractable matter (i.e., e.g.,
substances that can be removed by organic sol-
Benedict test
vents).
Perkins test
Bremer honeydew test
2.11.1. Trash and Dust Content of Cotton By means of extensive tests, the “Honeydew
(Nonlint Content) Working Group” of the International Cotton Test
Conference has found that these tests are not
Raw cotton contains various impurities such as fully applicable to industrial conditions. Various
stems, leaves, sand, seed-coat fragments, and measurement techniques in which the stickiness
dust which, collectively, are called trash and of fiber mats between heated metal plates is used
 Fibers, 6. Testing and Analysis 13

as a measure of the honeydew content are being

evaluated, and corresponding standards are in
preparation.

2.11.3. Grease Content of

Wool – Extractable Matter Content

Various solvents can be used to dissolve grease

or oil. Because other substances can be picked
up at the same time, depending on the solvent,
the term “extractable matter” is more accurate. Figure 17. Mature and immature cotton fibers
The following solvents are used for wool: a) Before husk is opened; b) After husk is opened

Ethanol ASTM D 584

Trichlorotrifluoroethane ASTM D 1574 Microscope. Fibers are swollen by addition
Dichloromethane ISO 3074; IWTO-10-62 of an 18 % solution of sodium hydroxide. Be-
cause of their smaller width, immature fibers can
Fiber samples are treated with the appropri-
be spotted and counted under a microscope. In
ate solvent in a Soxhlet extractor. The amount of
polarized light, immature fibers can be recog-
material extracted is referred to the dry or com-
nized even without swelling; the same is true for
mercial weight of the wool.
the microscopic examination of fiber cross sec-
tions. Standards are ISO 4912; ASTM D 1442;
DIN 53 943 T 2 and T 3.
2.11.4. Preparation and Finishing Agents
for Man-Made Fiber
Fiber Fineness. Fineness involves a deter-
A Soxhlet extractor is also used for man-made mination of the maturity index and is used to es-
fibers; however, a different solvent is employed. timate the linear density of loose cotton fibers by
No uniform international standard exists. The measuring, with an airflow instrument, the resis-
following solvents are specified in DIN 54 278: tance of a plug of cotton fibers to airflow before
and after treatment with a sodium hydroxide so-
Methanol: polyester, polyacrylonitrile, and lution (Causticaire method). The standards are
poly(vinyl chloride) fibers ASTM D 2480; DIN 54 943 T 4.
Petroleum ether: polyamide and cellulose ac- A new procedure measures the linear density,
etate fibers by using an airflow instrument, at two different
compression ratios of the cotton plug. The two
Another reference is ASTM D 2257, Stan-
readings are substituted in a formula, and the de-
dard Test Method for “Extractable Matter in
gree of maturity is calculated. The standards are
Yarns,” which can be applied to staple fiber.
ISO 10 306, EN 30 306, ASTM D 3818.
It uses Soxhlet extractions with trichlorotri-
fluoroethane and then ethanol.
Dyeing. Immature fibers acquire very differ-
ent coloration, especially with certain test dyes.
The red – green test is based on this property (red
2.12. Maturity of Cotton coloration = mature; green = immature). The de-
gree of maturity is estimated from a comparison
Cotton contains both fully matured and imma-
with standard samples.
ture fibers. The characteristic of immature cotton
fibers is a wall width less than the lumen width
Fibrograph. Another method for measuring
(Fig. 17). The degree of maturity can be deter-
cotton maturity is ASTM D 3817, Standard Test
mined by various procedures.
Method for “Maturity Index of Cotton Fibers
by Fibrograph” which uses the Uster Fibrograph
730 (see page 6).
14 Fibers, 6. Testing and Analysis

3. Tensile Properties relatively low tensile forces. The rates of elon-

gation are determined as a function of the ex-
3.1. Tensile Test pected elongation (Table 1). In addition to the
numerical indication of force and elongation,
To determine its deformation properties, a fiber the testing machine must be equipped with a de-
is clamped at each end in the jaws of a tensile vice on which the load – elongation curve can
testing machine and loaded in the longitudinal be recorded. Elongation rate (percent of initial
direction until it breaks. According to standards specimen length in mm) at the corresponding
in 1989, only tensile testing machines that oper- elongation at break
ate by constant rate of extension principles may Most testing machines on the market today
be used. The relevant terms are defined as fol- are combined with equipment for measuring
lows: fineness. Fineness is first measured by the vi-
Gauge Length. The gauge length is the dis- broscope method on each individual fiber, and
tance between the clamp jaws as traversed by the result is fed into a computer. The same fiber
the mounted specimen (which is not always a is then clamped in the tensile testing machine
straight line between the jaws, as is the case with and tested. The measured force is also fed into
capstan clamps). The gauge length should not the computer, which then calculates the tenac-
be less than 10 mm; 20 mm or more is preferred. ity at break. In addition, the computer calculates
The method ASTM D 2101, which is applied on an average of all the individual values and all
filaments, uses a 25-mm gauge length. other statistical parameters; as a rule, at least 50
Breaking Load. The maximum force applied individual values are required per test.
to a specimen in a tension test is called break- For wet testing, which is common for vis-
ing load. The force is expressed in newtons, cen- cose fiber, for example, the tensile testing ma-
tinewtons, or millinewtons. In ASTM standards, chine must be equipped with a suitable moist-
it is also expressed in gram-force (gf). ening device. The fiber clamped in the jaws is
Tenacity. The tensile stress expressed as force wetted directly.
per unit linear density of the unstrained spec- Standards are ISO 5079; EN 25 079; BISFA
imen is called tenacity. Tenacity is expressed Rules; ASTM D 3822. The method ASTM D
in centinewtons or millinewtons per tex; ASTM 2101 is used for longer fibers (25-mm gauge
also uses gram-force per tex (gf/tex). The tenac- length).
ity corresponding to the breaking load is called
breaking tenacity.
Elongation. Elongation is the increase in
length, expressed in units of length or as a per-
centage of the gauge length (Fig. 18). The elon-
gation corresponding to the maximum load is
called elongation at break.

Figure 19. Determination of elastic properties of fibers

A to B: load to required elongation
B to G: wait (simultaneous relaxing of stress)
Figure 18. Load – elongation curve G to C to A: back to zero elongation; wait
A to D to H: load to same elongation
Tensile testing machines must have the pre- Permanent deformation, % AD ·100
AE
cision necessary to measure fibers with suffi-
Tensile strain recovery, % DE ·100
cient accuracy at a gauge length of 10 mm and at AE
 Fibers, 6. Testing and Analysis 15
Table 1. Elongation rate (percent of initial specimen length in mm) at the corresponding elongation at break

Estimated elongation at break, % Elongation rate (ISO, EN) Estimated elongation at break, % Elongation rate (ASTM)

<8 50 <8 10
≥8 100 8 – 100 60
> 100 240

Figure 20. Determination of modulus

A)

Initialmodulus; B) Secant modulus; C) Tangent modulus
PB
AB/l0
where l 0 = specimen length (gauge length)

3.2. Elastic Behavior 3822; ASTM D 2101 is used for longer fibers
(25-mm gauge length).
The elastic properties of fibers are measured by
determining the amount of recoverable energy
exhibited by a fiber when it is stretched to a 3.4. Loop Tensile Test
predetermined extension at a specific elongation
rate, held at this extension for a specified length Loop breaking tenacity is a fundamental prop-
of time, and finally relaxed at the same rate at erty used to establish limitations on fiber pro-
which it was extended. The fiber can also be cessing and on end use. The specimen, consist-
loaded in multiple cycles, and the loading and ing of two single fibers looped in a configuration
unloading time in each can be varied. shown in Figure 21, is broken on a testing ma-
Permanent deformation and tensile strain chine with a constant rate of extension.
recovery can be determined from the load –
elongation curves (Fig. 19). These values can
be ascertained at various degrees of elongation,
e.g., 2, 5, and 10 %. Standards are ASTM D
1774; DIN 53 835.
Figure 21. Loop specimen configuration

3.3. Modulus 3.5. Bundle Stress Test

The modulus is the ratio of the change in tenac- Tensile testing of single fibers is very time-
ity, expressed in centinewtons per tex, to the consuming and requires careful handling. The
change in elongation, expressed as a fraction of relatively short fiber length of cotton presents
the original length. These values can be obtained additional problems. For this and other reasons,
in various ways from the tenacity – elongation collective test methods have been developed in
curve (Fig. 20). The standard used is ASTM D which a bundle of parallelized fibers is mounted
16 Fibers, 6. Testing and Analysis

in suitable clamps and broken. For some ma- IWTO-32-82; ASTM D 1445, D 2524. In prin-
chines, zero gauge length is recommended; for ciple, any tensile testing machine with suitable
others, the gauge length is 3.2 mm (1/8 inch). force range can be used to perform the bundle
test, provided appropriate clamps are available
Pressley Tester. For the Pressley tester, the (ASTM D 1294).
standard gauge length is zero, but it can be ad-
justed to 3.2 mm. A combed, parallelized bundle
of cotton is secured in two special clamps and 4. Behavior toward Water
loaded by releasing a weight that slides down
an inclined track. When the bundle breaks, the 4.1. Moisture Adsorption
weight stops on the track and the breaking force
can be read off the scale. The fiber bundle re- Fibers take up more or less water from the atmo-
maining in the clamps is then weighed so that sphere, depending on hygroscopicity and rela-
the breaking force can be related to fineness. The tive humidity (Fig. 22).
machine is calibrated with standard cotton (test Moisture uptake is subject to hysteresis
cotton), prescribed by the U.S. Department of (see Section 1.4); i.e., fibers take up different
Agriculture (USDA). The result is calculated as amounts of moisture, depending on whether they
the Pressley Index (DIN) or as breaking tenac- are brought into the standard climate from the
ity in gram-force per tex (ASTM). Standards are dry or from the wet state. Moisture affects vari-
ISO 300; ASTM D 1445; DIN 53 942. ous physical properties and is important in cal-
culating commercial weight.
Stelometer. In a stelometer, force is applied
by the pendulum principle. The gauge length is
3.2 mm. In addition to the breaking force, the
4.1.1. Oven Drying Test
elongation at break can also be read. By means
of fineness (weight and length) of the fiber bun-
The fibers are weighed, dried in an oven with hot
dle, tenacity at break is calculated in units of
air (105 ◦ C), and reweighed. The difference bet-
centinewtons per tex and, in the United States,
ween the original mass and the oven-dry mass
also in gram-force per tex. This instrument is
is the moisture content, expressed in percent.
available under the trade name Uster Stelometer
Standards are ISO 6741; IWTO-33-88, IWTO-
654.
34-85; BISFA Rules; ASTM D 629, D 1576,
D 2495, D 2654; DIN 53 800. For calculating
commercial weight, various organizations spec-
ify commercial moisture regain, but no uniform
international standard existed in 1989 (see also
BISFA Rules; ASTM D 1909; DIN 54 201).

4.1.2. Other Tests for Moisture Content of

Fibers

Fiber moisture also affects its electrical proper-

ties, e.g., electrical resistance or capacitive pa-
rameters in a condenser field. On this basis, in-
struments have been developed with which the
moisture content of fibers can be measured. They
are usually not accurate enough to determine
Figure 22. Moisture uptake of different fibers at 25 ◦ C [1] commercial weights, but because they can be
Test cotton or, if wool is to be tested, test read directly and are easy to use, they have been
wool can be used for calibration. Both are pre- adopted for control purposes.
scribed by the USDA. Standards are ISO 3060;
 Fibers, 6. Testing and Analysis 17

Measurement of Electrical Resistance. Two Glass transition temperature

needle-shaped electrodes are inserted in the fiber Softening range
material (e.g., in the bale) and moisture is mea- Melting point
sured via resistance. Decomposition temperature
Capacitive Measurement. Fibers, even Autoignition point
whole bales, are measured in the electrical field Char temperature
of a condenser. These instruments must be cal-
Two determinations used more frequently
ibrated by oven drying. This calibration should
with fibers – melting point and burning test –
be carried out at two different moisture levels
are discussed below.
for each fiber type.

4.2. Water Absorption 5.1. Melting Point

The melting point can be determined for fibers

Water is taken up from the liquid phase in differ-
by means of a microscope equipped with a spe-
ent ways. Part of the water enters the interior of
cial heating device. This is a way of distinguish-
the fiber, part of it is bound to the fiber surface,
ing nylon 6 from nylon 66, for example (standard
and part remains between fibers as a result of
ASTM D 276).
capillary action. The last is especially difficult
to measure because it is greatly affected by the
position of the fibers and the packing density.
Therefore, water retention is used as a measure 5.2. Burning Test
of water absorption because the conditions of
measurement are defined more precisely and are The burning test serves exclusively to iden-
easier to observe. tify fibers. Flammability, combustion behavior,
odor, and residue are characteristic of individual
Determination of Water Retention. A fiber types (see also Test Method 20 of AATCC).
fiber specimen is placed in a basket, immersed Some examples are
in water, and subsequently centrifuged. The Cellulose Fibers easily flammable; burns
conditions for centrifuging are defined by the (cotton, viscose rapidly with bright flame;
rayon) white-gray ash
standards Wool difficultly flammable; odor
of burnt hair; coal-like ash
ASTM D 2402: 1 h at an acceleration of 1000 g Polyamide moderately flammable;
(9800 m/s2 ) melts while burning, drips;
sphere-like residue
DIN 53 814: 20 min at an acceleration of 800 –
1000 g (7800 – 9800 m/s2 )
In this method, water retained by fiber masses
includes (1) water absorbed from the prevailing 6. Dyeing Properties
atmosphere, (2) water imbibed after immersion,
and (3) moisture adhering to fiber surfaces after
being subjected to acceleration.
6.1. Laboratory Dyeing

Dyeing tests are carried out preponderantly on

textile fabrics and yarns. If these are not avail-
5. Thermal Behavior able, test dyeings are carried out on fiber flock
in laboratory dyeing apparatus. In flock dye
Changes produced by thermal effects are almost houses, such test dyeings serve as control sam-
exclusively determined on the yarns or textile ples. The test dyeing itself can take place in sim-
fabrics made from fibers rather than on the fibers ple dye beakers or in a dyeing apparatus with stir-
themselves. Only a few characteristic tempera- rers and programmed heating cycles. For high-
tures can be measured on the fibers and be used temperature dyeing (above the boiling point), a
to identify fiber types: special apparatus is required.
18 Fibers, 6. Testing and Analysis

6.2. Identification of Fiber Type by machines are involved. For this reason, a test run
Dyeing (Neocarmine) under actual operating conditions on the produc-
tion machine itself is often preferred.
Neocarmine dyes (e.g., Neocarmine W
[51394-11-7], obtainable from FESAGO, Hei-
delberg, Federal Republic of Germany) are used 7.3. Electrostatic Charging
to identify fiber types by comparison with a
color scale. This is an especially useful method Fibers that absorb little moisture, which include
if a microscope or other expensive equipment is all synthetic fibers, tend to be electrostatically
not available. charged. They are, therefore, provided with an-
tistatic finishing agents. The antistatic effect de-
pends on the relative humidity of the atmo-
7. Processing sphere.
The tendency to be charged electrostatically
can be measured with the aid of so-called field-
7.1. General
intensity meters at the card or mini card or on
the drawing frame. The measured field intensity
The processibility of fibers into yarns or non-
in volts per meter, together with the relative hu-
wovens is important to spinners and nonwoven
midity, indicates the running properties that can
producers. This property is highly complex and
be expected and possible processing problems.
contains many subproperties and characteristics
which make laboratory testing difficult. Start-
ing with a processing test on production ma-
chinery, a scaled-down, semiworks machine is
constructed in which the number of production
units (e.g., the number of spindles on a spinning
machine) is reduced. The amount of fiber to be
processed is thus kept to a minimum, but a cer-
tain amount of information on processibility is
lost.
Occasionally, attempts are made to predict
processibility with the aid of specially developed
testing devices. This is only partially successful.
With the present state of the art, only a few pro-
cessibility characteristics can be estimated from
such devices and from spinning tests on semi-
works spinning units.
Figure 23. Principle of rotor ring method
a) Feeding of fibers; b) Feeder; c) Opener; d) Rotor ring
(fleece of parallelized fibers); e) Rotor; f) Feeding tube
7.2. Spinning Devices for Trials

A mini carding machine is used to open the

fibers. Next, the fiber web is parallelized on 7.4. Rotor Ring Method
small draw rolls and spun on a spinning tester.
The spun yarn can be checked for various prop- The rotor ring device developed at the Institute
erties. Rovings can also be fed to spinning po- for Textile Technology and Process Engineering
sitions to determine the behavior of fibers in the Denkendorf (Rotor Ring Device 580) consists,
spinning process or to investigate certain spin- in essence, of a rotor spinning unit. By measur-
ning parameters. ing the width of the fiber ring taken from the
Only limited conclusions concerning proces- rotor and the electrical output of the opening
sibility on production machines can be drawn roll, important conclusions can be drawn con-
from such tests, especially if high-production cerning the processibility of fibers, crimp, finish
 Fibers, 6. Testing and Analysis 19

properties, fiber – fiber friction, and fiber – metal – Fineness (Micronaire)

friction (Fig. 23) [13]. – Trash content (scanning)
– Color
Other combinations, including measurement
7.5. Combination of Micro Dust and of maturity or trash and dust content, are pos-
Trash Analyzer with the Rotor Ring sible. Two manufacturers have produced such
Method and a Spinning Device for Trials units, several hundred of which are in use world-
wide:
At the Institute for Textile Technology and Pro-
cess Engineering Denkendorf, a combination of 1) High Volume Testing (HVT) from Spinlab,
the following test methods has been developed Inc., Knoxville, Tennessee, and
and is marketed by Zellweger under the trade 2) High Volume Instruments (HVI) from Mo-
name Uster Quickspin System: tion Control, Inc., Dallas, Texas
– Micro Dust and Trash Analyzer, MDTA 3 The units are calibrated with test cotton
– Rotor Ring Method, Rotorring 3 (see Sec- whose properties are determined and approved
tion 7.4) with a large rotor (diameter ca. by a central test laboratory. This can be consid-
320 mm) ered something of a disadvantage. Calibration by
– Quickspin rotor spinning device for procuc- means of a standard independent of the material
ing a rotor yarn to be tested would be preferable. The advantage
A modified rotor ring device (see Fig. 23) sep- of these test lines is that complete measurement
arates micro dust and trash by filtration and suc- of several properties can be performed in a very
tion and weighs them. The cleaned fibers pass short time (a few minutes) by one person. With
through the feeding tube (f) into the rotor (e), a complete knowledge of raw materials data, di-
whose diameter of ca. 320 mm is such that the rected use in spinning becomes possible.
fiber ring removed from the rotor has a length
of ca. 1 m. The fiber ring is used for the deter-
mination of some of the properties described in 9. References
Section 7.4. The fiber ring is then cut to give a
ca. 1 m long sliver, which is spun into a yarn ca. General References
200 m in length. Physical investigations on the 1. H. Sommer, F. Winkler: Handbuch der
yarn then allow conclusions to be made about Werkstoffprüfung, “Die Prüfung der
the properties of the fibers. Textilien,” Springer-Verlag, Berlin 1960.
The Quickspin System is mainly intended for 2. P. M. Latzke, R. Hesse: Textilien,
rapid evaluation of raw cotton. It enables cotton Prüfen – Untersuchen – Auswerten,
Fachverlag Schiele & Schön GmbH, Berlin
dealers and processors to quickly evaluate the
1974.
quality of a cotton delivery on the basis of small
3. E. Wagner: Mechanisch-technologische
samples.
Textilprüfungen, Dr. Spohr-Verlag, Stuttgart
1966.
4. A. Agster: Färberei- und textilchemische
8. Automated Test Units Untersuchungen, Springer-Verlag, Berlin
1967.
Test lines have been developed for testing cotton
where several fiber properties can be determined Specific References
sequentially, largely in an automated or mech- 5. L. J. Lynch, N. A. Michie, Text. Res. J. 46
anized mode. Control of the operation, calibra- (1976) 653.
tion, recording, and analysis of results are per- 6. A. R. Edmunds, H. McNally, IWTO Technical
formed with the aid of computers. The essential Committee Report No. 7, June 1987.
properties measured are 7. P. Kusch, G. Stephani, Schriftenr. Dtsch.
Wollforschungsinst. Tech. Hochsch. Aachen
– Fiber length (fibrograph principle) 96 (1984).
– Fiber strength and elongation (bundle test)
20 Fibers, 6. Testing and Analysis

8. P. Kusch, W. Arns, Melliand Textilber. 64 11. H. H. Perkins, jun., Text. Bull. 97 (1971) no. 8,
(1983) 427 – 429. 21.
9. E. Kirschner, E. Bay, TPI Text. Prax. Int. 39 12. S. Sismann, A. Schenek, Melliand Textilber.
(1984) 985 – 990. 65 (1984) 642 – 644.
10. F. Hadwich, Melliand Textilber. 42 (1961) 487. 13. P. Ehrler, O. Schreiber, TPI Text. Prax. Int. 39
(1984) 347 – 352.

Fibrinogen → Blood
Fibrinolytics → Blood
Fillers → Paints and Coatings
Fillers → Paper and Pulp
Fillers → Plastics, Additives
Fillers → Rubber, 4. Chemicals
Film Deposition → Thin Films
 Films 1

Films
Peter Schmitz, Hoechst AG, Werk Kalle, Wiesbaden, Federal Republic of Germany

Siegfried Janocha, Hoechst AG, Werk Kalle, Wiesbaden, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . 2 6.3.1. Poly(Vinyl Chloride) (PVC) . . . . . 20

2. Production Technology . . . . . . . 3 6.3.1.1. Rigid PVC . . . . . . . . . . . . . . . . 20
2.1. Solution Casting . . . . . . . . . . . 3 6.3.1.2. Plasticized PVC . . . . . . . . . . . . 20
2.2. Thermoplastic Film Forming . . . 5 6.3.2. Poly(Vinylidene Chloride) (PVDC) 20
2.2.1. Calendering . . . . . . . . . . . . . . . 5 6.3.3. Fluoropolymers . . . . . . . . . . . . 21
2.2.2. Extrusion . . . . . . . . . . . . . . . . 5 6.3.3.1. Poly(Vinyl Fluoride) (PVF) . . . . . 21
2.3. Stretching . . . . . . . . . . . . . . . . 7
6.3.3.2. Poly(Vinylidene Fluoride) (PVDF) 21
2.3.1. Monoaxial Stretching . . . . . . . . . 7
6.3.3.3. Polytetrafluoroethylene (PTFE) . . 21
2.3.2. Biaxial Stretching . . . . . . . . . . . 7
2.4. Film Modification and Converting 9 6.3.3.4. Polychlorotrifluoroethylene
2.4.1. Corona Treatment . . . . . . . . . . . 9 (PCTFE) . . . . . . . . . . . . . . . . . 22
2.4.2. Coating . . . . . . . . . . . . . . . . . . 10 6.4. Poly(Methyl Methacrylate)
2.4.3. Lamination . . . . . . . . . . . . . . . 10 (PMMA) . . . . . . . . . . . . . . . . 22
3. Additives . . . . . . . . . . . . . . . . 10 6.5. Poly(Vinyl Alcohol) (PVA) . . . . . 22
4. Delivery Forms . . . . . . . . . . . . 11 6.6. Ethylene–Vinyl Alcohol Copoly-
5. Test Methods . . . . . . . . . . . . . 11 mer (EVOH) . . . . . . . . . . . . . . 22
6. Film Products . . . . . . . . . . . . . 13 6.7. Polyamide (PA) . . . . . . . . . . . . 23
6.1. Cellulose Derivatives . . . . . . . . 13 6.8. Polyester . . . . . . . . . . . . . . . . 23
6.1.1. Cellulose Hydrate . . . . . . . . . . . 13 6.9. Polycarbonate (PC) . . . . . . . . . 24
6.1.2. Cellulose Esters . . . . . . . . . . . . 13 6.10. Polysulfone (PSU) . . . . . . . . . . 24
6.2. Hydrocarbon Polymers . . . . . . . 18 6.11. Polyimide (PI) . . . . . . . . . . . . . 24
6.2.1. Low-Density Polyethylene (LDPE) 18 6.12. Other Films . . . . . . . . . . . . . . 24
6.2.2. High-Density Polyethylene (HDPE) 18 6.12.1. Polyetherimide (PEI) . . . . . . . . . 24
6.2.3. Linear Low-Density Polyethylene
6.12.2. Polyethersulfone (PES) . . . . . . . . 25
(LLDPE) . . . . . . . . . . . . . . . . . 18
6.12.3. Poly(ether ketone) (PEK) . . . . . . 25
6.2.4. Polypropylene (PP) . . . . . . . . . . 18
6.12.4. Poly(Phenylene Sulfide) (PPS) . . . 25
6.2.5. Poly(4-methyl-1-pentene) (PMP) . 19
6.2.6. Ionomers . . . . . . . . . . . . . . . . . 19 6.13. Composite Films . . . . . . . . . . . 26
6.2.7. Polystyrene (PS) . . . . . . . . . . . . 19 7. Summary of Uses . . . . . . . . . . . 26
6.3. Halogenated Hydrocarbon Poly- 8. Environmental Aspects . . . . . . . 28
mers . . . . . . . . . . . . . . . . . . . 20 9. References . . . . . . . . . . . . . . . 28

Abbreviations used in this article: LDPE low-density polyethylene

LLDPE linear low-density polyethylene
BOPP biaxially oriented polypropylene
MD machine direction
CA cellulose acetate
PA polyamide
CAB cellulose acetate butyrate
PBT poly(butylene terephthalate)
CAP cellulose acetate propionate
PC polycarbonate
ETFE ethylene–tetrafluoroethylene copoly-
PCTFE polychlorotrifluoroethylene
mer
PEI polyetherimide
EVM ethylene–vinyl acetate copolymer
PEK polyetherketone
EVOH ethylene–vinyl alcohol copolymer
PEN poly(ethylene-2,6-naphthalene dicarbox-
FEP tetrafluoroethylene–hexafluoropropyl-
ylate)
ene copolymer
PES polyethersulfone
HDPE high-density polyethylene

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11 085
2 Films

PETP poly(ethylene terephthalate) of these applications. These products provide a

PFA perfluoroalkoxy copolymer broad spectrum of mechanical, optical, and elec-
PI polyimide trical properties, as well as various degrees of
PMMA poly(methyl methacrylate) permeability and stability to temperature and ag-
PMP poly(4-methyl-1-pentene) gressive media.
PP polypropylene
Table 1. Worldwide consumption of some of the most important
PPS poly(phenylene sulfide) types of film in 1986∗
PS polystyrene
Material Consumption, 106 t
PSU polysulfone
PTFE polytetrafluoroethylene Low-density polyethylene (LDPE) 8.00
PVA poly(vinyl alcohol) Polypropylene, biaxially oriented (BOPP) 0.55
Poly(vinyl chloride) (PVC), rigid and 1.42
PVC poly(vinyl chloride) plasticized
PVDC poly(vinylidene chloride) Poly(ethylene terephthalate) (PETP),
biaxially oriented 0.55
PVDF poly(vinylidene fluoride) Cellophane 0.26
PVF poly(vinyl fluoride)
∗ Hoechst marketing research, Kalle Works, Federal Republic of
TD transverse direction Germany.

Historical Aspects [1]. Polymeric films were

1. Introduction first developed at the end of the 19th cen-
tury, when cellulose nitrate was introduced as a
The term film is applied to thin materials present base material for photographic emulsions. Other
in a continuous planar form, which are at the cellulose-based films followed, the most impor-
same time self-supporting and flexible. A film tant of which were derived from cellulose acetate
may consist of one or more layers, usually of dif- and cellulose hydrate. Cellulose triacetate films
fering composition. The term generally encom- quickly replaced the highly flammable cellulose
passes both metallic and polymeric substances, nitrate films in the photographic industry; cellu-
which may be either homogeneous or made het- lose hydrate films (cellophanes) became impor-
erogeneous by the presence of incompatible ad- tant packaging materials, maintaining their dom-
ditives or blending components. In this article, a inance until polyolefin films were introduced in
film is assumed to be a polymeric material which the 1950s. Cellophane coated with cellulose ni-
can be wound into a roll. Film thicknesses range trate or poly(vinylidene chloride) also played a
from 0.5 µm to ca. 1 mm. key role in this respect due to its low perme-
The characteristics of a film are determined ability to water vapor and oxygen, coupled with
primarily by the raw materials employed, but desirable sealing properties.
they are additionally affected by processing All cellulose-based films are prepared from
methods, modification, and converting (e.g., polymer solutions, however the subsequent in-
stretching, coating and lamination). troduction of totally synthetic polymers has led
Film materials are of considerable economic to new film production methods, as well as new
importance. In 1986, the annual worldwide con- types of films with unique properties. These de-
sumption of film for packaging and technical velopments have been encouraged by the close
applications was ca. 11×106 t. Figures for the working relationship between fiber and film pro-
worldwide consumption of the more important ducers, particularly in terms of polymer compo-
film materials are listed in Table 1. sitions and processing technology.
Films are used as flexible packaging mate- Important milestones in the development of
rials, as insulation for electrical conductors, as films included the introduction of
protective layers on sensitive surfaces, and as
1) poly(vinyl chloride) films in the late 1930s
windable base materials for subsequent applica-
2) low-density polyethylene films in the late
tion of magnetic coatings, electrically conduct-
1940s
ing, and light-sensitive layers as well as printing
3) biaxially oriented polyester and polypropyl-
inks. Multitudes of film and sheet types have
ene films in the 1950s
been developed to meet the increasing demands
 Films 3

Parallel and subsequent to these develop- solvent. The solution is normally very viscous
ments, a series of specialty films has emerged. (ca. 20 Pa · s) and is passed through a filter press
These films are distinguished either by high equipped with a cotton filter. After the viscos-
mechanical or thermal stability, or by special ity has been checked, the solution finally enters
properties such as impermeability to oxygen, the casting reservoir. Entrapped air is removed
advantageous electrical characteristics, or resis- either by evacuation or by heating.
tance to chemical attack. The solution is fed from the reservoir under
pressure through the die and is cast onto a ro-
tating drum or a moving metal belt. The die gap
2. Production Technology [2] is adjusted according to the desired thickness of
the film.
Generally speaking, the manufacture of films The metal belt may be made of copper, nickel,
from both natural and synthetic polymers relies or steel, and its surface finish is of critical impor-
on two basic techniques: tance in determining the characteristics of the re-
sulting film. For optical-grade films, the surface
1) solution casting must be polished and filtration must be highly ef-
2) thermoplastic film forming fective. Belt dimensions range from 25 to 55 m
in length and 1 to 2 m in width; belt speed varies
The method chosen is generally determined
from 1 to 60 m/min, depending on the desired
by the behavior of the starting materials with re-
thickness of the film.
spect to solvents and temperature. However, in
The film is dried on the belt by a countercur-
certain cases the desired product characteristics
rent of warm air and is then removed, further
are decisive.
dried, and wound. Typical thicknesses of films
For solution casting, the raw materials must
prepared in this way are 15 – 250 µm.
first be dissolved in an appropriate solvent. The
In some cases, the polymer solution emerges
solution is then pressed through a slot die either
from a slot die directly into a liquid precipita-
onto a moving belt or into a precipitation bath.
tion bath. The polymer solvent is miscible with
Thermoplastic film formingcan be divided
the bath fluid, whereas the polymer is insolu-
into two categories: (1) calendering (film forma-
ble in this fluid. Consequently, the polymer co-
tion in a rolling process) and (2) film formation
agulates in the bath to form a gel film with a
from a melt (an extrusion process).
microporous structure. Thus, this process is fre-
quently employed for the preparation of mem-
branes (→ Membranes and Membrane Separa-
2.1. Solution Casting tions).
Cellulose hydrate (cellophane) films [3] are
Solution casting is applicable to soluble poly-
produced by a modification of this process in
mers that are difficult or impossible to thermo-
which the gel film undergoes a chemical reac-
form. It also has advantages in the preparation of
tion. The casting solution is prepared by reacting
films for optical applications. Cellulose acetate,
cellulose with caustic soda solution and carbon
polycarbonate, and polyimide films are prepared
disulfide to form viscose. The resulting xanthate
in this way.
solution is then pressed into a spinning bath con-
Solution casting consists of three stages:
taining sulfuric acid, causing decomposition of
1) preparation of the casting solution the xanthate and forming a gel web composed
2) film formation on a moving surface (drum or of regenerated cellulose (see also → Cellulose,
endless belt) or in a precipitation bath Chap. 3.1.).
3) removal of residual solvent A slot die is immersed in the precipitation
bath (see Fig. 2). Shortly after its formation, the
Figure 1 is a schematic illustration of a belt gel film possesses sufficient stability to permit its
casting machine that is suitable for the produc- transport over rollers. The film is subsequently
tion of cellulose acetate film. washed and bleached, passed through plasticizer
The casting solution is prepared in a large baths, dried, and wound.
agitator vessel, if possible using a low-boiling
4 Films

Figure 1. Film production by solution casting on an endless belt

a) Agitator vessel; b) Filter; c) Degasser/casting reservoir; d) Die/caster; e) Metal belt; f) Solvent recovery; g) Air heater;
h) Final dryer; i) Winding

Figure 2. Production of cellulose hydrate film by casting into a precipitation bath

a) Casting solution, slot die; b) Precipitation bath; c) Regenerated film web; d) Regeneration bath; e) Wash and bleaching bath;
f) Plasticizer bath; g) Drying rolls

Film thickness ranges from 12 to 45 µm with The production of calendered (e.g., PVC)
a typical width of ca. 2 m. Production rates of film is shown in Figure 3; three steps are in-
80 m/min are common for films in the mid- volved:
thickness range. The normal slot die may be re- 1) preparation of a blend of the components in
placed by an annular orifice, in which case the a mixer
product is a tube of regenerated cellulose [4]. 2) homogenization and plastification
Further processing is as described above for flat 3) film formation in the calender
cellulose hydrate films.
The powdered mixture is usually converted
into a fused mass by continuous compounding in
2.2. Thermoplastic Film Forming a kneader or planetary-gear extruder using heat,
shearing forces, and pressure. The mass is then
2.2.1. Calendering [5–7] rolled into a film web, ideally with a four- or five-
roll calender, in which the nip rolls are mounted
Only polymers with a broad range of plasticity in an “L”-form. These rolls are made of steel or
and high viscosity can be processed by the calen- cast iron and they generally have a smooth sur-
dering method; these criteria are met by homo- face. The nip rolls are heated to 180 – 220 ◦ C,
and copolymers of poly(vinyl chloride) (PVC). depending on the process and the polymer mix-
ture; heating must be uniform. The calendered
 Films 5

Figure 3. Film production by calendering

a) Mixer; b) Kneader; c) Feed band; d) Calender; e) Cooling and tempering rolls; f) Winder

web then passes over cooling rolls followed by Various extruder designs can be used includ-
an edge-trimmer, in some cases a stretching fa- ing single-screw and twin-screw extruders, the
cility, and finally a winding unit. Calendering latter with either corotating or contrarotating
equipment operates at high pressure and must, screws. Extremely high outputs of 4 – 5 t/h can
therefore, be solidly constructed, making it very be achieved with two extruders combined in se-
expensive. The largest production facilities for quence (tandem extruder). Single-screw extrud-
processing plasticized PVC have nip rolls 85 cm ers are the most common. Screw geometry must
in diameter and are 280 cm wide. Calenders for be adapted to the raw materials being processed
rigid PVC utilize rolls up to 70 cm in diameter and has a major effect on the output and quality
and are 250 cm wide. Production rates of 50 – of the melt. The largest single-screw extruders
100 m/min are achieved depending on the de- currently in use have a screw diameter (D) of
sired film thickness; with stretching, line speeds 30 cm and a screw length of 30 D.
approach 300 m/min. These figures correspond The melt is filtered in one of several ways de-
to an output of 500 – 2000 kg/h. pending on the desired purity: wire mesh, sin-
tered metal, and wire–felt disks are all used.
The filtered raw materials are forced through a
2.2.2. Extrusion [8] slot die. The required pressure can normally be
Advantages of extrusion include a wide range of achieved with the extruder, however in special
attainable film thickness, large-scale processing, cases a gear pump is installed before the filter to
and the fact that recovery systems for expensive ensure constant metering of the melt. In coextru-
solvents are not needed. sion (see Section 2.4.2), the die combines several
The technique utilizes an extruder to melt the different melt streams. The width of the die and
polymer, a die to confer shape to the melt, and a the die gap determine the width and thickness of
cooling system to solidify it. The process is ap- the film, respectively. In large production units,
plicable only to raw materials for which there is the dies may be as wide as 3.5 m. Adjustment
a sufficiently large temperature difference bet- of the die gap permits the film thickness profile
ween melting and the onset of decomposition to be corrected during production. Initial adjust-
(e.g., polyolefins, polyamides, and polyesters). ment and readjustment can be performed either
manually or automatically, e.g., by thermal ex-
Chill Roll Extrusion . Figure 4 is a pansion of adjusting screws that are heated as a
schematic illustration of a chill roll extrusion function of the relative film thickness.
line. Moisture-containing raw materials (mois- When the melt film emerges from the die,
ture content usually 1 %) are subjected to it is cast onto a highly polished, chrome-plated
continuous or discontinuous drying, preferably chill roll. The takeoff speed depends on both
utilizing heated air or a vacuum, prior to melting film thickness and output and may be as high as
in the extruder.
6 Films

Figure 4. Film production by chill roll extrusion

a) Extruder; b) Filter; c) Slot die; d) Air knife; e) Cooling roll; f) Device for measuring film thickness; g) Tension rolls;
h) Corona treatment; i) Edge trimming; j) Winding

100 m/min. Entrapment of air between the melt The cooled tube is collapsed by transporting
and the roller surface is prevented by using an it through a convergent collapsing frame and a
air jet (air knife), electrostatic “pinning”, or a set of nip rolls. The film can then either be wound
vacuum device. directly as a flattened tube or slit open on both
The thickness of the film is measured with the sides and directed to two separate winding sta-
aid of a traversing radiation source and detector. tions. The largest film blowing systems utilize
The film is then edge-trimmed and wound to a annular dies with a diameter of 2 m and an out-
roll. If the film is to be printed, corona pretreat- put of 1.5 t/h.
ment can also be carried out (see Section 2.4.1). The film blowing process is employed mainly
The film is usually cut to the designated width for polyolefin and polyamide films. Multilayer
in a separate process–the actual width depending films can be produced by coextrusion of tubular
on the application. If monoaxial or biaxial ori- films (see Section 2.4.2).
entation is desired, the film is fed directly into
a stretching unit (see Section 2.3) without inter-
mediate winding. 2.3. Stretching [8]
Film Blowing (Blown-Bubble Extrusion). Many films acquire their desired properties only
In the film blowing process, the filtered melt is after stretching. Stretching below the softening
pressed through an annular die instead of a slot temperature orients the polymer molecules and
die; this results in the production of a tubular crystallites in the direction of stretch, leading to
film (Fig. 5). The tube (or “bubble”) is inflated changes in the stress–strain characteristics of the
by means of air blown through the center of the material. Both the modulus of elasticity and the
die. The film is thereby expanded at a tempera- ultimate strength are increased by this process,
ture close to its melting point and is then cooled but elongation at break and dimensional stability
by an airstream located above the die. A number with respect to temperature decrease. A number
of techniques are employed for air cooling; the of other characteristics may be altered as well,
most common involves passing the tube through depending on the type of film involved, e.g. gas
a cooling ring. Supplementary internal cooling permeability, electrical properties, heat sealabil-
is also usually used if a high throughput is re- ity, abrasion resistance, coefficient of friction,
quired. If biaxial stretching is to be performed, puncture resistance, density, and optical proper-
the melt must be solidified immediately after it ties. Stretching can be conducted either solely in
emerges from the die (see Section 2.3.2). the machine (longitudinal) direction (monoaxial
 Films 7

Figure 5. Film production by the blowing method

a) Extruder; b) Filter; c) Blowing air; d) Annular die; e) Air cooling ring; f) Film tube (bubble); g) Flattening; h) Nip rolls;
i) Tube separation (slitting); j) Winding

stretching) or in both the machine and the trans- 2.3.1. Monoaxial Stretching
verse directions (biaxial stretching).
Monoaxial stretching (see Section 2.3.1), Monoaxial stretching is accomplished by sub-
which is also commonly used in the produc- jecting a film to an increasing velocity gradient
tion of high-strength fibers, produces films of as it passes through one or more gaps between
enhanced strength in the direction of manufac- temperature-controlled rolls. Numerous stretch-
ture. The resulting films are thus anisotropic. ing machines are available; they differ with re-
Biaxial stretching (see Section 2.3.2) can be spect to the number and arrangement of the
conducted in one or two steps (simultaneous rolls. Monoaxial stretching is of particular im-
and sequential stretching, respectively). Sequen- portance in the manufacture of high-strength
tial stretching may result in either anisotropic or tape from polyethylene and polypropylene, as
isotropic films depending on the ratio of the final well as for the orientation of poly(vinyl chlo-
length to the initial length (the draw ratio). Si- ride), polycarbonate, and poly(vinylidene flu-
multaneous stretching tends to produce isotropic oride) films. Longitudinal stretching units are
films. also incorporated in film production lines that
The majority of films prepared from ori- employ sequential stretching technology for the
entable polymers are amenable to either sequen- manufacture of biaxially oriented films (see Sec-
tial or simultaneous biaxial stretching. However, tion 2.3.2).
films derived from polymers with a high rate of
crystallization during orientation (stress crystal-
lization) [e.g., some polyamides, poly(butylene 2.3.2. Biaxial Stretching
terephthalate), and ethylene–tetrafluoroethylene Sequential Stretching. Sequential biaxial
copolymer] can only be oriented by simultane- stretching is currently the preferred orienting
ous stretching. method for example with polyester and polypro-
pylene films. Figure 6 illustrates a production
8 Films

line that uses longitudinal–lateral stretching (the Simultaneous biaxial stretching of a flat film
so-called machine direction–transverse direc- is technically more complicated than that of
tion, MD−TD sequence) for the manufacture of tubular materials. Normally, a special stretch-
biaxially stretched film. The film line consists ing (stenter) frame is used in which the clips are
essentially of a chill roll facility coupled with not linked in a chain as described for sequential
forward and transverse stretching units. stretching. The clips are individually accelerated
The polymer is first dried, melted in an ex- as they pass through the transverse-stretching
truder, passed through a slot die, and vitri- zone by means of a progressive transport sys-
fied on a chill roll. Longitudinal stretching fol- tem.
lows using a system of rollers, whereas draw-
ing in the transverse direction occurs in an air-
heated oven (stenter) comprising several temper- 2.4. Film Modification and Converting
ature-controlled zones. When the longitudinally
stretched film enters the stenter, it is grasped at Films are normally intermediates from which
both edges by two series of continuously circu- end products are manufactured in subsequent
lating clips which are linked together in a chain. processing steps. The terms film modification
In the zone where the film reaches the stretching and converting refer to operations such as sur-
temperature, the two series of parallel-running face treatment, coating, or lamination, which en-
clips are gradually drawn apart and hence stretch hance the value of a film. Commonly encoun-
the film in the transverse direction (Fig. 6). The tered end products derived from films include
film is then heat-set (crystallized), cooled, re- packaging materials (e.g., printed bags and ad-
leased from the clips, and wound to a roll. Draw hesive tapes), capacitors, magnetic tapes, and
ratios for polyester lie typically between 3 : 1 photographic films.
and 4 : 1 [9], [10]. Untreated films often lack the specific char-
Facilities for edge-trimming, thickness deter- acteristics that are required in the final prod-
mination, and, where appropriate, corona treat- uct, e.g., stability during handling, heat sealabil-
ment (see Section 2.4.1) are located between the ity, wettability, adhesion of printing ink or other
stenter and the winding unit. Winding speeds coatings, and barrier properties. Further process-
range from 80 to 250 m/min. Film thickness ing is then needed to remedy these deficiencies.
varies from 1 to 350 µm. Sometimes the desired results can be obtained
Polyester films with a high modulus of elas- with additives (cf. Chap. 3), which include an-
ticity in the machine direction are best prepared tistatic agents and lubricants. However, surface
by a TD−MD stretching sequence, or in a three- treatment or coating is often necessary, and in
step process with MD−TD−MD stretching. some cases two or more films must be combined
to form a laminate.
Simultaneous Stretching. Simultaneous
biaxial orientation is most easily achieved by
inflation of a tubular film. In the continuous pro- 2.4.1. Corona Treatment
cess, a tube is first created by cooling the melt
in a water bath or with a cooling mandrel. This Corona treatment is the principal method of
tube is subsequently heated to the stretching preparing a film surface for printing or coating.
temperature with a ring of radiant heaters. It is A continuously moving film is exposed to an ion-
then inflated, collapsed, and transported as de- ized atmosphere, which is produced by an alter-
scribed for blown films (see Section 2.2.2). This nating electrical field [11]. The changes induced
technique is widely used for preparing biaxially in the film surface enhance both its wettability
oriented poly(vinylidene chloride), polyamide, and adhesion properties. Corona treaters can be
polyester, and especially polypropylene tubular integrated into the film production process (see
films; all of these films have a high shrinking Sections 2.2.2 and 2.3.2) and are widely utilized
potential. For this reason, oriented polypropyl- in the pretreatment of polyolefin films.
ene tubular films are normally slit, separated,
and then heat-set, either with the aid of heated
rollers or in a hot-air tunnel.
 Films 9

Figure 6. Production of biaxially oriented film by sequential stretching in a machine direction–transverse direction (MD–TD)
sequence [production unit viewed from the side (A) and from above (B)]
a) Dryer; b) Extruder; c) Slot die and chill roll; d) Stretching in the machine direction (MD); e) Preheating zone; f) Zone for
stretching in the transverse direction (TD); g) Heat-setting (crystallizing) zone; h) Cooling zone; i) Thickness measurement;
j) Winding

2.4.2. Coating Films with a different functional coating on

each surface possess a combination of proper-
Films may be coated with dissolved, dispersed, ties (e.g., sealing and barrier properties) and can
emulsified, or molten materials [8], [12]. The be produced on a large scale.
techniques employed differ considerably, de-
pending on whether the material is applied as Molten materials are applied to films with
a liquid or as a melt. the aid of a die by a process analogous to chill ex-
trusion (see Section 2.2.2). The film itself is sup-
Liquid materials are normally coated on ported by a roller. Extrusion coating can be con-
one or both sides of a moving film web either ducted either off- or in-line; the latter approach
by immersion or with the aid of applicator rolls. is employed with biaxially stretched films.
The coated film is then dried in a heated-air oven Coextrusion represents a special case of melt
or by means of rollers. coating [14], [15] in which two or more poly-
Coating is normally performed separately mer melt streams are combined either in the melt
from film production (off-line coating), although pipes or in a multimanifold die just before the
in some special cases, the two processes can be material emerges from the die lips. In the former
integrated (in-line coating) [13]. In in-line coat- case, special adapters of varying design ensure
ing (e.g., of polyester films), the coating assem- that the melt streams do not mix in the die and
blies are preferentially placed between the MD hence leave the die gap in the form of a multi-
and TD stretching units. layer film analogous to that produced by a mul-
Coating materials such as nitrocellulose, timanifold die. This process is also adaptable to
polyacrylates, and poly(vinylidene chloride) are annular die systems.
used to improve heat sealability and gas bar- Coextrusion has gained considerable impor-
rier properties. Adhesion is improved by coating tance. Sealable, biaxially oriented polypropyl-
films with polyurethanes, cross-linkable poly- ene film with a triple-layer structure is a particu-
acrylate, copolyesters, or epoxides. Other coat- larly important product in the packaging indus-
ings include antistatic or slip agents, scratchre-
sistant and antiadhesive materials.
10 Films

try. The thickness of the sealable layer is typi- Additives used in films that come into contact
cally 0.5 µm. with food must also comply with legal health
Coextruded, double-layer films are com- and safety requirements.
monly employed for magnetic tape and capac-
itors; they have a smooth side which can be Processing Stabilizers. The thermal decom-
coated, and a rough side, which ensures a low position of some film raw materials must be
coefficient of friction for adequate processabil- suppressed by addition of processing stabiliz-
ity. ers so that the melt can be thermoformed. The
choice of stabilizer depends on the decomposi-
tion mechanism involved. Thus, sterically hin-
2.4.3. Lamination [8], [12] dered phenols effectively stabilize polypropyl-
ene, while poly(vinyl chloride) responds to treat-
Two or more different films can be bonded to ment with metal salts (in particular organic tin
form a composite or multilayer film. Their indi- salts) or N,N -diphenylthiourea [102-08-9]. Ad-
vidual properties are thus combined, resulting in ditive concentrations range from <1 to 3 wt %.
a variety of high-quality materials for both the
packaging industry and the technical sector. For Plasticizers. Plasticizers are particularly
example, a heat-sealable film may be laminated useful for adjusting the flexibility of poly(vinyl
to a film that acts as a barrier to gases and/or chloride), cellulose acetate, and cellulose hy-
to a high-strength film. The potential number of drate films. The plasticizer concentration may
property combinations is very large. be as high as 40 % (plasticized PVC); typical ex-
Laminated composite films are commonly amples include esters of phthalic and phosphoric
prepared by the dry lamination process, in which acids.
a dissolved or dispersed adhesive is coated on
the surface of the film. After evaporation of the Slip or Antiblocking Agents. Films with
solvent in a dryer, the coated film is bonded to a smooth surfaces possess a high coefficient of
second film web in a laminating unit consisting friction and therefore tend to block during
of a pair of nip rolls, one made of rubber and the winding and other processing operations. To
other of steel. improve the frictional properties of these films,
The simplest laminating system is composed their surface is finely structured by adding small
of two unwinding stations, an adhesive appli- amounts of finely dispersed pigments. The sur-
cator, a dryer, a laminating unit, and a windup face of biaxially oriented polyester films can be
station. However, many different systems are in improved by adding inert inorganic pigments
use, depending on the desired number of lami- (e.g., calcium carbonate, silicon dioxide, or cal-
nate layers and the choice of adhesive. In some cium phosphate) or particles composed of cross-
cases, adhesion can be achieved without using linked polyacrylates. The particles are < 1 µm
solvents, e.g., by using hot melts, reactive adhe- in diameter, and are used at a concentration of
sives, or systems that can be hardened by irradi- < 0.5 wt %. Lubricants such as fatty amides or
ation. polysiloxanes may also be introduced.

Fillers and Dyes. The optical properties of

3. Additives films can be altered by the incorporation of fillers
and dyes. A wide range of concentrations is
Nearly all films contain additives which perform employed. Many fillers are inert inorganic sub-
two main functions: (1) stabilization of the poly- stances, e.g., titanium dioxide, barium sulfate,
mers and (2) improvement of processability and kaolin, and carbon black. Colored films are nor-
the potential uses of the film [16], [17] (see also mally produced from raw materials that have
→ Plastics, Additives, → Plasticizers). been dyed in bulk. However, in special cases the
Additives can be introduced when the poly- films themselves may be dyed either by a diffu-
mer is being prepared or processed, or during sion process or by printing the entire surface.
film production. An additive must withstand all
stages of processing without any loss of activity.
 Films 11

Antistatic Agents. Films are rendered anti- be measured from the viscosity of a film solu-
static by mixing the virgin polymer with a sub- tion. The identity of a film can often be deter-
stance bearing hydrophilic groups. The additive mined more simply with the aid of systematic
migrates to the surface layer. Quaternary am- analytical schemes (e.g., [20], Appendix B).
monium compounds, ethyl sulfonates and, es- The average thickness of a film is established
pecially with polyolefin films, ethoxylated alkyl according to DIN 53 370 or ASTM E 252. No
amines are used as antistatic agents. standard method for measuring thickness in both
the machine and transverse directions exists as
Weathering Stabilizers. Most films for out- yet. During manufacture, film thickness can be
door applications are prone to photooxidative determined by measuring the absorption of ei-
degradation and are stabilized by adding UV- ther β- or IR radiation or by a dielectric method.
absorbing substances. Piperidyl derivatives, for The uniformity of the thickness of a film sample
example, are effective stabilizers of polypropyl- can be determined mechanically, electrically, or
ene. optically. The accuracy of measurement in all
cases is 0.1 µm.
Methods for determining the mechanical
4. Delivery Forms properties of films are described in ASTM
D 882, D 1822, D 1894, D 1922; ISO 1184
Commercial quantities of films are available in (1983). Individual methods are as follows: tear
various thicknesses (ca. 1 – 1000 µm) and are strength, DIN 53 455; elongation at break, DIN
supplied in the form of rolls with cores of a stan- 53 457; modulus of elasticity, DIN 53 448; im-
dard diameter (e.g., 6 ). pact strength, DIN 53 374; tear resistance, DIN
Standardized thicknesses are demanded for 53 375; and tear propagation resistance, DIN
many applications. Attempts are being made to 40 634 and DIN 53 363.
establish a standardized system, since this also The coefficient of friction is of considerable
simplifies production planning and stock con- importance in the converting of films, and con-
trol. Films are offered in widths ranging from ventional methods for its determination are de-
a few millimeters to several meters. Standard scribed in DIN 53 375 and ASTM D 1894. Spe-
widths have only been established in a few areas cial techniques have been developed for some
of application. applications (e.g., for magnetic tapes).
The maximum length of a film depends on the Film density is determined according to
intended application as well as on the film thick- ASTM 1505 IC.
ness. For example, with poly(ethylene tereph- The electrical properties of films are tested
thalate) (PETP), films with a thickness of 5 µm according to VDE 0345/1.65 and 0303/7/1.65;
are supplied in rolls with a typical length of ASTM D 149, D 150, D 229, and D 252; and
30 km. DIN/sec 15 C. Parameters that are measured in-
Films that are precut to size are also marketed, clude the dielectric strength, dielectric constant,
although only to a very limited extent. dissipation factor, resistivity, surface resistance,
electrolytic corrosion, and glow discharge igni-
tion voltage.
5. Test Methods [18–24] The melting point, glass transition temper-
ature, crystallization and softening behavior,
Many of the test methods employed for pro- and decomposition temperature are easily deter-
cess control in film manufacture have been stan- mined by differential thermal analysis. The long-
dardized. However, the results obtained are not term thermal stability of films designed for use
always compatible because the test conditions as electrical insulators is normally determined
specified in different standards often vary. according to VDE 0530 or IEC 216; the films
The chemical composition of a film is nor- can then be classified according to the temper-
mally apparent from its IR spectrum. Trace el- ature at which they may be used, i.e., Class T
ements are determined by atomic absorption (90 ◦ C), A (105 ◦ C), E (120 ◦ C), B (130 ◦ C), F
spectroscopy, mass spectrometry, or neutron ac- (155 ◦ C), H (180 ◦ C), and C (> 180 ◦ C).
tivation analysis. Relative molecular masses can
12 Films

The coefficient of expansion, dimensional sta- films designed for the packaging industry. Infor-
bility, and thermal conductivity can be deter- mation regarding the extractable components of
mined by reference to the following standards, a film often serves as the basic for its legal ap-
which are not, however, exclusively designed for proval (e.g., FDA approval) [25].
films: DIN 1341, 40 634, 52 328; ASTM D 229,
D 1204; VDE 0530/1/1.66.
The following standards apply to the mea- 6. Film Products [20], [26], [27]
surement of optical properties (transparency,
haze, gloss, refractive index, and color): DIN A remarkable variety of film materials has been
5033, 53 491; ASTM 1003, D 307, D 1925, D developed as a result of several factors: Film
2457. The measurements are easy to perform, manufacturers have a wide choice of potential
but interpretation of the results can be difficult. raw materials and can also use special processing
Determination of permeability with respect steps such as stretching to modify certain prop-
to liquids, vapors, and gases is relatively com- erties of a film during its manufacture. Further
plicated, but this parameter is especially valu- variants are made possible by the introduction of
able, since films are widely used as packaging additives, by the application of functional coat-
materials. Appropriate procedures are described ings, or by lamination of two or more types of
in DIN 53 122 and 53 386, and ASTM D 1434 film. The following discussion is limited to re-
and E 96 (E). presentative examples from characteristic film
Chemical resistance is most easily deter- groups. Important physical properties of these
mined by examining the changes induced in ulti- materials are compiled in Tables 2, 3, 4, 5. (The
mate strength and elongation at break as a result lists of trade names supplied are by no means
of exposure to the substances concerned. How- exhaustive.)
ever, the following standards are also applicable:
DIN 53 476; ASTM D 543, D 756, D 1435, E
96; ISO/R 175 and R 511. 6.1. Cellulose Derivatives
Water absorption is determined according to
DIN 53 472 and ASTM 0570. 6.1.1. Cellulose Hydrate (→ Cellulose,
The most useful test of surface structure is Chap. 3.1.)
carried out with a profilometer. Since the 1980s
this technique has proved itself to be particu- Cellophane [9005-81-6] is a trade name applied
larly useful for examining film substrates used to films based on cellulose hydrate (regenerated
in the manufacture of magnetic tapes. The best cellulose).
known procedures are those described in DIN Cellophane is prepared from cellulose via the
4760 – 4774, the Japanese Industry Standard JIS sodium xanthate derivative in a solution cast-
0601-70, and ISO/DIS 4267/1. In special cir- ing process (see Section 2.1) and is available
cumstances, additional information can be ob- in thicknesses ranging from 12 to 45 µm. Un-
tained by using microscopy (interference meth- treated cellophane film is crystal clear, glossy,
ods and scanning electron microscopy). and highly permeable to water vapor; it is unsta-
The roll hardness of film rolls can be evalu- ble with respect to water, but stable to fats and
ated by using the Shore hardness as a criterion oils. Cellophane is not heat-sealable, but can be
(DIN 53 505, ISO 12 868). A better procedure bonded; it is odorless, tasteless, and authorized
makes use of a falling sphere [24]. for use as a food packaging material by the FDA
The flammability of films is evaluated accord- and similar institutions. It possesses desirable
ing to DIN 4102, ASTM D 1433, ISO R 1715, mechanical characteristics at the normal water
and Underwriters Laboratory Standard UL 94 content of 7 – 8 %. Properties are listed in Ta-
VTM. ble 2.
Measurement of the extraction of low molec- Cellophane is increasingly being replaced by
ular mass components of films with solvents has oriented polypropylene films; 70 – 80 % of its
not been standardized. Most studies are based original applications (mainly in packaging) have
on special procedures developed by individual already been affected.
manufacturers and end users. Interest centers on
 Films 13
Table 2. Properties of selected films a

Cellophane Cellulose Polyethylene (PˆE) Poly(4- Poly-

(uncoated) acetate methyl-1- propylene
(CA) b low-density high-density pentene) (BOPP)
(LDPE) (HDPE) (PMP)

Mechanical properties
Thicknesses, µm 12 – 45 12 – 350 25 – 200 50 – 1000 75 – 300 4 – 80
Density, g/cm3 1.45 1.3 0.92 0.95 0.83 0.91
Ultimate strength
longitudinal, N/mm2 100 100 25 g 23 g 140
24
2 g g
lateral, N/mm 60 100 20 23 280
24
Elongation at break
longitudinal, % 20 30 400 g 140
400 10
lateral, % 60 30 700 g 400 50
10
Modulus of elasticity
longitudinal, N/mm2 5 300 2 000
1500 170 900 1100
2
lateral, N/mm 2 800 1500 4 000
170 900 1100
Electrical properties
Dielectric strength c , kV/mm 100 150 200 200 65 340
Dielectric constant at 1 kHz 3.2 4.5 2.3 2.2 2.1 2.2
Dissipation factor 0.015 0.02 0.0002 0.0004 0.003 0.0002
Volume resistivity, Ω cm 1011 1014 1017 1017 1016 5×1017
Thermal properties
mp, ◦ C 110 130 235 165
Application temperature range d , ◦ C − 15 to + 150 − 15 to + 120 − 60 to + 95 − 50 to + 100 −20 to +130 − 20 to + 120
Optical properties n20
D 1.6 1.4 – 1.5 1.50 1.50 1.46 1.50
Dimensional stability
Coefficient of thermal expansion, K−1 6×10−5 6×10−5
Shrinkage at 100 ◦ C (30 min)
longitudinal, % 0.7 – 3.0 0.4 1.0 (80 ◦ C) 0.5 1.6 (160 ◦ C) 3
lateral, % 0.7 – 3.0 0.2 0 0 0 1
Physicochemical properties
Water absorption in 24 h, wt % 45 – 115 5 < 0.1 < 0.1 < 0.1 < 0.1
Stability toward
daylight good good limited limited poor limited
organic solvents moderate unstable good good good good
acid unstable unstable good good very good good
alkali unstable unstable good good very good good
salt solutions unstable stable good good very good good
Permeability
Water vapor, g m−2 d−1 very high 350 2.5 1.0 0.6 1.5
Oxygen e , cm3 m−2 d−1 bar−1 10 1 500 4 000 1 600 38 000 600
Carbon dioxide e , cm3 m−2 d−1 bar−1 100 10 000 16 000 7 000 110 000 1 800
Nitrogen f , cm3 m−2 d−1 bar−1 12 300 1 300 400 9 400 140
a
Standard values determined as described in Chapter 5.
b
Cellulose acetate film (2 1/2-acetate) containing plasticizer.
c
At 50 Hz, film thickness = 40 µm, plate/plate.
d
Temperature range over which no significant loss in strength or stiffness occurs.
e
Film thickness = 40 µm, 23 ◦ C.
f
Film thickness = 200 µm.
g
Film thickness = 50 µm.
h
Decomposition temperature.
i
For biaxially stretched (balanced) film.
j
20 ◦ C, 0 % relative humidity.
k
Film thickness = 25 µm.
l
40 ◦ C, 90 % relative humidity.
m
Film thickness = 100 µm.
14 Films
Table 3. Properties of selected filmsa

Polysty- Poly(vinyl chloride) Poly- Polytetra- Poly(vinyl

rene (PS) (PVC) (vinylidene fluoro- fluoride)
chloride) ethylene (PVF)
rigid plasticized
(PVDC) (PTFE)

Mechanical properties
Thicknesses, µm 4 – 500 30 – 700 10 – 1 000 25 12 – 1 000 12 – 50
Density, g/cm3 1.06 1.38 1.24 – 1.3 1.66 – 1.75 2.1 – 2.2 1.38 – 1.57
Ultimate strength
longitudinal, N/mm2 60 50 20 – 35 30 – 50 10 – 30 60 – 150
lateral, N/mm2 60 50 20 – 35 30 – 50 10 – 30 60 – 150
Elongation at break
longitudinal, % 10 70 250 150 – 250 100 – 350 100 – 200
lateral, % 10 40 250 150 – 250 100 – 350 100 – 200
Modulus of elasticity
longitudinal, N/mm2 3 000 2 500 300 – 1 000 230 400 1 400
lateral, N/mm2 3 000 2 500 300 – 1 000 230 400 1 400
Electrical properties
Dielectric strength c , kV/mm 200 60 f 50 – 100 f 28 m 140
Dielectric constant at 1 kHz 2.5 3.5 3.3 – 5.3 4.5 – 6.0 2.0 – 2.1 8.5
Dissipation factor 0.0005 0.02 0.03 – 0.1 0.06 – 0.07 0.0002 1.6
Volume resistivity, Ω cm 1016 1015 1011 – 1014 1013 – 1014 1018 1013
Thermal properties
mp, ◦ C 240 160h 150 330 200
Application temperature range d , ◦ C − 60 to + 100 − 15 to + 75 − 30 to + 50 0 to + 140 − 190 to +250 −70 to +110
Optical properties n20
D 1.59 1.54 1.62
Dimensional stability
◦
Shrinkage at 100 C (30 min)
longitudinal, % 25 3 0.5 10 – 35 1
lateral, % 25 3 0.5 10 – 35 1
Physicochemical properties
Water absorption in 24 h, wt % < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.5
Stability toward
daylight limited good good limited very good very good
organic solvents limited good good limited very good very good
acid good good good good very good very good
alkali good good good good very good very good
salt solutions good good good good very good very good
Permeability
Water vapor, g m−2 d−1 30 7.5 10 – 100 1.5 thickness 32
< 400 µm
e 3 −2 −1 −1
Oxygen , cm m d bar 3 000 80 700 – 1 000 30 contains 30
Carbon dioxide e , cm3 m−2 d−1 bar−1 17 000 160 3 000 – 5 000 200 micropores 110
Nitrogen f , cm3 m−2 d−1 bar−1 500 12 150 – 1 000 5 25
a
Standard values determined as described in Chapter 5.
b
Cellulose acetate film (2 1/2-acetate) containing plasticizer.
c
At 50 Hz, film thickness = 40 µm, plate/plate.
d
Temperature range over which no significant loss in strength or stiffness occurs.
e
Film thickness = 40 µm, 23 ◦ C.
f
Film thickness = 200 µm.
g
Film thickness = 50 µm.
h
Decomposition temperature.
i
For biaxially stretched (balanced) film.
j
20 ◦ C, 0 % relative humidity.
k
Film thickness = 25 µm.
l
40 ◦ C, 90 % relative humidity.
m
Film thickness = 100 µm.
 Films 15
Table 4. Properties of selected filmsa

Poly(ethylene Polycarbonate Nylon 6 Poly(methyl Ethylene –

terephthalate) (PC), (PA), methacrylate) vinyl alcohol
(PETP) monoaxially biaxially (PMMA) copolymer
stretched stretched (EVOH),
biaxially
stretched

Mechanical properties
Thicknesses, µm 1.0 – 350 2 – 500 12 – 25 50 – 500 12 – 25
Density, g/cm3 1.4 1.21 1.16 1.14 1.19
Ultimate strength
longitudinal, N/mm2 250
200 i 260 40 210
lateral, N/mm2 8
200 i 260 40 210
Elongation at break
longitudinal, % 30
100 i 100 – 120 75 50
lateral, % 100
i 100 – 120 75 50
100
Modulus of elasticity
longitudinal, N/mm2 2 100
4 000 i 1 400 1 900 3 600
lateral, N/mm2 800
4 000 i 1 400 1 900 3 600
Electrical properties
Dielectric strength c , kV/mm 320 300 50 90
Dielectric constant at 1 kHz 3.3 2.8 3. 4 – 3.7 4.4
Dissipation factor 0.005 0.0012 0. 016 0.046
Volume resistivity, Ω cm 1018 2×1017 5×1017 1016
Thermal properties
mp, ◦ C 260 260 200 h 160 181
Application temperature range d , ◦ C − 269 to −140 to −200 to −20 to
+180 +140 +180 +120
Optical properties n20
D 1.60 1.60
Dimensional stability
Coefficient of thermal expansion, K−1 2×10−5 7×10−5
Shrinkage at 100 ◦ C (30 min)
longitudinal, % −11 −4 (140 ◦ C)
<1 <1 <1
lateral, % 0 −0.5
<1 <1 <1
Physicochemical properties
Water absorption in 24 h, wt % 0.5 0.35 5 0.5 5.9
Stability toward
daylight limited limited good very good
organic solvents moderate moderate good good (aliph.) good
poor (arom.)
acid moderate moderate poor very good
alkali stable only at low stable only at low good very good
concentration concentration
salt solutions good good good very good
Permeability
Water vapor, g m−2 d−1 8 35 100 75 40
Oxygen e , cm3 m−2 d−1 bar−1 50 8 000 26 0.5 j
Carbon dioxide e , cm3 m−2 d−1 bar−1 250 25 000 100 12
Nitrogen f , cm3 m−2 d−1 bar−1 12 9 0.08
250
a b
Standard values determined as described in Chapter 5. Cellulose acetate film (2 1/2-acetate) containing plasticizer.
c
At 50 Hz, film thickness = 40 µm, plate/plate. d Temperature range over which no significant loss in strength or stiffness occurs.
e
Film thickness = 40 µm, 23 ◦ C. f Film thickness = 200 µm.
g
Film thickness = 50 µm. h Decomposition temperature.
i
For biaxially stretched (balanced) film. j 20 ◦ C, 0 % relative humidity.
k
Film thickness = 25 µm. l 40 ◦ C, 90 % relative humidity.
m
Film thickness = 100 µm.
16 Films
Table 5. Properties of selected filmsa

Polysulfone Polyimide Polyether- Polyether- Polyether- Poly-

(PSU) (PI) imide sulfone ketone (phenylene-
(PEI) (PES) (PEK) sulfide)
(PPS)

Mechanical properties
Thicknesses, µm 25 – 1 000 7.5 – 125 75 – 500 25 – 300 75 – 250 2.0 – 125
Density, g/cm3 1.24 1.42 1.27 1.37 1.24 – 1.30 1.35
Ultimate strength
longitudinal, N/mm2
80 180 100 85 120 220
lateral, N/mm2
80 180 100 85 120 220
Elongation at break
longitudinal, %
50 70 70 15 200 55
lateral, %
50 70 70 15 200 55
Modulus of elasticity
longitudinal, N/mm2
2 500 2 700 3 000 2 400 330 4 000
lateral, N/mm2
2 500 2 700 3 000 2 400 330 4 000
Electrical properties
Dielectric strength c , kV/mm 200 280 k
145 125 170 240
Dielectric constant at 1 kHz 3.14 3.5 3.56 3.90 3.5 3.0
Dissipation factor 0.001 0.003 0.0013 0.003 0.002 0.0006
Volume resistivity, Ω cm 5×1016 1018 3.4×1016 1.7×1016 1017 1017
Thermal properties
mp, ◦ C 370 406h 216h 223h 334 285
Application temperature range d , ◦ C − 80 to − 260 to ≤ 170 ≤ 180 ≤ 240 ≤ 180
+ 170 + 400
Optical properties n20
D 1.63 1.78
Dimensional stability
Coefficient of thermal expansion, K−1 5.6×10−5 2×10−5 4.5×10−5 4.4×10−5 4×10−5 3×10−5
Shrinkage at 100 ◦ C (30 min)
longitudinal, %
< 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
lateral, %
< 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
Physicochemical properties
l l j
Water absorption in 24 h, wt % 0.4 1.3 – 2.9 1.0 1.4 0.4 0.05
Stability toward
daylight good good good good
organic solvents moderate moderate satisfactory satisfactory very good very good
acid good good good good very good very good
alkali good stable only at good good very good very good
low
concentration
salt solutions good good good good very good very good
Permeability
Water vapor, g m−2 d−1 98 84 43.5 100 28.5 5
Oxygen e , cm3 m−2 d−1 bar−1 3.8 200 55 100
Carbon dioxide e , cm3 m−2 d−1 bar−1 6.9 500
Nitrogen f , cm3 m−2 d−1 bar−1 0.9 50

a
Standard values determined as described in Chapter 5.
b
Cellulose acetate film (2 1/2-acetate) containing plasticizer.
c
At 50 Hz, film thickness = 40 µm, plate/plate.
d
Temperature range over which no significant loss in strength or stiffness occurs.
e
Film thickness = 40 µm, 23 ◦ C.
f
Film thickness = 200 µm.
g
Film thickness = 50 µm.
h
Decomposition temperature.
i
For biaxially stretched (balanced) film.
j
20 ◦ C, 0 % relative humidity.
k
Film thickness = 25 µm.
l
40 ◦ C, 90 % relative humidity.
m
Film thickness = 100 µm.
 Films 17

Manufacturers.Wolff Walsrode, Federal Repub- 6.2. Hydrocarbon Polymers

lic of Germany; Chemiefaser Lenzing, Austria;
British Cellophane, United Kingdom; Flexel, 6.2.1. Low-Density Polyethylene (LDPE)
Atlanta, United States; Futamura, Japan. (→ Polyolefins)

Low-density polyethylene [9002-88-4] (LDPE)

6.1.2. Cellulose Esters (→ Cellulose Esters) has a molecular mass of > 50 000 and is prepared
by the high-pressure process. It is converted into
Films derived from cellulose acetate film mainly by the film blowing process at a melt
[9004-35-7] (CA) (2-acetate, 2 1/2-acetate, temperature of 150 – 210 ◦ C. For properties of
and 3-acetate), cellulose acetate propionate the film, see Table 2.
[9004-39-1] (CAP), and cellulose acetate bu- Film thickness of LDPE ranges between 25
tyrate [9004-36-8] (CAB) are available; they all and 200 µm. The films are transparent to crys-
contain plasticizers–phthalate esters, aliphatic tal clear, depending on the choice of relative
alcohols, triphenyl phosphate. Solution casting molecular mass and process technology. They
is the usual production method. Methylene chlo- are soft, flexible, and resistant to creases and
ride [75-09-2] is used as a solvent [9]. The cast- show high tear and tear propagation resistance.
ing solution has a cellulose acetate concentration Mechanical properties are stable at low tem-
of 18 – 26 % and a viscosity of 15 – 30 Pa · s. perature and chemical resistance is very high.
Cellulose acetate films are the most important Films made from LDPE display low permeabil-
of the cellulose ester films. The properties of cel- ity to water vapor but high permeability to gases.
lulose acetate vary as a function of the number They are nontoxic and contain neither plasticiz-
of acetate groups per cellulose molecule. The ers nor odorous materials. Low-density poly-
properties of cellulose acetate film (2 1/2 ac- ethylene films are easily welded and thermo-
etate) are listed in Table 2. Films with the high- formed. Specific shrinking characteristics can be
est acetate concentration, corresponding to the imparted to the films by stretching at low tem-
minimum number of hydroxyl groups, show re- perature.
duced sensitivity to moisture as well as minimal Films made from LDPE are used for pack-
absorption of water and low water-vapor per- aging and as protective coverings. They are also
meability. These films are crystal clear in their employed in the production of composite films.
untreated state; they are dimensionally stable at Low-density polyethylene has become commer-
ambient temperature and humidity and possess cially important. Worldwide annual production
good electrical properties. Special surface char- is estimated at more than 8×106 t.
acteristics (e.g., gloss, roughness) can be con- Trade Names. Plastotrans (Folienfabrik Forch-
ferred during manufacture by casting on an ap- heim, Federal Republic of Germany); Walo-
propriate type of metal belt. plast (Wolff Walsrode, Federal Republic of Ger-
Cellulose acetate films are used as supports many); Helioflex (Feldmühle, Federal Republic
for photographic coatings, as transparent win- of Germany); Bexthene (Bexford, United King-
dows, release films, decorative materials, and as dom); Cryovac L (Cryovac Div., W. R. Grace,
electrical insulators. United States).
Trade Names. Acetatfolie (Hoechst, Federal Re- Film derived from a copolymer of ethylene
public of Germany); Triafol (Bayer, Federal Re- with vinyl acetate (EVM film) is used similarly
public of Germany); Ultraphan (Lonza, Federal as a packaging material. Its exceptional adhesive
Republic of Germany); Bexoid (Bexford, United properties make it particularly suitable as a cling
Kingdom); Cellittor (British Cellophane, United and stretch-wrap film.
Kingdom). Trade Name. Montothene (American Can,
United States).
18 Films

6.2.2. High-Density Polyethylene (HDPE) Unstretched PP film is prepared either by

(→ Polyolefins) chill roll casting or by blowing. Its proper-
ties are comparable to those of LDPE film,
High-density polyethylene [9002-88-4] (HDPE) but with the advantages of greater transparency
prepared by the low-pressure method is also and a wider application temperature range. Un-
gaining importance as a raw material for films. stretched PP film is used exclusively for pack-
Films made from HDPE are produced both by aging purposes. West European consumption in
chill roll extrusion and by film blowing. Char- 1986 was 80 000 t.
acteristics of the films are given in Table 2. Monoaxially stretched PP film exhibits in-
Films derived from HDPE have a higher creased strength in the direction of orientation
chemical resistance than LDPE films and can and is used for three major applications: (1) ca-
be employed over a somewhat wider tempera- ble insulation, (2) tapes and industrial fabrics,
ture range; HDPE films are used in construction and (3) yarns and ropes.
and civil engineering as insulators. High-density Biaxially oriented polypropylene (BOPP)
polyethylene film can be welded and bonded, film is the most important type of polypropyl-
and is readily thermoformable. ene film; its properties are listed in Table 2.
Trade Names. Plastin (Folienfabrik Forchheim, Worldwide consumption in 1986 was 550 000 t
Federal Republic of Germany); Fortiflex (Crown of which 460 000 t could be attributed to the
Zellerbach, United States). packaging industry and 60 000 t to the technical
Polyolefins (mainly HDPE) are the basis of sector. An additional 30 000 t was processed into
several types of “synthetic paper,” which are also adhesive tapes. Films made of BOPP currently
prepared by film-forming techniques. The mar- occupy ca. 80 % of the packaging market once
ket for this material in Great Britain in 1985 was held by cellophane. Factors contributing to this
estimated to be 40 000 t/a. development include superior properties, lower
cost, and an ecologically preferable manufactur-
ing technology. Likewise, glassine (a thick semi-
6.2.3. Linear Low-Density Polyethylene transparent greaseproof paper) is being replaced
(LLDPE) (→ Polyolefins) by opaque BOPP films that are heat- and cold-
sealable. These films were introduced in the late
The 1980s witnessed the development of films 1970s by Hoechst [28].
derived from linear low-density polyethylene Biaxial orientation can be achieved by any
(LLDPE), which are produced in the same way of the standard methods (see Section 2.3.2), but
as LDPE films. Linear low-density polyethylene sequential stretching is preferred because this
films have better mechanical properties (greater method permits a wide range of thicknesses.
strength and higher ultimate strength) than or- Most BOPP packaging films are provided with
dinary LDPE films. As a result, LLDPE films a separate sealing layer, formed either by co-
have found applications as sacks for transporting extrusion or in an off-line coating process. Co-
heavy materials. Since LLDPE also has a higher extruded sealing coatings normally consist of
melting point (118 ◦ C) than LDPE (110 ◦ C), polyolefin copolymers, whereas polyacrylate or
these sacks can be filled with hot materials poly(vinylidene chloride) is used for off-line
(e.g., freshly produced cement). Stretch-wrap coating. Poly(vinylidene chloride) has the added
packaging represents another expanding market. advantage that it simultaneously improves the
Like other polyethylene films, LLDPE films can oxygen barrier properties of the film.
be combined with additional materials to form Biaxially oriented polypropylene films range
composite films. in thickness from 4 to 80 µm. They are used in-
dustrially in laminates and as release and capac-
itor films.
6.2.4. Polypropylene (PP) (→ Polyolefins) Trade Names. Trespaphan (Hoechst, Federal
Republic of Germany); Propafilm (ICI, United
Polypropylene [9003-07-0] (PP) film is avail- Kingdom); Shorco (British Cellophane, United
able in an unoriented form as well as in both Kingdom); Walothen (Wolff Walsrode, Federal
mono- and biaxially oriented versions.
 Films 19

Republic of Germany); Bicor (Mobil, Belgium); increase in impact strength is obtained at the ex-
Moplefan (Montedison, Italy). pense of reduced transparency. Film thicknesses
are between 4 and 500 µm.
The favorable dielectric characteristics of PS
6.2.5. Poly(4-methyl-1-pentene) (PMP) [29] film result in its use in high-voltage capacitors
(→ Polyolefins) and as an insulator for cables.
Trade Names. Styroflex (Norddeutsche Seek-
Poly(4-methyl-1-pentene) [9016-80-2] (PMP) abelwerke, Federal Republic of Germany);
films are produced by extrusion and pos- Trycite (Dow Chemical, United States).
sess the lowest density of all available films
(0.83 g/cm3 ). They have a higher softening point
(mp 240 ◦ C) than PP films (mp 165 ◦ C). Film 6.3. Halogenated Hydrocarbon
thickness ranges from 50 to 300 µm. For prop- Polymers
erties, see Table 2.
PMP films have been used only in combina- 6.3.1. Poly(Vinyl Chloride) (PVC) [6]
tion with other materials, mainly with cardboard [→ Poly(Vinyl Chloride)]
for the packaging of oven-ready meals.
Films formed from poly(vinyl chloride)
[9002-86-2] (PVC) may be either rigid or flexi-
6.2.6. Ionomers (→ Specialty Plastics) ble. Rigid films consist solely of PVC; flexible
films are produced by addition of plasticizers
The term ionomer describes a family of poly- or by copolymerization with acrylate esters or
mers incorporating both covalent and ionic vinyl acetate. Both rigid and plasticized PVC
bonds. Ionomers [25608-26-8] are based on films are produced by calendering processes,
polyethylene and have carboxyl groups located although chill roll casting and film blowing are
along their polymer chains. These groups pro- also possible. Some PVC films are also sub-
vide ionic cross-links between chains [20]. The jected to stretching.
corresponding films are prepared by extrusion. Rigid and plasticized PVC films are of great
Many of the properties of ionomer films are economic importance. Worldwide production is
comparable to those of LDPE films. However, estimated at 1.4×106 t/a.
ionomer films are more resistant at room tem-
perature to fats and oils than LDPE films, and
they possess exceptionally good sealing prop- 6.3.1.1. Rigid PVC
erties. They are also extremely tough and are
ideally suited for packaging. Rigid PVC film is available in a wide range of
Trade Name. Surlyn A (Du Pont, United States). thicknesses (30 – 700 µm); important properties
are listed in Table 3. The material varies from
crystal clear to transparent and may be colored
6.2.7. Polystyrene (PS) (→ Polystyrene and
by the addition of pigments. Rigid PVC is unaf-
Styrene Copolymers)
fected by water and is virtually impermeable to
odors. It possesses outstanding chemical resis-
Polystyrene [9003-53-6] (PS) films are available
tance and is also highly flame resistant. The film
in unoriented as well as in mono- and biaxially
can be welded, heat-sealed, embossed, thermo-
stretched form. They are produced by chill roll
formed, stamped, bonded, imprinted, and (un-
extrusion or by blowing. For properties, see Ta-
der high vacuum) metallized. These remarkable
ble 3. For foamed PS films see →Foamed Plas-
properties combine to produce a broad spectrum
tics, Chap. 4.2.2.
of applications for rigid PVC film both in pack-
Oriented films are crystal clear with a high
aging and the industrial sector. Adhesive tapes
gloss but are extremely brittle. Their most im-
account for a particularly large share of the mar-
portant application is for envelope windows. The
ket.
polymer must be modified with synthetic rubber
to increase its strength. However, the resulting
20 Films

6.3.1.2. Plasticized PVC are also available. Coextruded products are pre-
pared in both tubular and flat form. The PVDC
Plasticized PVC films have an even wider range generally is sandwiched between other poly-
of applications than rigid PVC because the meric layers which impart strength and tough-
properties of plasticized PVC can be modified ness. Adhesion problems are overcome by si-
by varying the type and amount of plasticizer multaneously extruding an adhesive tie layer.
added. Plasticized PVC films are available with Trade Names. Saran, Saranex (Dow Chemical,
a thickness of 10 – 1000 µm; for important prop- United States); Cryovac (Grace, United States);
erties, see Table 3. The material can be strained Krehalon (Kureha, Japan); Supralon (Asahi,
and shows little tendency to wrinkle; its consis- Japan).
tency varies from soft to hard. Plasticized PVC
film is resistant to both tear and tear propaga-
tion, and it can be embossed, welded, bonded, 6.3.3. Fluoropolymers [26]
and stitched. It is resistant to most inorganic and (→ Fluoropolymers , Organic)
organic chemicals, as well as to water and light.
It also shows good aging and weathering prop- Incorporation of fluorine into hydrocarbon
erties. Permeability to water vapor and gases is chains results in polymers that display antiad-
minimal. hesive characteristics, thermal stability, flame
Plasticized PVC film is used mainly in pack- resistance, insulating properties, and, most im-
aging and the building industry, as a protective portant of all, extreme stability with respect to
covering, in laminated films, and for the modifi- weathering and aggressive media. As a result of
cation of wood surfaces. It is also processed into these properties, which depend on the degree of
commercial adhesive tapes. substitution, these films are used mainly under
Trade Names. Genotherm, Guttagena, Genopak, extreme conditions.
Suprotherm (Hoechst, Federal Republic of Ger- From a chemical standpoint, the fluoropoly-
many); Mipolam (Dynamit, Federal Repub- mers used for film production fall into three cat-
lic of Germany); Folan, Polytherm (Folienfab- egories:
rik Forchheim (Federal Republic of Germany);
Pentafilm (Pentaplast, United States).
1) perfluorinated polymers,
2) partially fluorinated polymers,
6.3.2. Poly(Vinylidene Chloride) (PVDC) 3) polymers containing chlorine as well as flu-
[27], [30] [→ Poly(Vinylidene Chloride)] orine
Poly(vinylidene chloride) [9002-85-1] (PVDC)
films are made from a vinylidene chloride–vinyl Polytetrafluoroethylene (PTFE) is a perflu-
chloride–vinyl acetate copolymer [9003-20-7]. orinated polymer that cannot be processed
The comonomers render the product sufficiently from a melt by conventional techniques.
stable for extrusion. Plasticizers are also added Polytetrafluoroethylene films are prepared by
to improve processing properties. The films are isostatically sintering the powdered material,
manufactured by the tubular drawing process. followed by “skiving” (paring) of the sin-
Since the stability of the melt is low, the film tube tered block. All other fluoropolymers–including
must be cooled as it emerges from the die prior to copolymers of PTFE with perfluorinated vinyl
orientation by blowing (see Section 2.3.2). For components–are extrudable and can, therefore,
properties, see Table 3. be made into films either by the chill roll process
Poly(vinylidene chloride) film has been on or by film blowing.
the market under the trade name Saran since The market for fluoropolymer films in the
the late 1940s and is still widely used because United States is dominated by films made
of its outstanding water vapor and oxygen bar- from poly(vinyl fluoride) (PVF), PTFE and
rier properties. Its principal application is in the polychlorotrifluoroethylene (PCTFE). Extrud-
packaging of perishable foodstuffs. able copolymer films made from tetrafluoroeth-
The material is supplied as a shrinkable ylene–hexafluoropropylene copolymer (FEP),
monofilm or coextruded film; PVDC laminates
 Films 21

perfluoroalkoxy polymer (PFA), and ethylene– Two related copolymers are extrudable: FEP
tetrafluoroethylene copolymer (ETFE) have also [25036-53-7], derived from tetrafluoroethylene
become somewhat important, or at least have and hexafluoropropylene, and PFA [2645-79-6],
a considerable potential for development. Film a copolymer of tetrafluoroethylene and a perflu-
made of poly(vinylidene fluoride) (PVDF) is orovinyl ether. Films produced from these ma-
also worth mentioning because of its piezoelec- terials are not porous, but otherwise display es-
tric properties. sentially the same characteristics as PTFE itself.
The mechanical and optical properties of the
extruded films are superior to those of skived
6.3.3.1. Poly(Vinyl Fluoride) (PVF) PTFE films. Commercial products are available
in thicknesses from 12 –1000 µm. Their princi-
Poly(vinyl fluoride) [24981-14-4] (PVF) film is pal uses are as release films, in the electrical
commercially available in both transparent and industry, and especially as container linings.
pigmented form in thicknesses of 12 – 50 µm. Trade Name. Hostaflon (Hoechst, Federal Re-
For properties, see Table 3. Its antiadhesive public of Germany); Teflon (Du Pont, United
characteristics, together with its resistance to States); Fluon (ICI, United Kingdom).
mechanical, chemical, and weathering effects,
make PVF film suitable for use as a protective
lamination on both interior and exterior panel- 6.3.3.4. Polychlorotrifluoroethylene
ing. It also serves as a release film in the pressing (PCTFE)
of synthetic resin.
Trade Name. Tedlar (Du Pont, United States). Films made from polychlorotrifluoroethylene
[9002-83-9] (PCTFE) are used widely in the
6.3.3.2. Poly(Vinylidene Fluoride) (PVDF) packaging of pharmaceuticals and medical sup-
[31] plies; this is because the films possess excellent
moisture barrier properties and chemical resis-
Poly(vinylidene fluoride) [24937-79-9] (PVDF) tance, coupled with good processability, steril-
films are solvent cast or extruded with a thick- izability, and UV stability. These films are avail-
ness of 50 –500 µm. They possess excellent re- able in thicknesses ranging from 12 to 250 µm.
sistance to weathering and aggressive media. Trade Name. Aclar (Allied, United States).
Poly(vinylidene fluoride) film has an excep-
tionally high dielectric constant and a relatively
high dissipation factor. Because of its piezoelec- 6.4. Poly(Methyl Methacrylate)
tric properties, the monoaxially stretched film (PMMA) [32] (→ Polyacrylates)
is often employed as a mechanical–electrical
transducer in membranes. The consumption of Poly(methyl methacrylate) [9011-14-7]
film for piezoelectric applications is small (ca. (PMMA) films are prepared either by chill roll
1 t); its price is extremely high. extrusion or by film blowing; thicknesses range
Trade Name. Fluorex (Rexham, United States); from 50 to 500 µm. They show high resistance to
Kynar (Pennwald, United States). heat and weathering, but their ultimate strength
and elongation at break are relatively low. For
properties, see Table 4.
6.3.3.3. Polytetrafluoroethylene (PTFE) Poly(methyl methacrylate) film is frequently
used as a protective layer on metal and plastic,
Polytetrafluoroethylene [9002-84-0] (PTFE)
thereby competing with PVF film.
films have the highest resistance to aggressive
Trade Name. Korad (Polymer Extruded Prod-
agents of any polymer film and are thermally
ucts, United States); Plexiglas-Folie (Röhm,
stable up to 250 ◦ C. Since PTFE films are pro-
Federal Republic of Germany); Shinkolite Film
duced via sintering and skiving, they are some-
(Mitsubishi Rayon, Japan).
what porous; some properties are listed in Ta-
ble 3. Most of the PTFE film that is produced is
used for sealing pipe joints and flanges.
22 Films

6.5. Poly(Vinyl Alcohol) (PVA) [33] are primarily used in the form of laminates or co-
(→ Polyvinyl Compounds, Other) extrudates. Some properties of oriented EVOH
film are listed in Table 4.
Poly(vinyl alcohol) [9002-89-5] (PVA) is pro- The principal application of these materials
duced by hydrolyzing poly(vinyl acetate). Both is in food packaging.
the fully and partially hydrolyzed polymers Trade Names. Eval (Kuraray, Japan); Exceed
are utilized for film manufacture; the fully hy- (Okura, Japan).
drolyzed polymer is water-soluble.
Poly(vinyl alcohol) film can be prepared by
casting an aqueous PVA solution or by extru-
sion. Prior to extrusion, the poly(vinyl alcohol) 6.7. Polyamide (PA) [20] (→ Polyamides)
is compounded into a paste with water and a
plasticizer. Film thicknesses are in the range of Polyamide (PA) films (thickness 12 – 25 µm) are
20 – 75 µm. made mainly from nylon 6 [25038-54-4] and ny-
The characteristic features of PVA film in- lon 66 [32131-17-2] by chill roll extrusion or
clude its high transparency and gloss, toughness, film blowing. The films display high tensile and
absence of static charge, and, in the absence of tear strengths, as well as high resistance to punc-
moisture, desirable oxygen barrier properties. ture, abrasion, oils, and fats. Nylon films have
Water solubility varies, depending on the vinyl a low permeability to gases, depending on the
acetate content. atmospheric humidity. Nylon 11 [25035-04-5]
Poly(vinyl alcohol) is employed as a and nylon 12 [24937-16-4] are used for films
monofilm, but can also be coated with PVDC or with lower water-vapor permeability.
laminated with polyolefins. Biaxially oriented Orientation improves the properties of nylon
films can be produced by simultaneous stretch- films. Biaxially oriented films are produced from
ing [34]. nylon 6 by simultaneous stretching. Properties
Poly(vinyl alcohol) films are used as pack- of these films are listed in Table 4.
aging materials for food, textiles, and as release Polyamide films are used as monofilms but
films in the manufacture of synthetic resin prod- are employed mainly in composite structures
ucts. They are also employed in the manufacture produced by lamination, extrusion coating, or
of water-soluble sachets for disposable packag- coextrusion with sealing or barrier resins.
ing of hygienic products and as a basis for po- Trade Names. Capran (Allied, United States);
larized films. Dartek (Du Pont, United States); Bonyl (Ko-
Trade Names. Vinylon (Kuraray, Japan); hjin, Japan); Emblem (Unitika, Japan); Supronyl
Emblar-OV (Unitika, Japan); Bovlon (Nippon (Hoechst, Federal Republic of Germany).
Gohsei, Japan).

6.8. Polyester [10] (→ Polyesters)

6.6. Ethylene–Vinyl Alcohol Copolymer
(EVOH) The term polyester film generally refers to
films prepared from poly(ethylene terephtha-
A partially crystalline copolymer of ethylene
late) [25038-59-9] (PETP). However, other
and vinyl alcohol, EVOH [25067-34-9] is pre-
polyesters are also processed into film,
pared by hydrolysis of an ethylene–vinyl acetate
e.g., poly(butylene terephthalate) [24968-12-5]
copolymer. This material first appeared on the
(PBT) and poly(ethylene-2,6-naphthalene dicar-
market in the 1970s [35]; it can be processed
boxylate) [24968-11-4] (PEN) (trade name: Q-
into a film by extrusion.
Film, Teijin/Japan) [36].
Films derived from EVOH are excellent gas
Polyester films are manufactured by extru-
barriers. Biaxial orientation leads to increased
sion; the majority are biaxially oriented and pro-
strength and further reduction of gas permeabil-
duced in flat form; only a small amount of tubular
ity. Since the gas barrier properties of EVOH
film is made.
films are adversely affected by moisture, they
 Films 23

Biaxially oriented PETP films are prepared 6.9. Polycarbonate (PC) [20]
in thicknesses ranging from 1.0 to 350 µm and (→ Polycarbonates)
vary in appearance from clear to transparent, de-
pending on their end use. Pigments can also be Polycarbonate [25037-45-0] (PC) film first ap-
added for coloration. peared on the market in 1957 and is prepared
Polyester films have favorable mechanical from bisphenol A and phosgene. The principal
and electrical properties, are resistant to sol- manufacturers of both polycarbonate and poly-
vents, and display long-term thermal stabil- carbonate film are General Electric and Bayer.
ity up to 130 ◦ C (VDE 0530). They can be Polycarbonate films are produced either by
welded and bonded by special techniques. Fur- extrusion (chill roll) or by solution casting and
thermore, these films can be printed by flexo- are available with a thickness of 2 – 500 µm.
graphic, gravure, and screen printing techniques; The thinner grades are subjected to monoax-
they are also suitable for high-vacuum metalliza- ial stretching. The properties of monoaxially
tion without the need for special pretreatment. stretched PC film are listed in Table 4.
Some polyester films can be subjected to fur- The special characteristics of these films in-
ther deforming subsequent to their manufacture, clude their sterilizability, dimensional stability,
for example, by thermoforming or thermally in- thermoformability, and long-term thermal sta-
duced shrinking. Properties of PETP film are bility up to 130 ◦ C (VDE 0530). They are trans-
listed in Table 4; its permeability to gases and parent to crystal clear in appearance, and possess
water vapor can be significantly decreased by good electrical properties. Applications have
coating with PVDC. been found in packaging, the electrical indus-
Polyester films are used for more applications try, and above all in the field of graphics. Con-
than any other type of film. They are employed sumption of PC film in the United States is ca.
as packaging materials, dielectrics, and electri- 3000 t/a.
cal insulators, as base films for photographic Increased usage is anticipated, partly as a re-
and magnetic coatings, as release films in syn- sult of new developments in the raw material
thetic resin moldings, and as color and montage sector.
film in the graphics industry. These films also Trade Names. Lexan (General Electric, United
serve as a base for flexible printed circuits, as States); Makrofol (Bayer, Federal Republic of
drafting films, and as decorative film. Polyester Germany); Pokalon (Lonza, Federal Republic of
films have gained considerable importance in Germany).
the manufacture of videotapes. The demand for
polyester film as a base for thermal transfer tapes
is also increasing. 6.10. Polysulfone (PSU) (→ Specialty
Polyester films can be combined with other Plastics)
materials (PE film, paper webs, and aluminum
foil) to produce excellent composites. The first commercially available polysulfone
The economic importance of polyester film (PSU) was Udel, which was introduced by
is formidable: 550 000 t was sold worldwide in Union Carbide in 1965 (see also Section 6.12.2).
1986, most of this being used in the manufac- Udel polysulfone [25135-51-7] is produced by
ture of electrical insulation, magnetic tape, pho- reacting bisphenol A and 4,4 -dichlorodiphenyl
tographic film, and packaging film. sulfone. The material is amorphous, with a glass
Trade Names. Hostaphan (Hoechst, Federal Re- transition temperature of 190 ◦ C, and can be
public of Germany); Mylar (Du Pont, United converted into film either by extrusion or by so-
States); Melinex (ICI, United Kingdom); Lumir- lution casting.
ror (Toray, Japan); Tetoron (Teijin, Japan); Di- Polysulfone films are available in thicknesses
afoil (Diafoil, Japan); Terphane (Rhône Poulenc, ranging from 25 to 1000 µm. They are highly
France); Espet (Toyobo, Japan). transparent, possess high heat and dimensional
stabilities, and can be thermoformed. Their elec-
trical properties are comparable to those of biax-
ially oriented polyester films. Polysulfone films
are suitable for long-term use at temperatures up
24 Films

to 150 ◦ C, making them superior in this respect film production was first marketed by General
to polyester films. Polysulfone films are also sta- Electric in 1982 under the trade name Ultem and
ble to alkali, acid, oils, and detergents, although is an amorphous thermoplastic polymer with the
they are attacked by ketones and chlorinated or structure:
aromatic hydrocarbons. The properties of Udel
PSU film are listed in Table 5.
Principal applications are in packaging, the
electrical industry, adhesive tape manufacture,
and display technology [37].
Trade Names. Sumilite FS 1200 (Sumitomo
Bakelite, Japan); Europlex-Folie (Röhm, Fed- Poly(etherimide) film is prepared by the
eral Republic of Germany). chill roll process at an extrusion temperature of
350 ◦ C and is available with a thickness of 75 –
500 µm.
6.11. Polyimide (PI) (→ Polyimides) This film is especially suited for electrical ap-
The most important polyimide [25036-53-7] plications due to its favorable mechanical and
(PI) for film production is derived from pyromel- electrical properties. The maximum temperature
litic acid and 4,4 -diaminodiphenyl ether [38]. for long-term use is 170 ◦ C; thus, thermal sta-
Films made from this material do not melt, and bility is substantially less than that of conven-
they have the highest thermal stability of any tional polyimides. Nonetheless, stability is ade-
synthetic film. They are suitable for long-term quate for many purposes and significantly higher
applications at temperatures up to 240 ◦ C and than that of polyester film [37]. The film is used
short exposure to peak temperatures of up to mainly for electrical insulation. For properties,
400 ◦ C. For properties, see Table 5. see Table 5.
Polyimide films are prepared by dissolving Trade Names.Ultem Films (Westlake, Dixon,
the appropriate monomers in a suitable solvent United States); Sumilite FS-1400 (Sumitomo
(e.g., N,N-dimethylacetamide), in which they Bakelite, Japan); Europlex PEI (Röhm, Federal
react to form a soluble intermediate (polyamic Republic of Germany).
acid). The film is cast from this solution and is
subsequently converted into the insoluble poly-
imide by intramolecular condensation at 300 ◦ C. 6.12.2. Polyethersulfone (PES) (→ Specialty
The combination of high thermal stability and Plastics)
flame resistance, along with stability to radiation
and favorable electrical properties, makes this The poly(ethersulfone) (PES) used in film manu-
film attractive for applications in the aerospace facture is an amorphous, thermoplastic material
industry (e.g., as an electrical insulator), and manufactured by ICI under the trade name Vic-
the manufacture of electronic components [39]. trex. It consists of aromatic rings linked alter-
Commercial grades range in thickness from 7.5 nately by ether and sulfone groups:
to 125 µm.
Worldwide capacity in 1986 was 1400 t/a
with an expected annual growth rate of 10 %.
Trade Names. Kapton (Du Pont, United States;
Toray/Du Pont, Japan); Upilex (Ube Industries,
Japan); Novax (Mitsubishi Chemical, Japan).
Poly(ethersulfone) film is normally manufac-
tured by the chill roll process, although it can
6.12. Other Films also be cast from solution. Thicknesses vary
from 25 to 300 µm. Its range of applications is
6.12.1. Polyetherimide (PEI) determined by its electrical and optical proper-
ties combined with its thermostability and flame
The backbone of polyetherimides (PEI) contains resistant behavior [37], [40], [41].
both ether and amide linkages. The PEI used for
 Films 25

Poly(ethersulfone) films are used in electri- stability [43]. Thus, it is mainly used in the elec-
cal insulation, interior aircraft fittings, and liquid trical industry, although it also has potential as
crystal displays. a magnetic storage medium.
Trade Names. Stabar (ICI, United Kingdom); Trade Names. Torelina (Toray, Japan).
Victrex PES-5200 G (Westlake, United States);
Talpa 1000 (Mitsui Toatsu, Japan); Sumilite FS
1300 (Sumitomo Bakelite, Japan); Europlex- 6.13. Composite Films [44]
Folie (Röhm, Federal Republic of Germany).
The most important production methods for
composite films are adhesive lamination, extru-
6.12.3. Poly(ether ketone) (PEK) sion coating (see Section 2.4.3), and, more re-
cently, the simultaneous extrusion (coextrusion)
Poly(ether ketones) [2738–27–4] can be ex- of several raw materials (see Section 2.4.2). The
truded into either fibers or films in the tempera- latter approach is unique in that it can produce
ture range 350 –420 ◦ C. very thin multilayer films (ca. 12 µm) that still
Films made from PEK display high thermal display combined properties.
stability (up to 240 ◦ C), solvent and chemical re- The incorporation of PETP, BOPP, PA, and
sistance, good dimensional stability, flame resis- PVC into composite films permits optimization
tance, and stability to both radiation and hydro- of ultimate strength, elongation at break, and
lysis. Properties are listed in Table 5. Since PEK puncture resistance.
film also possesses favorable electrical proper- Composite films are especially important as
ties and is a low-density material, it is used in packaging materials, particularly for bulk mate-
the aerospace industry. rials regardless of their state, i.e., gases, liquids,
Both crystalline and amorphous unoriented and solids.
films are commercially available in thicknesses Composite films that contain polyethylene
from 75 to 250 µm [37], [41], [42]. Oriented can be welded by either heat impulse or thermal
films are still being developed. sealing methods. Thin polyethylene layers (ca.
Trade Names. Stabar K and XK (ICI, United 30 µm) may suffice for packaging lightweight
Kingdom); Sumilite FS 1100 (Sumitomo Bake- goods, provided that no need exists for evac-
lite, Japan); Talpa 2000 (Mitsui Toatsu, Japan). uation or a controlled atmosphere. Moderately
thick layers (≥ ca. 40 µm) are required for vac-
uum and inert atmosphere packings. Thicker PE
6.12.4. Poly(Phenylene Sulfide) (PPS) film (≥ ca. 60 µm) is employed if the material to
(→ Specialty Plastics) be packaged is a liquid or a paste.
The combination of plastic films with alu-
Poly(phenylene sulfide) [9016-75-5] (PPS) was minum foil produces semirigid composites with
marketed as early as 1973 by the Phillips exceptionally low permeability to gases, wa-
Petroleum Company under the trade name Ry- ter vapor, and odors. Special heat-sealable,
ton. However, it was not until 1985 that Phillips, polyolefin-based layers result in composite films
in collaboration with Toray, succeeded in pro- that can be separated by peeling. Composite
ducing the material in film quality. films incorporating ionomers are especially suit-
Poly(phenylene sulfide) is a partially crys- able for packaging oily materials.
talline polymer prepared from sodium sulfide
and 1,4-dichlorobenzene. Poly(phenylene sul-
fide) film is manufactured by extrusion at 300 ◦ C 7. Summary of Uses [2], [10], [26], [27]
and is similar to PETP film in that it can be bi-
axially oriented and heat-set. Properties of PPS The most important uses of individual films have
film are given in Table 5. Thicknesses are in the been described in Chapter 6 and are summarized
range 2 – 125 µm. in Table 6. They can be divided into three main
Poly(phenylene sulfide) film combines favor- categories: packaging, electrical insulation, and
able electrical characteristics with high thermal use as bases for other active materials.
Table 6. Uses of films

26
Application Film material∗

Cellophane CA PE BOPP PMP Ionomer PS PVC PVDC PVF PTFE PCTFE PMMA PVA EVOH PA PETP PC PSU PI PEI PES PEK PPS

Packaging
Food (incl. snack x x x x x x x x x x x x x
and

Films
convenience
foods)
Nonfood items x x x x x x x x x x x x x
Electrical
Insulation
Capacitors x x x x x x
Insulation x x x x x x x x x x x x
Printed circuits x x x x x x x
Base Film for Functional Coatings
Adhesive tapes x x x x x x x
Magnetic tapes x
Floppy disks x x
Photographic x x
film
Reprography x x x x
Decoration x x x x x
Transfer x x
metallization
Graphics x x x
Miscellaneous
Office supplies x x x x x x
Heat mirrors x
Protective x x x x x x x x x x x
lamination
Solar collectors x x
Release film x x x x x x x x
Protective covers x x x
Display items x x x

∗ For explanation of abbreviations, see abbreviations list.

 Films 27

Packaging. Packaging is the most important tra strength with defined surface roughness have
application of films; virtually every type of film been developed for this purpose. Magnetic tapes
finds some application in the packaging field. based on these films are marketed internation-
Plain and printed films are commonly used in ally for audio cassette players, video recorders,
packaging a wide range of foods and nonfood computers, and other commercial and industrial
articles. Legal requirements for food packaging recording equipment (→ Information Storage
are described in [25] (see also → Foods, 4. Food Materials).
Packaging, Chap. 8.4.). Films with a high dimensional stability (e.g.
Tubular film prepared either directly by blow- PETP) are used as substrates for drafting and
ing or by the subsequent sealing of flat film photocopying. Films are also used in the print-
is used for the manufacture of a wide variety ing industry as carriers for transferring color to
of bags, sacks, and blister or cushion packs. paper or plastics (stamping foil). Film coated
Thicker films are thermoformed into bottles, with deformable materials are used as emboss-
containers, cups, trays, and bowls. Shrinkable ing films. Iridescent films and films coated with
film is employed in palette packaging. Film is firmly bonded layers of metal and/or lacquers are
also the basis of skin packings, packing tapes, frequently used for decorative or display pur-
and even tear-off bands. Decorative iridescent poses. Films are also the basis for most adhe-
packaging films are available which consist of sive tapes. The introduction of a wide range of
layers of two or more different polymers with film-based typewriter ribbons are another appli-
different refractive indices. The iridescent color cation.
is produced by light interference [45]. Special
characteristics such as impermeability to gases Miscellaneous. The furniture industry em-
and water vapor can be obtained by applying ploys films as veneers for the surface treatment
coatings or using laminated structures. of sheet materials. Thicker films (sheets) are
thermoformed into ceiling and wall panels, as
Electrical Insulation. Films with a high di- well as decorative fixtures and reproductions.
electric constant and a low dielectric loss factor The use of films in heat mirrors and solar
are particularly useful in a.c. and d.c. capaci- collectors (→ Solar Technology) is a more re-
tors. Such films may be as thin as 1.0 µm. The cent development. Heat mirrors employ coated
films themselves are dielectrics, but they can be films (mostly PETP) that transmit visible light
converted to electrodes either by vacuum met- and reflect infrared light. In solar collectors, so-
allizing or by combining them with aluminum lar energy is absorbed and passed to a flowing
foil. Polyester and PI films, either alone or in heat-transfer medium (e.g., water). Solar collec-
combination with paper or synthetic nonwoven tors may be constructed from UV-stable film.
materials serve as insulating material in electri- Film is frequently used as a protective cov-
cal equipment. Polymer films are also employed ering for equipment and materials. Many mod-
in cable sheathing; thin strips of film are often ern greenhouses are constructed almost entirely
used as electrical insulation or labels; they also from transparent film material. The building in-
create plasticizer barriers, provide thermal and dustry generally makes frequent use of films on
mechanical insulation, and, in combination with account of their waterproofing properties. Small
metallic film, confer protection against static amounts of films are used for rainwear and cloth-
charging. Polyester (PETP), PC, and PI films are ing.
used in the production of flexible printed cir-
cuits because of their exceptional dimensional
and thermal stability. Film switches represent 8. Environmental Aspects
a new area of application, especially for PETP
film. Most of the scrap rolls and waste generated in
film production as a result of edge trimming and
Base Films for Functional Coatings. manufacturing problems is collected and recy-
Polyester film in particular has acquired ma- cled. Special facilities are required for shredding
jor significance as a base material for magnetic the film and compressing it into granules suitable
coatings. Special polyester films combining ex- for reprocessing.
28 Films

Film constitutes 1 – 2 % of normal house- 7. R. A. Elden: “Calandering of Film and

hold waste. Separate collection and recycling of Sheeting” in A. Whelan, J. L. Craft (eds.):
waste film is in theory possible, but is expen- Developments in PVC Production and
sive and requires considerable organization. All Processing – 1, Applied Science Publ.,
films can be regarded as environmentally harm- London 1977, pp. 205 – 221.
less, provided that they are disposed of properly. 8. F. Hensen, W. Knappe, H. Potente (eds.):
Combustion of film waste presents no particular Handbuch der Kunststoff-Extrusionstechnik,
technological problems. Even PVC film can be “Extrusionsanlagen,” vol. II, Hanser Verlag,
München – Wien 1986; G. Winkler:
safely incinerated, although public controversy
“Extrusion von Blasfolien,” pp. 76 – 106; R.
suggests otherwise; modern combustion facili-
Hessenbruch: “Coextrusion von Blasfolien,”
ties are capable of trapping any hydrogen chlo- pp. 107 – 124; H. Bongaerts: “Extrusion von
ride vapor that is formed. Flachfolien nach dem Kühlwalzenverfahren,”
Films can create litter problems; a number of pp. 125 – 186; F. Hensen: “Extrusion von
film additives and other chemical modifications gereckten Folien,” pp. 243 – 270; E.
have been proposed for accelerating the rate at Schöllkopf, K. Roesch: “Beschichten und
which films undergo photooxidative decompo- Kaschieren durch Extrusion,” pp. 320 – 353.
sition. However, apart from one exception these 9. S. Janocha: “Herstellung von
suggestions have not been implemented, primar- Polyethylenterephthalat Folien,” in
ily because the required precision in formulation Winnacker-Küchler, 7, 520 – 523.
for a given application is difficult to achieve. In 10. E. Werner, S. Janocha, M. J. Hopper, K. J.
addition they conflict with the present ideas of Mackenzie: “Polyesters, Films” in
litter prevention. The sole exception is the mulch Encyclopedia of Polymer Science and
film employed in agriculture for stimulating seed Engineering, 2nd ed., vol. 12, J. Wiley & Sons,
germination and growth; this product is designed New York 1988, pp. 193 – 216.
to have a lifetime of only one growing season. 11. R. J. Ashley, D. Briggs, K. S. Ford, R. S. A.
Kelley: “Adhesion Problems in the Packaging
Industry” in D. M. Brewis and D. Briggs
(eds.): Industrial Adhesion Problems, Orbital
9. References Press, Oxford 1985, pp. 213 – 218.
12. H. L. Weiss: Coating and Laminating
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New York 1969, pp. 3 – 9. 14. S. Levy: Plastics Extrusion Technology
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Polymer Films, vol. I, II, Interscience, New 1981.
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 Films 29

21. ASTM Standards,Parts 26, 27, 1967. EVAL-Resin,” CEER Chem. Econ. & Eng. Rev.
22. DIN-Taschenbuch 18, 21, Beuth-Verlag, 9 (1977) no. 10, 32 – 37. Data Sheet, EVAL EF,
Berlin 1986. Biaxial Oriented EVAL-Film, Kuraray, Osaka.
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29. Data Sheet 1982 A, Mitsui Petrochemical Ind., 41. Data Sheet, High Performance Film
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34. Data Sheet, Emblar-OV, Biaxially oriented 44. Data Sheets Hoechst, Werk Kalle, Wiesbaden
PVA-Film, Unitika Ltd., Osaka. Data Sheet, 1980 – 1987.
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Nippon Gohsei, Osaka. Information Sheet TIB-G, The Mearl
35. H. Iwasaki, K. Sato, K. Akao, K. Watanabe: Corporation, 1050 Lower South Street,
“Development and Commercial Production of Peekskill, New York 10566, April 1980.

Filters, Optical → Optical Materials

 Filtration 1

Filtration
See also → Solid – Liquid Separation, Introduction

Walter Gösele, Heidelberg, Federal Republic of Germany (Chaps. 1 – 7)

Christian Alt, München, Federal Republic of Germany (Chaps. 8 – 11)

1. Terminology . . . . . . . . . . . . . . . 3 4.1.5. Shrinking and Cracks in Filter Cakes 23

2. Filtration Models . . . . . . . . . . . . 4 4.2. Deliquoring by Expression . . . . . . 23
2.1. Cake Filtration: Calculation of the 5. Optimal Cycle Time . . . . . . . . . . 24
Pressure Drop . . . . . . . . . . . . . . 4 6. Understanding the Filter Resistance 26
2.1.1. Definition of Filter Resistance and 6.1. The Equation of Carman and
Cake Permeability: The Darcy Equa- Kozeny . . . . . . . . . . . . . . . . . . . 26
tion . . . . . . . . . . . . . . . . . . . . . 4 6.2. Interparticle Forces, DLVO Theory 27
2.1.2. The “Cake Filter Equation” . . . . . . 5 6.3. Mathematical Simulation of Cake
2.1.3. Evaluation of Experiments with Linear Formation . . . . . . . . . . . . . . . . . 28
Diagrams . . . . . . . . . . . . . . . . . . 6 7. Solving Filtration Problems in
2.1.4. Compressible Cake Filtration . . . . . 8 Small-Scale Tests . . . . . . . . . . . . 29
2.2. Blocking Filtration and other Modes 7.1. Laboratory Tests . . . . . . . . . . . . 29
of Filtration . . . . . . . . . . . . . . . . 10 7.2. Handling of “Unfilterable” Suspen-
2.3. Deep Bed Filtration . . . . . . . . . . . 11 sion . . . . . . . . . . . . . . . . . . . . . 30
2.4. Cross-Flow Filtration . . . . . . . . . 14 8. Filtration Equipment . . . . . . . . . 32
3. Washing of Filter Cakes . . . . . . . . 15 8.1. Bag Filters . . . . . . . . . . . . . . . . 33
3.1. Basic Effects, Mass Balances . . . . . 15 8.2. Belt Filters . . . . . . . . . . . . . . . . 33
3.2. Example of Experimental Results . 15 8.3. Candle Filters . . . . . . . . . . . . . . 38
3.3. Test Procedures and Pitfalls . . . . . 17 8.4. Deep-Bed Filters . . . . . . . . . . . . . 40
3.4. “Intermediate” Deliquoring before 8.5. Disk Filters . . . . . . . . . . . . . . . . 42
Cake Washing . . . . . . . . . . . . . . 18 8.6. Drum Filters . . . . . . . . . . . . . . . 43
4. Deliquoring of Filter Cakes . . . . . 18 8.7. Leaf and Plate Filters . . . . . . . . . 50
4.1. Deliquoring by Gas Pressure . . . . 18 8.8. Nutsche (Pan) Filters . . . . . . . . . . 53
4.1.1. Equilibrium Saturation of Filter Cakes 19 8.9. Pressure Plate Filters . . . . . . . . . 54
4.1.2. Kinetics of Deliquoring by Gas Pres- 8.10. Tubular Filters . . . . . . . . . . . . . . 59
sure . . . . . . . . . . . . . . . . . . . . . 20 8.11. Special Filter Types . . . . . . . . . . . 60
4.1.3. Approximate Solution for Coarse, In- 9. Filter Selection . . . . . . . . . . . . . . 62
compressible Cakes . . . . . . . . . . . 21 10. Filter Media . . . . . . . . . . . . . . . 63
4.1.4. Practical Scale-Up of Deliquoring by 11. Filter Aids . . . . . . . . . . . . . . . . . 65
Gas Pressure . . . . . . . . . . . . . . . . 22 12. References . . . . . . . . . . . . . . . . . 66

Symbols I ionic strength, mol/L

a intercept in Figure 5, s/mL KH proportionality volume of cake/volume of
A cross-sectional area, filter area, m2 filtrate, m3 /m3
b slope in Figure 5, s/mL Km proportionality mass of cake/volume of
B creep constant filtrate, kg/m3
C creep constant KN proportionality number of parti-
d pore capillary diameter, m cles/volume of filtrate, m−3
dS Sauter mean diameter of particles, m k permeability = 1/αh , m2
E electrostatic potential at the solids sur- L distance from the inlet face of the filter
face, V bed, m
H cake thickness, m m mass of dry filter cake, kg
J Boucher’s filterability index, m−3 mi molar concentration of ion “i”, mol/L

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b02 10
2 Filtration

N number of pores in the filter medium the fluid phase of the mixture being separated. In
n compressibility index earlier times, this process was carried out with
∆P dimensionless pressure difference felts, and the word “filter” has a common deriva-
pc capillary pressure, Pa tion with “felt”.
pce capillary entry pressure, Pa Often however, purification of a liquid or gas
pci capillary suction pressure, Pa is called filtration even when no semipermeable
pL pressure in the liquid, Pa medium is involved (as in electrokinetic filtra-
pS compressive stress on the solids, Pa tion). This chapter deals only with the filtration
q exponent describing blocking behavior of solid – liquid mixtures (suspension, slurries,
r distance from the solids surface, m sludges). For the treatment of gases by filtration,
rD Debye length, m → Dust Separation.
S saturation (volume of liquid/volume of The liquid more or less thoroughly separated
pores) from the solids is called the filtrate, effluent, per-
SR reduced saturation meate or, more rarely, clean water. As in other
S∞ irreducible saturation separation processes, the separation of phases is
t reg regeneration time for cleaning and never complete: Liquid adheres to the separated
preparing a run, s solids (cake with residual moisture) and the fil-
Uc consolidation rate trate often contains some solids (solids content
V volume of filtrate, m3 in the filtrate or turbidity).
V̇ volumetric flow rate, m3 /h The purpose of filtration may be clarification
zi valency of ion “i” of the liquid or solids recovery. In clarification
αH cake resistance relative to cake thickness, the liquid is typically the valuable product and
m−2 the solids are of minor quantity and are often
αm cake resistance relative to dry mass, m/kg discarded without further treatment. If however
β resistance of filter medium, m−1 the solids are to be recovered, they very often
ε porosity = pore volume/total volume have to be washed, deliquored and dried (see
η viscosity, Ns/m2 Fig. 1). In this article, washing means the clean-
Θ dimensionless time ing of a product (filter cake) and it is distin-
λ filter coefficient of deep bed filters, m−1 guished from cleaning parts of the filter itself,
ζ surface potential, V which will be called rinsing (e.g., rinsing a filter
screen or a filter cloth by jets of water). A fur-
ther distinction is to be made between washing
Indices and extraction or leaching. Washing eliminates
av average liquid contaminants from the pores between the
e end of filtration particles of a filter cake. Extraction recovers sol-
H related to cake thickness (height) uble matter from the solid particles themselves
L liquid (→ Liquid – Solid Extraction). The term drying
loc local means thermal drying, while the elimination of
m related to cake mass liquid from the filter cake by mechanical forces
N number is called deliquoring or dewatering, e.g., deli-
S solid quoring by gas pressure or by expression.
w wash liquor Filtration is effected by application of vac-
pore pore (volume) uum, pressure, or of centrifugal force (see
Fig. 2). Vacuum filtration requires a vacuum
pump. The pump evacuates the gas from a filtrate
receiver, where the filtrate is separated from the
1. Terminology gas. The filtrate is drained either by a barometric
leg of at least 8 to 10 m or by a pump that is able
Filtration is the separation of solid particles or to “run on snore” (i.e. with a deficiency of feed
liquid ones (droplets) from liquids and gases liquid so that it tends to draw in air). Pressure
with the help of a filter medium also called a filtration typically only requires a pump for de-
septum, which is essentially permeable to only livering of the suspension and the filter is placed
 Filtration 3

Figure 1. Solids processing chain

within a pressure vessel, hence less easily acces- early, proportional to the quantity of solid
sible. Centrifugal filtration is done in perforated deposited. This model can be applied par-
centrifuge rotors (→ Centrifuges, Filtering). ticularly well for all hard, particulate solids.

– Blocking filtration: The pressure drop is

caused by solid particles blocking pores.
Soft, gelatinous particles retained by a sieve
exhibit such a behavior. If the flow rate dV /dt
is constant, the pressure drop increases expo-
nentially with the quantity filtered, the num-
ber of open pores asymptotically approach-
ing zero. The pores may belong to a filter
medium (screen or filter layer) or it may be
pores within a filter cake of coarse particles,
Figure 2. Driving forces in filtration which are blocked by migrating fine parti-
Vacuum filters have the great advantage that cles.
the cake is freely accessible. This facilitates au- – Deep bed or depth filtration: Solid particles
tomatic cake handling. However, vacuum filters are retained in a deep filter layer. This takes
cannot handle hot liquids, or solvents with high place for example in sand filters for clarifi-
vapor pressure. The pressure difference across cation of drinking water, which retain even
vacuum filters is very limited, and the resid- colloidal particles. The typical effect of deep
ual moisture of the filter cake is higher than bed filtration is adhesion of solids to the
with pressure filters. Pressure filters in turn are grains of the filter layer, comparable to char-
preferred when the product must be kept in a coal adsorption. Only rather big particles are
closed system for safety reasons, or if the resid- retained by the screening effect. When the
ual moisture content is important. The handling filter bed has been saturated with solids, the
of the filter cake is obviously more difficult in solids concentration in the filtrate leaving the
a pressure filter. Filtration by centrifugal force bed progressively approaches that of the in-
requires more technical equipment, but as a gen- coming suspension.
eral rule it yields solids with lower residual mois- – Cross-flow filtration: In cross-flow filtration
ture (→ Centrifuges, Filtering). the suspension flows with high speed tan-
Various models can describe the physical pro- gentially to the filter surface, preventing the
cess of filtration. This chapter concentrates on formation of a cake. Only a small flow of liq-
four idealized filtration models depicted in Fig- uid passes through the filter medium. A cer-
ure 3. tain layer of solids accumulates in the bound-
– Cake filtration is the most frequently used ary layer on the filter surface, and reduces
model. Here it is assumed that the solids are the flow of filtrate. After an initial period, a
deposited on a filter medium as a homoge- dynamic equilibrium is established between
neous porous layer with a constant perme- convective transport of solids to the filter sur-
ability. Thus, if the flow rate dV /dt is con- face and removal of solids by turbulence and
stant, the pressure drop will increase lin- by diffusion.
4 Filtration

Figure 3. Filtration models

Surface filtration is the antonym to depth fil- 2) The cake thickness H

tration. The solids are retained on the surface of 3) the viscosity η of the liquid
a filter medium. Generally the models of cake 4) A constant αH describing the “specific filter
filtration or of blocking filtration can be applied. resistance” of the cake:
Screening designates a classification process,


which retains the particles below a certain size V̇
and lets pass the smaller ones (→ Screening). ∆p1 = ·H ·η·αH (1)
A
Often the term screening filtration is also used
 3  
to designate a surface filtration with a screen The SI-units are Pa = mm2/s ·m·Pa·s·m−2
as a filter medium. Its mode of action resem-
bles screening (or straining) as long as the filter The unit of αH must therefore be m−2 in order
medium is clean, but it is clearly a cake filtration to satisfy the Darcy equation (1). The reciprocal
as soon as a layer of solids has formed. of the filter resistance αH is also called perme-
ability k of the filter cake:
1  2
k= m (2)
2. Filtration Models αH
Sometimes it is more convenient to define cake
2.1. Cake Filtration: Calculation of the thickness in terms of solid mass per unit area
Pressure Drop (unit kg/m2 ). This leads to a slightly different
definition of filter resistance, the factors being:
2.1.1. Definition of Filter Resistance and 1) The flow rate per unit area V /A
Cake Permeability: The Darcy Equation 2) The cake thickness m/A
3) The viscosity η of the liquid
The resistance to flow of a filter cake can be de- 4) A constant αm with the unit m/kg describing
scribed by Darcy’s law [1] (see Fig. 4). Consider the resistance of the cake.
a liquid flowing through a filter cake (or a stream
of water percolating through soil as considered Then the following expression is obtained in-
by Darcy). The pressure drop ∆p of this flow is stead of Equation (1)
proportional to:

V̇ m
∆p1 = · ·η·αm (3)
1) The flow rate per unit area V /A A A
 Filtration 5

For practical reasons the viscosity η is very of-

ten not measured separately. Then it is legitimate m
Km = (8)
to include it in a term αH η (unit mPa · s/m2 ) or V
αm η (unit mPa · s · m/kg), respectively. this gives
Using this latter term αH η or αm η filter re-
sistances lie between 1011 mPa · s/m2 (filtering αH ηKH dV βη dV
∆p = ·V · + + (9)
very rapidly) and 1016 mPa · s/m2 (nearly unfil- A2 dt A dt
terable), or between 108 and 1013 mPa · s · m/kg, or
respectively. αm ηKm dV βη dV
∆p = ·V · + + (10)
A2 dt A dt
Equations (9) and (10) are identical under the
generalization αH · K H = αm · K m . Nevertheless
the distinction between both equations is useful
for clarity.
The differential Equations (9) and (10) can
be integrated either for constant flow rate or for
constant pressure. Integration for constant flow
rate dV /dt = const gives the trivial solution:
 
Figure 4. Definition of filter resistance η· V̇ α H KH
∆p = · ·V + β (11)
ηαH = Cake thickness H related filter resistance; A A
ηαm = Solid mass related filter resistance
or
 
η· V̇ α m Km
∆p = · ·V + β (12)
A A
2.1.2. The “Cake Filter Equation”
For ∆p = const. the integration yields:
The pressure drop in a filter is composed of a
αηK βη
pressure drop ∆p1 across the cake according to dt = ·V ·dV + ·dV (13)
A2 ·∆p A·∆p
Equation (1) and a pressure drop ∆p2 across the αH ηKH βη
filter medium, which can be written as: t= ·V 2 + ·V (14)
2A2 ·∆p A·∆p


V̇ or
∆p2 = β ·η· (4)
A αm ηKm 2 βη
t= ·V + ·V (15)
2A2 ·∆p A·∆p
where b (unit m−1 ) is the resistance of the filter
medium.
The total pressure drop is therefore:
2.1.3. Evaluation of Experiments with
V̇ V̇
∆p = ∆p1 + ∆p2 = αH η·H · + βη (5) Linear Diagrams
A A
or Linear Diagram in the Differential Form.
It is often very helpful to plot the instantaneous
m· V̇ V̇
∆p = ∆p1 + ∆p2 = αm η· + βη (6) resistance to flow as a function of the quantity
A2 A
filtered. The resistance is characterized by the
If the suspension is homogeneously mixed, the pressure drop ∆p related to the instantaneous
cake height H (or m/A) will be proportional to flow rate dV /dt. Using Equation (5) or (6) this
the quantity of filtrate. The concentration is de- can be written as:
scribed by a factor K:
dt αH ηKH βη
= ·V +
H ·A dV ∆pA2 ∆pA
KH = (7)
V αm ηKm βη
= ·V + = b·V + a (16)
or ∆pA2 ∆pA
6 Filtration

As shown in Figure 5 left diagram [2], inter- On the other hand Equation (20) is correct
polation gives a straight line with slope b and only for ∆p = const. Furthermore, the resulting
intercept a. The intercept diagram shows less clearly the deviations from
linearity than a diagram based on instantaneous
βη
a= flow rates. If for example a cake stops growing
∆p
and keeps a constant resistance this gives a well
represents the resistance at the very first mo- discernible plateau in a differential diagram, but
ment of filtration, before a cake is formed, hence only a gradual hyperbolic bend in the integrated
the resistance of the filter medium including the diagram.
boundary layer to the cake.
The slope b contains the filter resistance α Example. The interpolation of the test results
according to shown in Figure 5 leads to the intercept a and the
  slope b
dt
∆ ∆p· dV αηK
b = slope = = (17) a = 3.6s/mL = 3.6 × 106 s/m3 (21)
∆V A2
Inserting K H or Km respectively, gives and
    28s/mL
dt
∆ ∆p· dV A2
dt
∆ ∆p· dV A·V b= = 1.87·10−11 s/m6 (22)
αH η = · = · 150mL
∆V KH ∆V H
  The following parameters are known:
dt A
= ∆ ∆p· · (18)
dV e He Filtration pressure p = 1 bar = 105 N/m2
Filter area A = 20 cm2 = 20 × 10−4 m2
and Viscosity η = 0.001 Pa · s = 10−3 Ns/m2
    Cake height H e = 37 mm
dt dt
∆ ∆p· dV A2 ∆ ∆p· dV A2 ·V
αm η = · = · Cake mass me = 24.3 g
∆V Km ∆V m Volume of filtrate V e = 154 cm3
 
dt A2
= ∆ ∆p· · (19) Solids in suspension
dV e me
A·He 20·10−4 ·0.037
KH = = = 0.481 (23)
Ve 154·10−6
Linear Diagram in Integrated Form. An- or
other approach starts from the integrated filter
Equations (14) or (15). The experimental results me 24.3·10−3 kg kg
Km = = · = 158 3 (24)
are plotted in the form of Ve 154·10−6 m3 m

t This gives for the filter medium resistance

= f (V )
V
∆p·A 105 ·20·10−4 −1
If the pressure is constant during the experiment, β = α· = 3.6·106 · m
η 103
a straight line should be obtained = 7.2·1011 m−1 (25)
t αm ηKm βη
= ·V + From Equations (18) or (19) follows the cake
V 2A2 ·∆p A·∆p filter resistance
αH ηKH βη b
= ·V + = ·V + a (20)
2A2 ·∆p A·∆p 2 A2 ·∆p 400·10−8 ·105 −2
αH = b· = 0.187·1011 · m
KH η 0.481·10−3
This kind of plot is still very popular in prac-
= 1.56·1014 m−2 (26)
tice because the evaluation is often easier than
with Equation (16). Experimental values mea- A2 ·∆p 400·10−8 ·105 −2
sured with a bucket and a stopwatch can be in- αm = b· = 0.187·1011 · m
Km η 158·10−3
serted directly into Equation (20), while for a m
= 4.73·1011 (27)
differential diagram they have to be converted kg
into momentary flow rates dV /dt.
 Filtration 7

Figure 5. Linear plots according to Eqs. (8) and (11) [41]

Deviations from Linearity. Experimental Determination of the beginning or the end

data very often differ from the linear charac- point of filtration may not be correct. The
teristic shown in diagrams “I” or “II” of Fig- end point is particularly difficult to deter-
ure 5. The kind of deviation indicates the nature mine if there is no sight glass in the filter.
of secondary effects (see Fig. 6): It is therefore common practice to neglect
some points at the end of the measure-
– A: Theoretical linear curve without sec- ment.
ondary effect. Unusual properties of the suspension
– B: Some solids have settled before the filtra- like foam bubbles or oil droplets, non-
tion started, apparently increasing the resis- Newtonian rheology of the liquid or non-
tance of the filter medium. isometric, plate-like particles with special
– C: At the beginning of filtration the filtrate orientation can produce a great variety of
has been turbid. The solids loss diminishes effects.
the amount of cake, apparently indicating a The sediment may be so voluminous that
negative medium resistance. (When no tur- it fills the whole suspension. The process
bidity is found in the filtrate, this curve may then resembles rather an expression than
indicate that solids accumulate inside the fil- a filtration (Section 4.2).
ter medium, blocking it in the long run!). Freshly precipitated solids sometimes
Similar curves may be observed when the continue to agglomerate or to “ripen” dur-
solids float and clear liquid is filtered in the ing filtration, changing their effective par-
beginning. ticle size.
– D: The solids settle out completely, increas-
ing the speed of cake growth. At the end of
filtration clear liquid flows through the cake
of constant resistance. 2.1.4. Compressible Cake Filtration
– E: Only coarse particles settle. After some
time only the remaining fines are filtered and Most filter cakes are compressible, which means
the resistance increases progressively. that their resistance increases with growing pres-
– F: Fine particles trickle through the cake sure. An x-fold increase in filtration pressure
and block the pores of the cake or of the therefore normally gives rise to a less than x-
filter medium. The process can perhaps be fold increase in flow rate. The compression of
described as a blocking filtration (see Sec- the cake is caused by the compressive stress ps
tion 2.2). on the solids which is caused by the drag of the
– Further causes of deviations might be: flowing liquid (see Fig. 7). The loss in liquid
8 Filtration

Figure 6. Typical deviations from linearity [41]

A) Differential plot according to Eq. (16); B) Integral plot according to Eq. (20)

pressure pL translates into solids pressure pS , However, only the average resistance αav of
the sum of both being constant: a filter cake, all layers combined, is important for
practical scale-up purposes. It can be calculated
∂ pS = −∂ pL (28) from αloc measured in the CP-cell [3]
∆p
pS + pL = p0 (29) αav = (30)
p dp
αloc
0

Normally however it is much easier to mea-

sure αav directly with filtration experiments in
a pressure filter as described in Section 7.1. The
uneven distribution of local porosity and filter
resistance is then ignored.
The dependence of filter resistance αav or
αloc on pressure can be approximated over a lim-
ited pressure range by
 n
pS
α = α0 · (31)
unitpressure
where α0 is the resistance at unit pressure drop
and n is a compressibility index (equal to zero
for incompressible cakes). Both parameters can
be determined easily from a logarithmic plot
α = f (pS ), where the slope indicates the com-
pressibility factor n. Introducing αloc according
Figure 7. Hydraulic pressure pL and solids pressure pS as to this approximation into Equation (19), it can
function of cake height. Curve (a) represents a more com- be shown that for 0 < n < 1
pressible cake than curve (b)
nav = nloc (32)
The local filter resistance αloc in the cake is
a function of the local compressive stress pS and α0,av = (1 − n) ·α0,loc (33)
it is therefore low at the surface of the cake and Thus the approximation Equation (31) has the
high near the interface with the filter medium. advantage that it applies to both the local and the
This αloc = f (pS ) can be measured in the Com- average resistance. However, such an approxi-
pression Permeability cell (CP cell) described in mation is valid only for a limited range of pres-
Chapter 7, where a sample of the cake is subject sures and Equations (32) and (33) are restricted
to a known compressive stress. to 0 < n < 1.
 Filtration 9

Tiller and coworkers [4] give an integration with V̇ 0 (m3 /s) being the flow rate at the start
of the filter equation also for n > 1. According of filtration with a clean filter medium.
to their equations the flow rate quickly reaches In real filtration processes not every particle
a constant value with increasing pressure. For in the suspension will block a pore of the fil-
practical purposes it can be approximated that ter medium. Some particles will be retained by
such “supercompactible” filter cakes with n > 1 adhesion to the walls of a pore without block-
(e.g., a great number of waste water sludges) ing it totally; others will pass through the filter
yield the same flow rate independently of the medium without being retained at all. Different
pressure applied: increasing pressure only in- formulae (or “filtration laws”) exist to describe
creases the compressed layer adjacent to the fil- such moderate blocking. A generalized model is
ter cloth. (The hypothetical cake which yields based on the equations
the highest flow at an “optimal pressure” and  q
less flow at higher pressures apparently does not d2 t dt
= const· (36)
exist. In practical application, however, the out- dV 2 dV
put of a filtration may be best with moderate for constant pressure filtration and
pressure, since this avoids excessive blocking of
the filter medium). d (∆p)
= const· (∆p)q (37)
For practical purposes Equations (31) – (33) dV
are often ignored and compressible cakes are
for constant rate filtration.
treated with the same equations as incompress-
The exponent q in this equation varies bet-
ible cakes, provided α is defined as average spe-
ween 0 and 2 and describes the “blocking
cific cake resistance under the conditions of op-
speed”:
eration.
Concerning deliquoring of compressible q = 0 cake filtration, slow blocking
cakes, it is important to know that the porosity q = 1 so-called intermediate filtration
is unevenly distributed after filtration. The filter q = 3/2 so-called standard blocking filtration
resistance often is concentrated in a thin, com- q = 2 complete blocking.
pressed layer facing the filter medium, the rest
A summary of the corresponding equations
of the cake being very porous and wet. Deliquor-
for flow rates and filtrate quantities is given
ing by expression (see Section 4.2) will then be
in [6], [7]. Figure 8 visualizes some examples:
very effective, even at moderate pressures, since
Surface straining represents the classical exam-
it acts also on the upper layer of the cake.
ple of complete blocking (q = 2), but also depth
straining follows the same characteristic. Nor-
2.2. Blocking Filtration and other mal depth filtration in contrast (with particles
much smaller than the filter pores) leads to pres-
Modes of Filtration
sure drop by diminishing pore size and can
According to the idealized idea of blocking fil- be described by the standard blocking equation
tration, every particle in the suspension is re- (q = 3/2).
tained on the filter medium and blocks one pore. In most filtrations it is highly probable that
The remaining number of open pores is then more than one filtration mode occurs. Cake fil-
given by the equation tration for example often is preceded by an ini-
tial period before cake build-up which can be
N (t) = N0 (1 − KN ·VL ) (34) described as standard blocking. This period is
where N 0 is the number of pores in the clean characterized by depth filtration (particles pen-
filter medium, N(t) is the remaining number etrating into the filter medium) and/or by fines
of open pores and K N (m−3 ) is the concentra- passing through the filter medium (creating ini-
tion of particles by number in the suspension. tial turbidity of the filtrate). For scientific inves-
At constant pressure drop the volume of filtrate tigations it may then be helpful to identify the fil-
V (t)∆p = const will follow the equation [5] tration mechanism more precisely by parameter-
1
  fitting the experimental data and quantifying the
V (t) = · 1 − exp −KN · V̇0 ·t (35) above-mentioned “blocking speed”.
KN
10 Filtration

is “Boucher’s filterability index”. If J = 1 Equa-

tion (38) and (39) are identical to an “intermedi-
ate filtration” with q = J = 1. For other values of
J however the physical meaning of J is unclear.
For scientific purposes this approach is there-
fore not so well accepted. For practical purposes,
however, it is very useful.

2.3. Deep Bed Filtration [9], [10]

In deep bed filtration (as opposed to cake filtra-
tion and cross-flow filtration), the solid particles
are separated mainly by deposition within the
pores of the filter medium. The filter medium
may consist of
– a 0.5 – 3 m layer of coarse grains (e.g., sand
0.3 – 5 mm) or
– a layer of a few centimeters of fibers (e.g.,
wound or resin bonded cartridge filters) or
– sheets of a few mm thickness (e.g., made of
cellulose).
– a layer of granular filter aid (e.g., precoat
layer)
All these filter elements have pores that are
larger than the particles to be retained. The par-
Figure 8. Three possible modes of filtration: Surface strain-
ing and depth straining are described as “complete block- ticles stick in the pores by adhesion and their
ing” (q = 2). Depth filtration of particles much smaller accumulation weakens the filtering action and
than the pore size is best described as “standard blocking” increases the pressure drop, so that the filter must
(q = 3/2) [6] be cleaned or replaced periodically. This is why
deep bed filtration should be used not to recover
solids from a suspension such as cake filtration,
Simplified Evaluation of Experimental but instead to produce a very clean effluent from
Data. A very pragmatic approach is often used suspensions with low solids loading (typically
to describe the mode of filtration. The pressure < 0.1 g/L) and with very fine particles. Depend-
drop at constant flow rate is depicted on a semi- ing on the particle size, the prevailing effects of
logarithmic scale as a function of the volume fil- retention are summarized in Figure 9:
tered. Normally the values can be approximated
by a straight line according to [8] 1) Particles larger than the pores are trapped
mechanically. This is typically true for par-
 
p ticles  10 µm.
log = −J ·VL (38)
p0 2) Particles 1 – 10 µm in diameter hit the solid
surface mainly due to inertia effects and stick
For the flow rate at constant pressure drop the there due to surface forces.
same approximation holds 3) Particles < 0.1 µm reach the solid surface

 mainly because of diffusion and again they
V̇
log = −J ·VL (39) stick there due to surface forces.
V̇0
In the range between 0.1 and 1 µm the effects
Here p0 is the initial pressure drop of the clean of both inertia and diffusion are small and a min-
filter; and the gradient J, which represents some- imum in transport and hence in the effectiveness
thing like the above-mentioned blocking speed, of deep bed filters is observed.
 Filtration 11

the pores. The quantity of deposit is gener-

ally small compared to the pore volume, and
the additional pressure loss per unit depth
can be described as proportional to the local
specific deposit. For constant solids concen-
tration at the inlet and constant retention the
increase in this pressure drop with time is
therefore approximately constant.
2) In addition there is often a pressure drop due
Figure 9. Retention mechanisms in a deep bed filter to deposits on the surface of the filter bed.
a) Particles > 10 µm are retained by mechanical intercep-
tion; b) Particles of ca. 1 µm size are subject to inertial im-
This is a typical blocking filtration and can
pact + adhesion; c) Particles <1 µm follow mainly Brown- be described by Boucher’s law (Eqs. 38 and
ian diffusion + adhesion 39).
Thus the transport of particles to the solid The total pressure drop of a deep bed filter at
surface is rather well explained and can be de- constant flow rate can then be approximated by
scribed mathematically. The mechanism of ad- an equation of the type
hesion to the filter grains however and the re-
sulting “sticking probability” is less well under- p (t) = const1 ·t + const2 ·eJ ·t (42)
stood. (Some aspects will be discussed in Sec-
tion 6.2). Consequently the clarification effect The pressure drop should be measured in a
must be summarized in an empirical “filter co- test filter with a vertical height close to that
efficient” λ describing the local decrease in con- of the full-scale unit (Fig. 10 A) [11]. For the
centration of the suspension flowing through the case that the driving force is gravity, the pres-
bed: sure profile is shown in Figure 10 B. In the static
equilibrium, at flow zero, 1 m of pressure head
∂C is gained for every meter of depth. The down-
− = λC (40)
∂L stream consumers may then draw a constant flow
where c is the concentration of the suspension rate. When flow has started, the pressure drop
and L is the distance from the inlet face of the within the media increases linearly with depth.
filter. For uniform conditions, this differential As solids are deposited in the pores, the local
equation can be integrated: pressure loss will increase in the upper layers
and the pressure line becomes distorted. When
c = c0 ·exp (−λ0 ·L) (41) the pressure line touches the atmospheric pres-
sure value, the required flow cannot be main-
here λ0 is the initial filter coefficient of a clean, tained and the filter should be cleaned.
homogeneous filter bed. As soon as the bed is
loaded with solids, its efficiency will diminish Cleaning of Deep Bed Filters. Sand filters
and that is why the solution of the differen- can be cleaned by backflushing. The flow is re-
tial equation becomes rather difficult. Different versed to wash off deposited solids and flush
models exist to describe the process, but they them, e.g., to a wastewater station. Often air
are rarely used for practical purposes. To find a scour is used to increase the turbulence and re-
suitable filter medium in a deep bed filter which duce the amount of water necessary for fluidiza-
shows good retention efficiency over a long cy- tion. A typical set of data of a sand filter for
cle time, laboratory tests over a realistic cycle cleaning of water could be [12]:
time have to be carried out with filter layers of
realistic depth. Medium depth 1m
Medium size 0.5 – 1 mm (as uniform as possible)
The pressure drop in a deep bed filter can be Flow rate during 5 – 10 m3 m−2 h−1
interpreted as an effect of two different phenom- filtration
ena of blocking filtration: Flow rate air scour 60 m3 m−2 h−1 for 10 min
Flow rate water 15 – 30 m3 m−2 h−1 for 3 – 8 min after air
backflow scour
1) The filter media exhibit a resistance to flow,
which is increased by the solids deposit in
12 Filtration

Figure 10. A) Laboratory test equipment for sand filters

B) Pressure profiles in test filter [11]

During backflow the sand grains are classi- Special Variations of Deep Bed Filters. As
fied, the smallest ones are entrained to the top, mentioned above the sand grains are classified
the coarse ones sink to the bottom of the filter during backflush and the uppermost layer is
bed. This effect is undesired, since it leads to most efficient in collecting and becomes clogged
premature blocking of the top layer. Therefore rapidly by captured solids. This disadvantage is
it is important to use sand with grain sizes as diminished when a second layer of coarse mate-
uniform as possible. rial with lower specific weight is added on top of
the sand layer. During backflow these low den-
Sizing of a Deep Bed Filter. The sizing of a sity grains collect at the bed surface and form
deep bed filter consists of the following steps: a coarse layer able to retain a great quantity of
dirt (so-called multimedia filters or dual media
– Preselection of the filter material by com- filters, e.g., with a layer of anthracite particles
parative laboratory tests with small layers of 1 – 2 mm in size on top of a main layer of sand
different materials under standard conditions grains 0.5 – 1 mm in size.)
and with the filtrate quality as a criterion. Other designs of sand filters (especially in
– Selection of the right grain size in tests with the United States) convert the disadvantage of
a filter column of 1 m height and a realistic classification into an advantage by operating in
flow rate and pressure drop. If necessary the the upflow mode with filtering and backflush-
grain size must be adapted so that the bed ing from below. This offers the advantage that
is saturated (the filtrate gets turbid) at the large quantities of incoming dirt are retained
same time as the maximum pressure drop in the lower layer of sand, which contains the
is reached. If the maximum pressure drop coarser grains and larger pores. These upflow
is reached first, the grains should be coarser filters however need special safeguards against
and vice versa. breakthrough of dirt when the pressure drop be-
comes high.
 Filtration 13

In order to increase the retention capacity in parallel flow strong enough to flush off the finest
a given volume, it has also been proposed to fraction of particles in the suspension. (In most
use porous grains instead of sand grains. Small practical applications colloidal particles are also
pieces of polymeric foam have indeed this effect present and they are transported according to the
[13]. Cleaning by simple backflush is, however, mechanisms of ultrafiltration.)
not possible with this material, it must be cleaned
by backflush combined with compression, and
this method has therefore not yet found practical
application.

2.4. Cross-Flow Filtration

In cross-flow filtration the deposition of particles
on the filter membrane is prevented by a strong
flow parallel to the filter surface. This so called
cross-flow is achieved in most cases by pumping
the suspension through bundles of membrane Figure 11. Forces and transport effects onto a particle in
tubes (see Section 8.10, Figs. 77, 78). Alterna- cross-flow filtration
tively the cross-flow is achieved by rotating in- Br = Brownian motion; F A = adhesion to the membrane;
serts (Section 8.9, Fig. 76). The elimination of a F D = drag from the cross-flow; F F = friction force;
F L = hydrodynamic lift force; F Y = drag from then filtrate
cake enables to filter very fine particles, which flow
otherwise would form a cake with prohibitively
high resistance. Even submicron, nonparticulate
matter can be retained by semipermeable mem- Ultrafiltration retains colloidal particles or
branes according to this principle. In this chap- macromolecules. The cut-off sizes are ca.
ter a short overview will only be given, covering < 0.1 µm. Such particles are subject to Brow-
both the filtration of particles and the separation nian diffusion (Br in Fig. 11) and only weakly
of non-particulate matter. For more details see influenced by the hydrodynamic lift force [15].
→ Membranes and Membrane Separation. De- The smaller these particles are, the more they are
pending on the size of the “particles” retained, a transported away from the filter medium by dif-
distinction is made between microfiltration, ul- fusion. This is why in ultrafiltration the smaller
trafiltration, nanofiltration, and reverse osmosis. particles are preferably swept away and the big-
Typical parameters of cross-flow filtration are ger ones are collected on the membrane (con-
summarized in Table 1. trary to microfiltration). The cut-off size of an ul-
trafiltration is usually defined as the molar mass
Microfiltration retains solid particles (see (in g/mol) of a test suspension (generally protein
Section 8.11). According to the usual definition or dextran molecules of defined molar mass in
of “solid particles” these are visible in the mi- the range of 103 – 105 g/mol). In practical appli-
croscope, hence > 0.1 µm in size. In steady-state cation the cut-off size depends not only on the
cross-flow filtration these particles are conveyed pore size of the membrane, but to a large degree
onto the membrane by convection due to the fil- on a “gel” layer on the membrane consisting of
trate flow and transported away from it by hydro- retained colloids.
dynamic lift forces due to the parallel shear flow
(forces F Y and F L in Fig. 11). For particles be- Nanofiltration is a relatively new technique
low a certain size the lift force becomes smaller combining features of ultrafiltration and reverse
than the convection, F L < F Y , and they are de- osmosis with a high selectivity. Its name is de-
posited on the membrane [14]. After deposition rived from its approximate cut-off size of some
they are retained by van der Waals’ adhesion nanometers or more exactly molar masses of
forces F A and not easily swept away even if there 200 – 1000 g/mol. This is achieved with special
is no filtrate flow (irreversible cake formation). nanofiltration membranes which still have pores
Steady state microfiltration therefore requires a of a defined size, but their retention depends
14 Filtration

on the electrostatic charge of the molecules to Curve 3 is still more realistic; taking into ac-
be separated (bivalent anions are typically re- count that a filter cake contains stagnant zones
tained). or dead-end pores, that are not reached by the
flow. They deliver their contaminant content by
Reverse osmosis retains molecules or ions diffusion to the effluent. Diffusion is an asymp-
using selective membranes without pores. Cer- totic process and depends on the time elapsed,
tain molecules permeate through the membrane not on the quantity of liquid. This curve is typ-
because they are soluble in the membrane mate- ical for most washing processes. The first part
rial. Other molecules are not (or less) soluble and depends on the “wash ratio”, the end however is
are retained (or concentrated) on the upstream an asymptotic process depending on time.
side of the membrane. A particular feature of When the curves 1, 2 and 3 were drawn, it was
reverse osmosis is the high pressure required to supposed that the mass m of contaminant elim-
overcome the osmotic pressure of the retained inated was contained in the pore volume V pore .
molecules. An important application is desalina- The integral below the curves is therefore the
tion of seawater. In the food industry it is applied same for all three curves:
to concentrate juices at low temperatures.
∞
m= c·dV = c0 ·Vpore (45)
0
3. Washing of Filter Cakes
Curve 4 finally depicts an example
3.1. Basic Effects, Mass Balances where the washing resembles an extraction
(→ Liquid – Solid Extraction) because the con-
The purpose of washing is to remove the mother taminant is not contained in the pores only,
liquor left behind in the cake after filtration when but also in the solid (liquid inclusions or solu-
this liquid is regarded as contaminant or must be ble solid matter). The integral under curve 4 is
recovered as a valuable component. Wash liquid therefore not related to the pore volume V pore
flows through the filter cake and displaces the but to a higher total quantity of contaminant.
mother liquor, a mixture of both liquids leaving Theoretically such curves could be used to
the cake as a wash filtrate. The concentration in determine the residual mother liquor content in
this filtrate may help to explain some basic facts. the cake from analyses of the filtrate. In prac-
In Figure 12 this concentration is reported as a tice this is impossible since the required residual
function of the filtrate volume V . In the begin- contents in the cake are much smaller than the
ning it is c0 = 1 (concentration of contaminant precision of such a mass balance. Nevertheless
in the mother liquor). Four characteristic curves analyses of the filtrate are often used to judge
are reported: the progress of washing. This is possible if an
Curve 1 represents the idealized piston flow. empirical correlation between the two concen-
The pore volume V pore is ideally displaced and trations in the filtrate and in the cake exists for
leaves the cake with the concentration c0 = 1. In the particular process. The validity of such em-
this idealized case the washing would be finished pirical correlation is, however, restricted to the
with a quantity of wash liquid V w equal the pore particular equipment and operating parameters.
volume or a
Vw
“washratio = =1 (43) 3.2. Example of Experimental Results
Vpore

Curve 2 takes into account that even in an ide- An illustrative example of a washing process is
alized cake the flow passes through streamlines given in Figure 13 A and B [16]. A kaolinite sus-
with different lengths and speeds. Because of pension contaminated with NaCl was filtered to
this “axial dispersion” the required wash volume varying cake thickness and washed with varying
is several times the pore volume or quantities of water. After every test the residual
salt content in the cake was measured and the re-
Vw
“washratio = >1 (44) sults are reported as a function of washing time
Vpore
 Filtration 15
Table 1. Typical parameters of cross-flow filtrations

Microfiltration Ultrafiltration Nanofiltration Reverse osmosis

Cut-off size > 100 nm 10 – 100 nm > 1 nm < 103 g/mol

103 – 105 g/mol 200 – 103 g/mol
Transmembrane pressure 0.02 – 0.5 MPa 0.2 – 1 MPa 0.5 – 3 MPa 2 – 20 MPa
Permeate flow 50 – 1000 L m−2 h−1 < 100 L m−2 h−1 < 100 L m−2 h−1 10 – 35 L m−2 h−1
Cross flow speed 2 – 6 m/s 1 – 6 m/s 1 – 2 m/s < 2 m/s
Important mechanism of screening by the pores of screening by the membrane electrostatic repulsion and solubility and diffusion in
retention the membrane and the gel layer screening the membrane
Important mechanism of hydrodynamic lift force back-diffusion back-diffusion back-diffusion
transport

Figure 12. Concentration of contaminant in the effluent of a filter cake during washing
a) Idealized piston flow; b) Effect of axial dispersion; c) Effect of diffusion from dead-end pores; d) Effect of contaminant
extracted from the solid

Figure 13. Residual concentration of salt in filter cakes of kaolin. The same test results are reported either as a function of the
quantity of wash water (A) or as a function of washing time (B) [16]
16 Filtration

and of wash ratio. (In contrast to Fig. 12 the wash in changing size and positions even in cakes with
ratio is related to the solids mass, not the pore no visible fissures or shrinkage. This is not sur-
volume. Also the residual content of the cake is prising because the contact forces between the
reported, not the concentration in the filtrate.) particles change dramatically when the ion con-
Figure 13 A shows how at the very beginning tent of the surrounding liquid is washed off (see
of the washing process the residual concentra- Section 6.2). The phenomenon has not yet been
tion depends on the wash ratio, disregarding the investigated thoroughly, but its stochastic effects
cake thickness. In this example this is true up to on the washing results should be similar to the
the dash-dotted line which corresponds to less above-mentioned “fingering”.
than a one-fold displacement of the pore vol-
ume. As the wash ratio increases to several times
the pore volume, the mechanism of axial disper-
sion becomes more important, and the effect of
a given quantity of wash liquid becomes better
for thick cakes than for thin ones.
Figure 13 B shows how at the end of an exper-
iment the washing time is the most relevant pa-
rameter for the result. In this example this seems
to be true below a residual concentration of
c
≈ 10−3
c0

3.3. Test Procedures and Pitfalls

As can be seen in Figure 13, washing of filter

cakes gives scattering results even under labo-
ratory conditions. This explains why only few
experimental results are found in the literature:
many experimentators are discouraged by incon-
clusive test results and never publish them. The
reason of scattering results are stochastic influ-
ences:

Fingering. In most washing processes the

wash liquid has a lower viscosity than the mother
liquor. It tends to flow through the cake in finger-
like streams past isles of viscous fluid, as shown
in Figure 14 [16]. This is a stochastic process,
and the local concentration in the cake and the
momentary concentration in the effluent will
vary stochastically. Scale-up from a laboratory Figure 14. Visualization of “fingering” flow in a transparent
test filter with only small-scale fingering can be laboratory nutsche filter. A wash liquid of lower viscosity
displaces dark mother liquor [16]
misleading as well as the results of few small
samples taken from a big cake. If shrinking during washing presents a seri-
ous problem, it can be helpful to reslurry the cake
Instabilities, Shrinking. If small electrodes in wash liquid and filter it again. Many nutsche
are placed in a filter cake during the washing pro- filters (see Section 8.8) are used this way. The
cess, they indicate wildly varying local conduc- second cake (with less ions in the liquid during
tivity. This reveals the existence of small cracks cake build-up) is often less porous and less prone
 Filtration 17

to shrinking (but also less permeable) than the amount of mother liquor to be washed out.
original one. Sometimes however this “intermediate” deli-
In order to get meaningful results from wash- quoring has detrimental effects:
ing experiments in spite of all these pitfalls, If deliquoring is done by gas pressure, cracks
the following procedure is useful (see Fig. 15). may appear which let pass the washing liquid
Wash liquid flows at constant pressure through (see Section 4.1.5). In this case any deliquoring
the cake. The quantity of filtrate and its compo- before the washing has to be avoided carefully.
sition are recorded automatically. Often the pH On belt filters (see Section 8.2) an overlap of
and the conductivity Q of the filtrate are used as filtering and washing zones is therefore often
indicators for concentration; sometimes its color accepted, even if mother liquid and wash liq-
may be more informative. The washing is con- uid get mixed. Some nutsche filters (Section 8.8)
tinued until the filtrate reaches a pre-set crite- have even been equipped with optical sensors to
rion for purity (chosen according to some pre- avoid premature deliquoring [17]. They measure
liminary experience so that cake purity is near to the light reflected by the liquid surface and detect
the required specification). At this point the flow when the cake surface runs dry, so that the gas
of wash water is automatically stopped. This pressure can be released before cracks appear.
should be done automatically, since it will prob- If deliquoring is done by compression (see
ably happen during the night. The next morn- Section 4.2), the cake may get rather imperme-
ing, the cake is deliquored by air blowing and able. Thus, according to a rule-of-thumb the ap-
its residual content is analyzed. In small-scale plied pressure should be raised monotonously
experiments the whole cake should be analyzed, during the sequence of filtering – intermediate
in large-scale experiments several samples must deliquoring – washing – final deliquoring, i.e.,
be taken from different parts of the cake. the squeezing pressure for intermediate deli-
quoring should be lower than the pressure for
washing.

4. Deliquoring of Filter Cakes

4.1. Deliquoring by Gas Pressure

The moisture in the pores of a filter cake can be

displaced by gas flowing through the cake under
pressure. The residual saturation with moisture
as a function of time then asymptotically ap-
Figure 15. Test arrangement for washing test proaches a final equilibrium value as represented
in Figure 16. Thus, an equilibrium is established
The following results must then be evaluated: with regard to mechanical displacement of the
– The required washing time, liquid. Thermal drying by airflow will of course
– The required quantity of wash liquid, and further reduce the moisture down to total dry-
– The resulting purity of the cake. ness if the air flows long enough. But gener-
ally thermal effects are small as compared with
Each of these criteria taken alone will scatter
mechanical effects because of the comparably
stochastically, but all three together will often
small mass of air flowing through a filter cake
allow a meaningful interpretation.
[18].
The final “equilibrium” moisture for mechan-
ical dewatering depends on the nature of the cake
3.4. “Intermediate” Deliquoring before
and the applied pressure difference. The initial
Cake Washing deliquoring speed however depends in addition
Normally it is advantageous to deliquor the on the cake thickness. For both values the flow
cake partly before washing, thus reducing the rate of gas is apparently without importance, if
18 Filtration

it is not to produce the pressure difference. In down to an irreducible saturation S ∞ after infi-
the next sections first the equilibrium conditions nite time beyond which no further reduction is
will be examined. reached. This corresponds to the amount of liq-
uid, which is trapped in isolated domains within
the cake.
Figure 18 also shows the imbibition curve.
When the pressure is reduced again, and pro-
vided the bottom of the cake is still in contact
with the expelled liquid, then the cake will be re-
imbibed by capillary suction. At equal moisture
content the suction pressure will be smaller than
the capillary pressure difference for deliquoring.
Figure 16. Deliquoring by gas pressure – residual saturation This is easily explained because the capillary
as a function of time pressure for imbibition depends on the larger
“waist”-diameter of the pores (see Fig. 18):
4.1.1. Equilibrium Saturation of Filter 4·σ·cosδ
pci = (47)
Cakes dpore,waist

A plot of saturation of the cake versus pressure Also imbibition does not go to full saturation,
difference in an equilibrium state is called a cap- because some air remains trapped in the pores.
illary pressure curve. It can be measured in a The following conclusions can be drawn from
device according to Figure 17 [19]. The satu- the capillary pressure curve:
rated filter cake (b) is placed in the filter (a) on
1) Deliquoring is caused by pressure difference
a semipermeable membrane (c) (the membrane
between gas and liquid. Gas flow is normally
is permeable for liquid, but it is impermeable
required to maintain this pressure difference,
for gas at the applied pressure). Gas pressure is
but not for the deliquoring itself. No gas
applied via port (e). The quantity of liquid dis-
flow is necessary if the cake is placed on a
placed from the cake is drained by the valve (d)
semipermeable membrane, which is imper-
and collected. (The standpipe is used to obtain
meable for gas. (This principle can also be
an exact liquid level when the pressure gauge is
used technically for dewatering without gas
adjusted to zero).
flow [20]).
A typical capillary pressure curve is shown
2) A certain threshold pressure must be ex-
in Figure 18 (incompressible cake of glass beads
ceeded before liquid is displaced from the
with a mean diameter of 79 µm and water). Start-
pores; this is the capillary entry pressure pce .
ing from the completely saturated cake (S = 1)
This implies technical consequences:
the gas pressure is slowly increased, at each
Vacuum filters are restricted to pressure dif-
set point the equilibrium is established and the
ferences < 1 bar. This means that cakes can-
quantity of displaced liquid is registered, yield-
not be deliquored by suction if their pce is
ing a point of the deliquoring curve. Liquid is
near or above this limit. A pressure filter
displaced from the pores when the pressure ex-
with ∆p> 1 bar has to be considered for such
ceeds a certain threshold pressure. This is the
cakes, even if its installation is much more
capillary entry pressure pce (in this example
expensive than that of a vacuum filter. Theo-
0.062 bar). Each time when a pore is emptied,
retically suction can dewater filter cakes with
the gas pressure overcomes the capillary pres-
pores > ca. 3 µm: with pure water and a small
sure at the neck of the pores with a diameter
contact angle (δ ≈ 0) Equation (46) yields
d pore,neck :
p = 1 bar for d pore = 2,9 µm.
4·σ·cosδ
pce = (46) Filter cakes of submicronic particles like
dpore,neck
wastewater sludge have such a high capillary
Further increase of the pressure displaces liq- entry pressure that their pores cannot be dewa-
uid from finer pores and reduces the moisture tered mechanically: with pure water and a small
 Filtration 19

Figure 17. Test installation for measuring the capillary pressure pk [19]
a) Filter vessel; b) Filter cake; c) Semipermeable membrane; d) Draine; e) Entry for gas

contact angle Equation (46) yields p > 10 bar for sure onto the adjacent liquid and both gas and
d pore < 0.29 µm. liquid flow in the same direction, however with
different speeds and different pressures (the lo-
cal pressure difference between gas and liq-
uid is equal to the local capillary pressure).
The difference in saturation between bottom
and top of an incompressible filter cake is nor-
mally rather small, see Figure 19 left. This is
in contrast to the deliquoring by gravity (or by
a centrifugal field), shown in Figure 19, right.
In this latter case always a saturated bottom
layer exists, corresponding to the capillary suc-
tion height of the cake. Even in equilibrium this
layer remains saturated. Sometimes this height
is negligibly small. In scraper-type centrifuges
(→ Centrifuges, Filtering) for example, the sat-
urated bottom layer must in any case be smaller
than the residual layer which the scraper does
not remove.
The permeability of a completely saturated
cake is the same if either liquid or gas flows
Figure 18. Example of a capillary pressure curve for imbi- through the pores. When, however, gas and liq-
bition and for deliquoring [19] uid flow simultaneously through the cake, the
pores filled with liquid and the pores filled with
gas form two separate capillary systems, each
4.1.2. Kinetics of Deliquoring by Gas of them with reduced permeability. The local
Pressure permeabilities (for liquid or air) in relation to
the permeability of the saturated cake are called
In most cases there is no semipermeable mem- “relative permeabilities” k rel . They depend on
brane below the cake but a “normal” filter the local saturation of the cake and can be repre-
medium that is permeable for gas, like a fil- sented as:
ter cloth. Gas and liquid flow simultaneously for the wetting fluid (the liquid)
through the cake. The gas exerts capillary pres-
20 Filtration

Figure 19. Kinetics of deliquoring by gas blowing (left) and by gravity or a centrifugal field (right)

are known, the local values of capillary pressure,

kw α gas permeability, and liquid permeability are de-
krel,w = = (48)
k αw fined as functions of the local saturation. The
for the non-wetting fluid (the gas) deliquoring kinetics by gas flow can then be de-
scribed mathematically. The resulting system of
kn α interdependent differential equations is however
krel,n = = (49)
k αn extremely complex and not suited for practical
Such relative permeabilities are shown schemat- application. For scientific purposes approximate
ically in Figure 20 as a function of cake satura- solutions have been verified by comparing them
tion [21]. The permeability for the liquid (the to experiments [19].
wetting phase) declines to zero at a finite satu-
ration. This value corresponds to the irreducible
saturation S ∞ . At the other extreme the flow of 4.1.3. Approximate Solution for Coarse,
air ceases when the saturation is above 90 %. Incompressible Cakes
Some of the voids are filled with air without al-
lowing an appreciable airflow. For the particular case of incompressible cakes
with threshold pressures much smaller than the
applied gas pressure pce  p (hence for rather
coarse solid particles), Wakeman has described
the process of deliquoring by gas pressure by
three dimensionless parameters [22]:
reduced saturation
S
SR = (50)
1 − S∞

dimensionless time
pce ·t
Θ= (51)
αH ·η·H 2 · (1 − S∞ ) ·ε

dimensionless pressure difference

pentry pexit
∆P = − (52)
pce pce

Figure 20. Relative permeability as a function of saturation According to this approach, the cake is charac-
[21] terized by its porosity e, the filter resistance αH
If the curves for capillary pressure and for the (of the saturated cake) and the capillary pressure
relative permeabilities as a function of saturation curve which itself is approximately described by
 Filtration 21

the capillary entry pressure pce and the “irre- 4.1.4. Practical Scale-Up of Deliquoring by
ducible” saturation S ∞ (see Fig. 18). The rela- Gas Pressure
tive permeabilities are described by generalized
interpolation formula. With these approxima- The deliquoring kinetics are normally investi-
tions the residual saturation and the theoretical gated by measuring the residual moisture as
gas flow rate can be read from the dimensionless a function of cake thickness, blowing time,
charts, shown in Figures 21 and 22. An exam- and pressure difference. The results are interpo-
ple how to apply these charts is given in [23]. lated to give the parameters necessary for scale-
However, the validity of these charts is limited up. Extrapolation beyond the investigated range
to pce  p and to incompressible cakes. Also the of cake thickness, blowing time, and pressure
gas flow rate indicated on the chart does not take should be avoided. In addition it is important to
into account the possibility of cracks in the cake measure and to scale-up the gas flow from realis-
which can increase the gas flow tremendously tic experiments, since in most cases the capacity
(see Section 4.1.5). of the compressor is the limiting factor, not the
pressure. Particular attention has to be paid to the
possible formation of cracks. In case of doubt,
a filter test with sufficiently large filter area is
recommended, because the cracks may not be
pronounced and obvious on a small laboratory
filter. Typically the cracks appear at a charac-
teristic liquid saturation which then represents
the limit for deliquoring by gas blowing with
technically reasonable gas flow rates (see Sec-
tion 4.1.5).
Interpolation of the test results with a mini-
mum of tests is made easier if the residual mois-
ture is reported as a function of a dimensionless
time Θ. The results from a given kind of fil-
ter cake are then supposed to fit approximately
Figure 21. Reduced cake saturation vs. dimensionless time a straight line in a logarithmic chart. As a first
[23] approach, when nothing is known about the del-
iquoring behavior of the cake, the experimental
values are reported as a function of
∆p·t ∆p·t
Θ0 = ≈ const· (53)
η·H · (α·H + β) H2

Here ∆p = pentry − pexit is the pressure dif-

ference applied. This approach gives gener-
ally good results for centrifugal dewatering, as
shown in Figure 23 (the pressure difference be-
ing calculated from the centrifugal force) [24].
For dewatering by gas blowing, the fit is how-
ever often unsatisfactory (see Fig. 24) [24]. A
dimensionless time taking into account the cap-
illary entry pressure pce will always permit a
good fit. Two equations are proposed in the lit-
erature [24]:
 
∆p·t pentry pce
Θ1 ≈ · · 1−
Figure 22. Reduced air (gas) flow rate vs. dimensionless η·H · (α·H + β) pexit ∆p
 
time (Wakeman and Purchas 1986; reproduced from [23]) ∆p·t pentry pce
≈ const· · · 1− (54)
H 2 pexit ∆p
22 Filtration

and [25] gas blowing. When the remaining “shrinking po-

  tential” (this is the remaining shrink when the
∆p·t 2 pce
Θ1 ≈ · · 1− cake is reduced to total dryness) is small enough,
α·η·H 2 ε ∆p
  no cracks will appear anymore [27]. Some fil-
∆p·t pce
≈ const· 1 − (55) ters are equipped for this purpose with mem-
H2 ∆p branes or with pressure belts (see Sections 8.6
Here pentry and pexit are the pressures applied and 8.10). According to a proposal of Shirato
above and below the cake and pce is the capil- and coworkers this compression can also be
lary entry pressure. This pce is not measured, but achieved by adding a layer of very fine mate-
derived as a “best fit” to the experiments (this is rial (hence a cake layer with high pce ) onto the
why the fit is generally rather good, see Fig. 25 surface of the cake [28].
[24]). Some remedy against cracks is also possible
with nutsches equipped with agitators (see Sec-
tion 8.8). With their paddles they smear over the
4.1.5. Shrinking and Cracks in Filter Cakes surface of the cake during deliquoring so that the
cracks are closed as soon as they appear. This
Deliquoring of compressible filter cakes by gas does, however, not eliminate the cracks totally
pressure very often produces cracks in the cake, but only down to a certain depth below the sur-
a problem of great practical impact. The mech- face of the cake, so that some cracks can exist
anism of crack formation is represented in Fig- invisibly below the surface. Without such equip-
ure 26. During filtration the viscous forces from ment the formation of cracks can be reduced
the flowing liquid compress the cake. As de- (but only to a very limited degree) if the cake
scribed in Section 2.1.4, only the layer near the is formed with high final filtration pressure, and
filter medium is subjected to the full amount of hence with somewhat less porosity.
pressure, while the “upper” layer of the cake re-
mains uncompressed and porous. When filtra-
tion is finished, the liquid surface reaches the 4.2. Deliquoring by Expression
cake surface. Before gas enters into the capil-
laries of the cake, the capillary entry pressure When soft filter cakes are compressed, the void
pce must be overcome. The surface tension of volume of the cake is reduced by expelling liq-
the liquid thus exerts a pressure p ≤ pce onto the uid, while the voids remain saturated with liquid.
cake, comparable to an elastic membrane spread Such compression often is applied in combina-
over the cake. As long as pce is not exceeded, the tion with a subsequent deliquoring by gas pres-
cake is compressed monoaxially like by action sure; it reduces the subsequent gas flow and pre-
of a piston, the cake thickness is reduced, but no vents the formation of cracks (see Section 4.1.5).
cracks appear. However, when pce is exceeded, But there are many applications where deliquor-
gas penetrates into the largest capillaries, and the ing by gas pressure is not possible, and expres-
solid structure is compressed by lateral forces. sion is the only way to reduce the liquid con-
This may lead to lateral compression of the cake tent by mechanical means. Classical examples
and hence to cracks. The criterion for cracks for applications of mechanical forces are juice
to occur thus probably depends on the lateral and oil pressing from fruits and also the dewa-
compressive strength of a cake after monoaxial tering of wastewater sludge in membrane filter
consolidation. But until now the precise mech- presses (see Section 8.10) or in pressure belt fil-
anism of crack formation is not understood and ters (see Section 8.2). Such sludges form filter
the great variety of crack patterns shown in Fig- cakes with very high capillary entry pressure pce
ure 27 [26] cannot be explained. so that deliquoring by gas blowing is technically
Cracks in a filter cake are very detrimental to not feasible.
further deliquoring and also to subsequent wash- Mathematical description of expression gen-
ing (see Section 3.4) because gas and wash liq- erally starts from modifications of the Terzaghi
uid flow through the cracks without great resis- model for soil mechanics. The ratio of liquid
tance and without effect. The only sure remedy collected to the amount of liquid, which can be
against cracks is compression of the cake before expressed, is [29]
 Filtration 23

Figure 23. Residual saturation of filter cakes dewatered by centrifugal force as a function of dimensionless time Θ0 [24]

Figure 24. Residual saturation of filter cakes dewatered by gas blowing as a function of dimensionless time Θ0 [24]

Figure 25. Residual saturation of filter cakes dewatered by centrifugal force as a function of the modified dimensionless time
Θ1 [24]

H1 − H (t) different compression models can be found in

Uc = = 1 − B ·exp (−C ·t) (56) [30].
H1 − H∞
where U c is the consolidation rate, H(t) the
cake thickness, H 1 the original cake thickness 5. Optimal Cycle Time
and H ∞ the thickness after infinite time. B and
C are “creep” constants and t c is the consoli- When sizing a filter installation, the right cycle
dation (= compression) time. A comparison of time has to be chosen (example: the same task
24 Filtration

Figure 26. Formation of cracks by gas blowing through a compressible cake

Figure 27. Patterns of shrinking cracks [26]

can be performed in a small filter which must be est overall throughput is obtained when the
cleaned frequently or a bigger one with longer straight line from the start of this regenera-
cycles). With a long filtration time the filter cake tion to the end of filtration is tangential to
becomes thick and the flow rate per filter area the yield curve. In other words: the filtration
declines. On the other hand for very short fil- should be stopped when the instantaneous
tration the downtime for frequent cleaning will flow (as indicated by a flow meter) falls be-
reduce the capacity. This leads to two questions: low the mean throughput according to the
(1) What is the optimal cycle time with the high- definition:
est overall throughput? (2) What is the optimal
cycle time with the lowest overall cost? V
V̇mean = (57)
t + treg
1) Figure 28 shows the quantity of filtrate pro-
duced as a function of time. Before the start This criterion can for example be imple-
of filtration a time t reg is needed for regen- mented in a computerized process control.
erating the filter (extracting the cake from For design purposes it can be useful to cal-
the previous cycle, cleaning the filter, rear- culate the optimal cycle time in advance. For
ranging the filter elements, etc.). The high- this purpose a rule-of-thumb will be derived
 Filtration 25

assuming cake filtration and negligible resis-

tance of the filter medium (β = 0). The quan-
tity of filtrate according to Equations (14) or
(15) is then

V = c1 ·t1/2 (58)
and Equation (57) becomes

c1 ·t1/2
V̇mean = (59)
t + treg
The highest V̇ mean is obtained if the filtra-
tion is stopped at t opt , which is defined by Figure 28. Optimal cycle time derived from the yield curve.
the differential equation t opt,1 for maximal flow per time and t opt,2 for maximal
  yield per cost
d 1 1 −1/2
=0= ·t (60)
dt V̇mean 2c1 opt
treg −3/2
− ·t
2c1 opt
This leads to the rule-of-thumb for maxi-
mum throughput:
topt,1 = treg (61)
2) Quite analogous considerations are valid for
the optimal cycle time in terms of cost per
quantity filtered. During filtration, the run-
ning cost is proportional to time (capital
cost and pumping energy), cost = c2 t. In Fig-
ure 28 all costs are converted with this pro-
Figure 29. Filter resistance vs. particle size
portionality factor c2 into an equivalent run- The range of usual values is compared to the calculated lines
ning time: t = cost/c2 . according to Carman – Kozeny, Equation (66)
Regeneration represents a considerable cost,
including downtime, labor, new filter ele-
ments, and disposal of waste. If this cost is These rules have been derived here for con-
called creg , the mean specific cost is stant pressure filtration. They can also be derived
cost c2 ·t + creg for filter runs with different but constant flow
= (62) rates until a pre-set final pressure. Practitioners
filtrate V
With the approximation of Equation (58) therefore apply the rule-of-thumb rather gener-
this is ally (e.g., also for filtration with a pump with a
characteristic curve anywhere between constant
cost c2 1/2 creg −1/2 pressure and constant flow).
= ·t + ·t (63)
filtrate c1 opt,2 c1 opt,2
The minimum is defined by
 
d cost c2 −1/2
dt filtrate
=0= ·t
2c1 opt,2
(64) 6. Understanding the Filter
creg −3/2 Resistance
− ·t
2c1 opt,2
As result the rule-of-thumb for maximal 6.1. The Equation of Carman and
yield per cost is obtained: Kozeny

c2 ·topt,2 = creg (65) The resistance α of a filter cake depends on the

size and number of pores in the cake. In a first
or “cost for the filter run = cost for regener-
ating the filter”.
26 Filtration

approximation it can be related to the size of – Van der Waals forces are part of the cohe-
particles and the porosity of their arrangement sive forces between the molecules within the
according to the classical Kozeny equation [31]. solid particle. They reach also a certain dis-
(The theoretical basis of the Kozeny equation is tance beyond the surface, but their range is
subject to criticism, see for example [32], never- less than that of electrostatic forces. The de-
cline is proportional to the distance accord-
theless the Kozeny equation is a very useful ap- ing to
proximation. More recent correlations are given
const
in [33].) For spherical particles this equation is: Eattraction = − (67)
r
2
(1 − ε) ·36 When two particles approach to distance
αH ≈ 5· (66)
ε3 ·d2S zero, these attractive forces become very
where ε is the porosity of the cake and d S is the strong and should in principle become equal
Sauter mean diameter of the particles, i.e., the to the cohesive force inside the particle. The
diameter giving the same specific surface. The reality is, however, more complicated be-
filter resistance resulting from this equation is cause there are always absorbed molecules
depicted in Figure 29 as a function of particle on the surface.
size d S and porosity ε. In practical applications An example of the superposition of both
the filter resistances cover a very wide range of forces according to DLVO theory is represented
porosity. Fine particles, especially dry dust, of- in Figure 31. The graph shows the resulting en-
ten form cakes with surprisingly high porosities ergy potential. A positive gradient of the curves
(see Fig. 30). The same quantity of powder (fil- describes attraction, negative gradient repulsion.
ter aid, mean particle size ≈ 5 µm) has settled in At very small distances, attraction prevails. At
water with different pH and in air. The settling larger distance electrostatic repulsion prevails (if
volume (and the clarity of the supernatant) is it is not zero).
quite different. Filter resistance depends there-
fore to a large degree on cake porosity and hence
on the surface forces producing this porosity!

6.2. Interparticle Forces, DLVO Theory

According to the theory of Derjaguin,
Landau, Verwey, and Overbeek (= DLVO
theory after the researchers’ initials), the forces
between suspended particles of equal material
are described by repulsion due to electrostatic
charges and attraction due to van der Waals’
forces:
– Particles in suspension (especially in po-
lar liquids like water) have an electrically
charged surface, due to adsorption and disso-
lution of ions. The order of magnitude of this
charge ζ is − 120 mV < ζ < 120 mV, and it
depends on the pH of the liquid. The charge
reaches relatively far, depending on the ion
content of the surrounding liquid. The reach
is characterized by the Debye length r D .
In pure distilled water this length is excep-
tionally long with 0.9 µm. In most technical Figure 30. Settling volumina of the same quantity of fil-
aqueous solutions it is much smaller, in sea ter aid (mean particle size ca. 5 µm); left: in water at pH 7;
water for example only 0.4 nm [34]. center: in water at pH 2; right: dry powder compacted by its
own gravity [44]
 Filtration 27

tral (point of zero charge, isoelectric point). At

this particular pH, the particles can more easily
agglomerate and are easier to filter. This opti-
mal pH is often determined empirically without
knowledge of the zeta potential.

Figure 31. Energy potential vs. particle distance (DLVO-

theory)
Attraction and repulsion between two particles in suspen-
sion. The superposition of electrostatic repulsion and attrac-
tion by van der Waals forces is represented by the resulting
energy potential. High ion content in the surrounding liquid
reduces the reach of electrostatic repulsion (Debye length).

Concerning interparticle contact this means:

– Electrostatically charged particles repulse
one another. Seen from their equally charged
neighbors they show some kind of smooth
and slippery repulsive skin. (The smooth re-
pulsive skin can be made visible with modern
atomic force microscopy, see, e.g., [35].) The
Debye length characterizes the thickness of Figure 32. A particle in suspension
this skin (see Fig. 32). Seen from a particle with the same surface charge, it is co-
vered with a repulsive skin of a thickness near the Debye
– Without electric charge (as for example in length. This skin has no roughness and no friction; hence it
air), there is no such skin. The particles touch is rather slippery.
their neighbors with their rough surfaces and
tend to adhere due to van der Waals’ forces.
This explains why the dry powder in Fig- 6.3. Mathematical Simulation of Cake
ure 30 has the lowest packing density. Formation
– Particles in aqueous suspension with weak
electric charge most probably have oppo- Different attempts have been made to simulate
sitely charged patches on their surface what numerically the structure and porosity of filter
may enhance mutual adhesion and the for- cakes. Until now such calculations are restricted
mation of loose flocs. to spherical particles with homogeneous surface.
Starting from randomly chosen locations the tra-
The surface charge of suspended particles can jectories of particles in a filter flow are calculated
be measured as a “zeta potential” (→ Colloids, (generally in two dimensions). When they touch
Chap. 4.; → Emulsions, Chap. 11.6.). This po- the cake surface, the deposition is simulated us-
tential varies with the suspending liquid, espe- ing either a sticking angle [36], [37], or a fric-
cially with its pH: High pH means a high concen- tion angle and an adhesive force [38], [39], or by
tration of OH− ions, which can be absorbed, cre- estimating the interparticle forces from van der
ating a negative surface charge. Low pH means Waals’ and electrostatic forces according to the
high concentration of protons and a positive sur- DLVO theory [40]. After calculating the deposi-
face charge. At a certain pH the surface is neu- tion of a large number of particles, the packing
28 Filtration

density of the resulting cake is found. These cal- dency to slip into densely packed positions when
culations help to understand and explain some deposited on the filter cake.
empirical facts:
1) High adhesion forces and large friction an-
gles make the particles adhere at the first con-
tact and produce a randomly stacked “house
of cards” with high porosity and permeabil-
ity. Low adhesion forces or even repulsion
between the particles make them slip to more
stable positions and produce dense packing.
Figure 33 shows as an example of the cake
structure calculated for different friction an-
gles and adhesive forces [39].
2) An opposite effect can be observed when the
particles are very small (colloidal). Here the
Debye length is often not negligible com-
pared to the particle size and the repulsion
can be strong enough to keep the particles at
a distance. In this case the porosity and per-
meability will increase by repulsion and de-
crease by adhesion, contrary to what was said
above. This is for example observed with
clay soil in marshland near the sea. The per-
meability of such soil is reduced after flood-
ing with salt water and increases again when
the salt is washed out, i.e., the Debeye length
increases with falling ion content. For indus-
trially filterable suspensions however the ef-
fect is not yet reported in the literature. It
seems that for particles > 0.1 µm either the
Debye length is to small (at high ion content)
or the zeta potential is not strong enough (as
in distilled water) for this effect.
A comprehensive simulation of cake forma-
tion has not yet been proposed. The above men-
tioned approaches are restricted to spherical par-
ticles with uniform surface charge. Often, how-
ever, the electric charge is unevenly distributed, Figure 33. Simulation of the cake build-up for two differ-
and there may even exist oppositely charged ent adhesion forces and friction angles (upper diagram for
4 × 10−8 N adhesion force and 20◦ friction angle, lower
spots on the same particle. This would explain diagram for 1 × 10−8 N and 5◦ ) [39]
why many suspensions form loose flocs when
the stirrer is stopped. This is quite often ob-
served even if the pH is not exactly at the iso- 7. Solving Filtration Problems in
electric point (the term “isoelectric range” would
therefore be more appropriate than “isoelectric
Small-Scale Tests
point”). The flocs disappear when the stirrer
starts again, but nevertheless they probably have
7.1. Laboratory Tests
an impact on filterability because the particles The most common technique for laboratory fil-
are prearranged in a way that they touch with ter tests uses a laboratory pressure filter accord-
their rough, adhesive spots and have less ten- ing to Figure 34 [41]. It consists of a pressure
 Filtration 29

vessel about 16 cm long with a filtration area of lated from pressure drop and flow rate according
20 cm2 (corresponding to a diameter of 50 mm). to Equation (1) or (3).
Suspension (250 – 300 cm3 ) is charged into the
filter, and the lid is closed. Filtration starts when
pressurized gas (air or nitrogen) is applied from
above. This should be done quickly (within a
few seconds) to prevent sedimentation. The fil-
trate is collected in a vessel on a balance or in a
graduated cylinder and its quantity is registered
as a function of time. When the filtration is fin-
ished, the compressed gas is applied for about
another minute to deliquor the cake. The quan-
tity of gas applied during deliquoring is mea-
sured with a flow meter or it is estimated from
the capacity of the feed line and its pressure
drop on gas withdrawal from the feed. After fil-
tration and deliquoring the filter is opened, the
cake thickness is measured and the cake is re-
moved to determine its wet and dry mass and
calculate the moisture content. The quantity of
filtrate obtained is interpreted in a linear dia-
gram (see Section 2.1.3) and the corresponding
filter resistance is calculated. Several measure-
ments at different pressures (e.g., 0.5 + 1 + 6 bar)
provide the compressibility coefficient “n” from
Equation (31). For more details see [42], [43]. Figure 34. Bench pressure filter with balance and recorder
Another very simple test is the bench leaf test. for yield curve
The filter leaf includes a filter cloth fixed on a a) Compressed air; b) Heating fluid; c) Filter medium; d) Fil-
plate (100 cm2 ) with grooves and sealing around trate; e) Balance; f) Recorder
the edges. It is connected to an evacuated filtrate
receiver via a rubber hose with a valve. The filter
leaf is plunged into the suspension and filtrate is 7.2. Handling of “Unfilterable”
sucked through the leaf by applying of vacuum. Suspension
It requires, however, considerable skill to get
In industrial filtration often suspensions are en-
well reproducible results with this arrangement,
countered with a high filter resistance. Several
since the solids are sucked to the leaf against the
possibilities for handling of these “unfilterable”
effect of settling, and their composition depends
suspensions are given below.
on the way the leaf is plunged into the suspen-
sion. This is why the bench leaf test is used less Optimization of Upstream Steps (Crys-
frequently nowadays, only for sizing rotary vac- tallization, Precipitation). Considerable im-
uum filters, which operate in a quite similar way. provements in filterability are achieved by
For research purposes it may be interest- producing coarser particles. Good knowl-
ing to measure the filter resistance as a func- edge is available about crystallization
tion of compressive pressure. To this behalf the (→ Crystallization). If, however, the solids are
Compression-Permeability Cell (CP cell) has formed by precipitation, i.e., by mixing two
been developed (see Fig. 35). This is a cylin- reactants, this quick process often depends
drical cell with a porous bottom and a porous strongly on the mixing conditions and the reac-
piston from above. Mechanical load is placed tion speeds. In this case the filterability must be
on the piston and the filter cake is compressed. improved empirically. Improvement has been
Then liquid is percolated through the cake with achieved with the following parameters:
moderate pressure and the permeability is calcu-
1) Continuous mixing instead of batch mixing,
30 Filtration

Figure 35. Compression – permeability cell

a) Filter cell; b) Filter cake; c) Filtrate receiver; d) Pressure recorder; e) Pump; f) Slurry tank; g) Recirculation; h) Movable
plate

2) Recycling of suspended solids to the zone of Criteria for the flocculation effect are settling
solids formation, speed, clarity of the supernatant, and aspects of
3) Variation of temperature, mixing ratio, stir- the flocs (small, dense flocs are sometimes pre-
ring speed etc. ferred, because they are more stable).

Application of Flocculants (Polyelec- Adaptation of pH. As explained in Sec-

trolytes). Synthetic, water-soluble polymers are tion 6.2, the interparticle forces depend on the
highly effective as flocculating agents. They ag- pH of the surrounding liquid. With a pH in the
glomerate fine particles in aqueous dispersion isoelectric range the particles can aggregate and
to voluminous flocs, which settle and filter eas- their filter resistance and settling speed is in-
ily. As a general rule, however, the resulting creased.
filter cake or sediment has a higher porosity and
residual moisture than without flocculation. Checking of Alternatives to Cake Filtra-
Synthetic flocculants are commercially avail- tion. Possible alternatives to filtration are pro-
able as nonionic, anionic, or cationic grades with cessing in:
more or less ionic character. A charge opposite – Settling centrifuges (→ Centrifuges, Sedi-
to the zeta potential of the solids to be separated menting) or static settlers. Even poorly fil-
gives theoretically the best effect. In practice it terable suspensions sometimes settle readily,
is, however, easier to observe the flocculation vi- either the solids have high specific weight
sually without knowledge of the surface charge. or big, soft flocs make an impermeable cake
Samples of the suspension are prepared in grad- (e.g., wastewater sludge).
uated cylinders and gently mixed with different – Cross-flow filtration (see Section 2.4). This
flocculants in 0.1 % solution. The high dilution alternative however yields the solids as a
is necessary to reduce the viscosity and facilitate thickened suspension only.
mixing. The required quantity of polyelectrolyte – Evaporation of the liquid (→ Evaporation).
is generally in the range of 0.5 – 10 kg per ton dry This alternative may be attractive if the re-
solids, equivalent to 10 – 100 mL of solution for quired energy is not to high (highly concen-
1 L suspension. trated suspension or a liquid with moderate
 Filtration 31

heat of evaporation, like many organic sol- Operation: discontinuous, continuous,

quasicontinuous, automatic
vents). self-controlling, programmed,
precoating
Filter element:
Selection of Filter Aids. Filter aids are inert
1) bag, belt, candle/cartridge, disk,
powders added to the liquid to be filtered and drum, leaf/plate, nutsche, press
increasing the porosity and permeability of the plate, tube
cake (see Chap. 11). They are very helpful, pro- 2) horizontal, vertical,
single-element, multi-element,
vided the presence of filter aid in the solid can stationary, rotating
be accepted. Filter aids are used in two ways: 3) open, closed

Solids discharge: scraper removal, vibration,

– As a precoat layer to protect the filter centrifugation, back blow, tipping,
medium and improve filtrate clarity and manual
– As a body feed to increase flow rates. Application: rapid settling systems, moderate and
slow settling systems, clarification
of liquids, pastes, pulps, sludges,
Preliminary laboratory tests help to identify and nonfluid systems.
the proper kind of filter aid. The selection pro-
cedure is done in three steps: Because of numerous overlaps with respect
1) Selection of the right material according to to process engineering and design, any system-
the chemical resistance and purity (perlite, atic arrangement entails a loss of clarity. In the
diatomaceous earth, cellulose, carbon). descriptions that follow, the design element is
2) Selection of the grade (particle size) of the given top priority.
filter aid. The particle size should be as The principles of operation and the design
coarse as possible to give low filter resis- of filter equipment have changed little for many
tance, but fine enough to prevent the dirt par- years. Only with recent efforts to improve the
ticles from trickling through the pores of the economics of processes have some crucial de-
cake. For selection of the grade a precoat sign changes and additions taken place. The
layer is prepared by filtering a diluted sus- most important of these involve
pension of filter aid. Then the solution to be 1) automation of operating modes and cycles
cleaned is filtered through this layer. After 2) increases in specific throughput capacities
filtration the precoat layer is broken in half. and separation efficiencies, especially aimed
The dirt should form a separate layer on the at reducing residual moisture
top and should not have penetrated into the 3) optimization in the context of the overall pro-
precoat. cess
3) Selection of the quantity of filter aid. As a 4) improvement of operational reliability
first guess the quantity of filter aid is calcu- 5) increased concern for environmental protec-
lated which gives a cake volume equal to the tion and worker safety
volume of dirt to be separated. It is then ad- 6) adaptation to new, more difficult separation
mixed to the suspension and the filterability tasks
of this mixture determined. If the flow rate 7) development of new separation methods for
is to low, the next trial should be made with existing filtration problems
a higher quantity of filter aid.
For example, classical filter presses have been
replaced by completely automatic, unattended
equipment. Mechanical dewatering devices have
8. Filtration Equipment been installed on belt and drum filters. Classi-
cal open nutsches have been modified into “pro-
Filters can be classified in accordance with dif- cess filters,” which combine several downstream
ferent criteria: operations (e.g., washing, dewatering, and dry-
Solids retention: surface, deep-bed ing) in a single apparatus. For difficultly fil-
Filtration technique: cake, cross-flow, screening terable suspensions, dynamic filters with mem-
Driving force: pressure, vacuum, expression,
magnetic or electric field, capillary
branes have been designed; together with elec-
32 Filtration

trokinetic filters, these open up new possibilities open corner of the filter bag is sealed against
for mechanical liquid–solid separations. the filtrate pipe. In order to increase the filtra-
Important advances in the performance of ex- tion area, the bags are made up to three times
isting filters have come about through better un- wider than the inserts, so that folds are pro-
derstanding of the theoretical relationships in all duced when they are slipped on; in this way,
areas, such as filtration, washing, and dewater- the space requirement per square meter of fil-
ing and expression. In particular, the automation tration area is greatly reduced. Filter units up to
and optimization of processes, based on knowl- 250 m2 are available. After filtration, the bags
edge about the interactions of the many process can be cleaned by spraying and blowing with
parameters, are currently being pursued in ex- compressed air.
tensive programs.

8.1. Bag Filters

The filter element in this type of filter is a bag
made of the filter medium. A typical bag has an
opening at one end. The bags are mounted in var-
ious kinds of containers; they allow an uncom-
plicated design, are easy to service, and are rel-
atively versatile in view of the large selection of
filter media available. For example, solids in the
range of 80 – 800 µm are successfully collected
with bags made of fabrics woven from monofil-
ament yarns; solids between 1 and 200 µm are Figure 36. Pocket-type bag filter
separated with needled felt bags or by precoat
filtration (in which deep-bed filtration is active
at the same time). 8.2. Belt Filters
As batch filters, are opened by hand, they are
employed only where relatively small charges A belt filter resembles an ordinary belt conveyor
with extremely low solids contents are to be clar- driven by one of the guide rollers. Slurry is fed
ified. They therefore find use chiefly in clarify- onto the filter belt from above and the filtrate
ing and polishing filtration (sterilization), where drains or is pulled by suction from the bottom of
the solids to be removed are impurities or unde- the belt. Belt filters are operated as simple grav-
sirable byproducts. Applications include chemi- ity, vacuum and pressure filters. Whether oper-
cal and pharmaceutical products, paints and var- ation is continuous or intermittent (semicontin-
nishes, juices, edible oils, waxes and resins. uous), slurry is fed onto one end of the belt. The
Bags open on one side are charged from the filtrate drains into vacuum tanks, which can be
inside, so that the solids are collected as a fil- stationary or can move intermittently with the
ter cake in the bag. Service times range from belt. The cake can be washed and dewatered in
hours to days. In pressure bag filters, where the downstream zones. If necessary, the filter belt
bags are inserted in supporting cages, pressures is washed during recycling. In another design,
between 0.5 and 1 MPa are common; in special the belt is made up of a number of individual
designs, the pressures are up to 2.5 MPa. Ca- cells, which bear the filter cake. In this way, a
pacities are in the range of 1 m3 m−2 min−1 at more careful separation of the filtration stages
1.6 MPa. Filter units with several bags in hous- (see also Fig. 1) is achieved.
ings are available at total capacities of up to In general, belt filters are applied for read-
2.4 m3 /min (4.8 m3 /min maximum) and down ily filterable suspensions that contain coarser,
to quite small values. and therefore easily sedimented, solids (groups
Pocket-shaped filter bags are charged from F and M in Table 2), where the filtrate and the
outside; they are slipped over collapsible filter wash liquor are to be collected separately and the
inserts attached to the filtrate pipe (Fig. 36). The solids must have gentle handling. The maximum
 Filtration 33
Table 2. Filterability of cakes

Filtration characteristics Group of suspension, symbol

Fast Medium Slow Dilute Very dilute

(F) (M) (S) (D) (VD)

Initial cake formation rate, min/cm 0.005 – 0.1 0.1 – 1 1 – 10 10 – 100 no cake
Slurry concentration, % > 20 10 to 20 1 to 10 <5 < 0.1
Settling rate rapid medium slow slow
Leaf test rate, kg/m2 h > 2500 250 to 2500 25 to 250 < 25 no test
Filtrate rate, m3 /m2 h > 10 0.5 to 10 0.0025 to 0.05 0.025 to 0.05 0.025 to 0.05
Typical slurry crystalline solids salts pigments wastewater water

filtration area is 120 m2 . Fluctuations in product moves on. Slurry and wash liquors used are fed
call for control of the belt speed or slurry rate. continuously.
For especially sensitive filtrations, belt filters Vacuum belt filters are usually installed in
are used with filter media that remove the liq- open frames, or in closed housings if no va-
uid from the cake by capillary action alone. The por is to be released into the environment. Good
filter cloth runs over felt or similar filter media. filtration capacities and washing effects can be
achieved only with uniform loading of the filter
Vacuum Belt Filters. A continuous vac- medium or filter cake. For this reason, the feed
uum belt filter consists of the moving filter cloth and wash liquor are distributed over the width of
supported on a profiled elastomer transport belt the filter belt by flat nozzles or washing grooves.
(Fig. 37). To provide better sealing for the vac- Downstream dewatering of the filter cake is done
uum space, sliding belts can be placed under by double-belt expression (see twin-belt press,
the transport belt, or a specially shaped belt can page 36) or a plate press.
travel along with the filter cloth. The difficul- Because of the versatility of vacuum belt fil-
ties met with in ensuring a good vacuum with ters, they have found use in nearly every field of
moving seal systems are overcome when the fil- liquid–solid separations where slurries are rela-
ter belt or filtrate box move intermittently. Fig- tively easy to separate.
ure 38 shows an example. When the belt is sta- Even difficultly filterable slurries with com-
tionary, slurry is fed to the filter and at the same paratively finely dispersed solids can be sep-
time the filter cake is washed, dewatered and, arated on belt filters if suitable belt materials
if necessary, pressed. In the intermittent move- are employed and the solids do not immedi-
ment of the belt, the discharge roller shifts the ately block the medium. In such cases, pres-
belt, while the retaining roller holds the belt in sure is most commonly used instead of vacuum
place. The movement is compensated by move- (see page 36).
ment of the compensating roller in the opposite Belt filters for gravity and suction filtration
direction. The vacuum is let down when the belt offer low equipment costs. With a suitable filter
is moving. medium (nonwovens are generally used), they
Another continuous vacuum belt filter has can successfully clean up slurries that are not too
vacuum tanks of pan-shaped sections each 1.4 m highly concentrated (solids down to 50 mg/m3 )
long. Each section is divided into two parts with and of the filterability group F in Table 2. Feeds
flexible connections to the vacuum system (vac- include machine-tool cooling and cutting lu-
uum pumps). In this way the individual filtra- bricants (emulsions), electrolysis cell slimes,
tion stages are divided into arbitrary lengths as beer (for removal of turbidity and yeast), waste-
needed. The vacuum tanks are designed with waters, and chemical solutions.
grids that allow the filtrate to drain freely. Dur- A gravity or hydrostatic filter with a contin-
ing filtration, the tanks move along with the belt uous belt (Fig. 39) consists of a tank, in which
at the same speed, as the vacuum builds up. At a moving support belt made of coarse woven
the end of the co-moving path, the vacuum is fabric or a flexible belt forms a depression. The
broken and the tank vented, while the filter cloth filter belt proper rests on this support belt. Op-
eration is intermittent: slurry is fed in until the
34 Filtration

Figure 37. A), B) Vacuum belt filter (reproduced with permission of Dorr – Oliver)
a) Filter cloth take-up assembly; b) Feed box; c) Cake wash; d) Vacuum pan; e) Filter cloth; f) Filter cloth wash; g) Drip pan
drain; h) Drainage belt; i) Tensioning device; j) Filter cloth aligning; k) Drainage belt

Figure 38. Jerking-type vacuum belt filter (BAS Sonthofen)

a) Filter cloth take-up assembly; b) Cake wash; c) Vacuum trays; d) Filter cloth; e) Movable discharge roller; f) Cloth wash
assembly; g) Blocking roller; h) Tensioning assembly; i) Floating roller

increasing resistance to flow causes the liquid There are two designs of suction belt filters,
above the filter belt to reach a predetermined also called flat-bed filters. One, used chiefly for
depth. The hydrostatic head promotes the fil- wastewater treatment, consists of a receiving
tration rate. The belt is then advanced, the fil- tank for slurry, with a drag chain conveyor. The
ter cake carried out of the tank, and new filter perforated or slotted floor of the tank holds the
medium transported into it. The filtrate flow rate filtrate receiver, which is connected to the pump.
is 0.2 m3 m−2 min−1 . The filter medium is guided between the scrap-
ers and the tank floor. After a filter cake has built
 Filtration 35

Figure 39. Hydrostatic belt filter

a) Sludge bin; b) Float control; c) Filter trough; d) Filter medium; e) Carrier belt; f) Filtrate tank

up to a predetermined thickness, the increasing

pressure drop causes the conveyor to begin mov-
ing. It advances some 20 – 50 cm along with the
filter cloth. These filters are made with filtration
areas up to 21 m2 .
The other design consists of a vacuum tank
with lid; the paper filter tape is fed between the
tank and the lid. This type of filter also operates
intermittently. At a filter area of 1 m2 a through-
put of 0.1 – 0.5 m3 /h can be achieved, depending
on the amount of solids in the suspension and the
presence of filter aids.

Pressure Belt Filters. A pressure belt filter

of the flat bed type consists of a filtrate receiver Figure 40. Schematic processing in twin-belt pressure fil-
and a pressure chamber. The filter medium is ters
guided between the two chambers, which are
situated in a housing. Operation is necessarily This type of filter has made it possible to re-
intermittent, since the pressure chamber, which duce the relatively high 70 vol % residual mois-
is provided with slotted gates, is pressurized dur- ture in municipal sewage sludges by as much
ing filtration. In smaller units, the use of slotted as 10 vol %, corresponding to a decrease of
gates is replaced by pivoting up the pressurized 35.7 % in the moisture content per cubic meter
section. Pressure belt filters are also made with of sludge. Further applications have also been
expression devices (up to some 2 MPa). tested, and this class of filter has been adopted
A twin-belt pressure filter is a belt filter with for some dewatering jobs, such as slimes from
a second, co-moving belt, which exerts an addi- coal washing, large-scale animal husbandry, cel-
tional mechanical compressive load on the filter lulose and pulp production, electrolysis, and off-
cake with pressure rollers. Such a filter can be gas treatment. An average dewatering capacity
employed provided the cake is deformable. This for designs now current is 6 m3 of municipal
condition holds especially for bulky flocculated sewage sludge per meter of belt width and hour.
slimes such as occur with filter cakes made up of With sludges that are readily dewaterable, the
relatively fine solid particles (mainly of organic influent rate can be increased to 15 m3 /h.
origin) having a broad particle size distribution. Machines with multistage dewatering are
Twin-belt pressure filters have proved them- used in nearly all these sample applications. Fig-
selves for the dewatering of sewage sludges that ure 40 shows a simplified diagram. The floccu-
have been treated with polyelectrolytes (based lated sludge is put through preliminary dewater-
on poly(acrylic acid) and polyacrylamide) to ing in a simple screen drainage (rotating or flat
produce relatively large, stable flocs. screens), since part of the liquid bound up in the
36 Filtration

Figure 41. Twin-belt pressure filter (reproduced with permission of Flottweg)

sludge is released in the flocculation step. Vac- over rolls that vary in diameter, the cake is
uum filtration usually follows before the filter sheared and compressed (up to somewhat over
cake reaches the expression zone. 100 kPa). The modification of Figure 42 B ap-
A special feature of twin-belt pressure filters plies a further increased compressive load with
is that the belts change direction several times, a third moving flat belt.
on rollers that shear and press the cake, thus Figure 42 C shows a filter in which an over-
promoting its compaction. Usually the filtrate flow (for gentle handling of the flocculated
produced in the several stages, which is not en- solids) directly connects the flocculation vessel
tirely clear, is recycled to the first stage, where to the gravity filtration and dewatering stages;
the solids still dispersed in the filtrate are re- the filter cake passes downward through the suc-
flocculated. The filtrate resulting here is largely cessive expressing zones. The last stage is sup-
free of solids and can be passed on to, for exam- plemented by a device that exerts a controlled
ple, biological treatment. linear pressure.
Quite a variety of arrangements of the indi- Cake compression in twin-belt pressure fil-
vidual process stages and design features has ters is rather modest in comparison with the com-
come into being. The performance of these ma- pressions achieved in membrane filter presses
chines thus varies widely, being influenced as (see page 58). The twin-belt devices have the ad-
well by the properties of the influent sludges. vantage of continuous operation and relatively
Twin-belt pressure filters will find additional low cost. A recent development demonstrates
use in food treatment, for instance in juice ex- the possibility of reaching pressures in twin-
traction from fruits and vegetables. Figure 41 belt expressing filters that are similar to those
shows a typical arrangement of that twin-belt in membrane filters (up to 2 MPa). A filtration
press filters including horizontal press section zone with filter belts converging in wedge fash-
and several turns of the belts. Here the recov- ion is followed by compaction as the cake turns
ery of juice may reach 65 – 70 % in a 2500 mm around a drum pressurized by hydraulically ac-
machine and 7 – 10 t/h throughput. tuated elements.
In the modification of Figure 42 A, the sludge Experience and theoretical analyses (see Sec-
enters the expression zones from below, through tion 4.2) lead to the conclusion that optimal per-
a straining zone (gravity dewatering). Passing formance is attained in twin-belt pressure filters
 Filtration 37

Figure 42. Modifications of twin-belt pressure filters (A, B, and C)

a) Press zone; b) Gravity strainer zone; c) Pre-compression zone; d) Press belt high compression; e) Low compression zone;
f) Flocculation; g) Cake break-up; h) Line compression

when the cake is relatively thin, the filtrate drains either suspended from an overhead tube sheet or
on both sides, the expressing times are long (es- upright on a plate (except where each element
pecially for readily compressible cakes), and the has its own housing). There are advantages to
expressing force is as great as possible. the suspended design, but great care is required
with elements that break easily.
Most candle filters are operated as pressure
8.3. Candle Filters filters. The elements can be cleaned by back-
washing, or they may be replaceable. Some
Candle filters (cartridge filters) consist of tubular multiple-element filters offer filtration areas of
elements, mostly covered by sleeves of a filter far more than 100 m2 . As typical clarifying fil-
medium. They are widely used in the filtration of ters, these devices have a broad field of applica-
weakly to extremely weakly concentrated slur- tion (groups D and VD in Table 2). The filtra-
ries that contain solids more or less as impuri- tion surface can take a wide variety of shapes,
ties at concentrations down to the ppm range. depending on the job being done.
This class includes all filters with cylindrical el-
ements mounted, singly or multiply, more or less Sheet Candles. A simple candle of this type
vertically in tanks (Fig. 43 A). consists of wire mesh or perforated screen made
All candle filters have the fundamental ad- of AISI 316 stainless steel, phosphor bronze or
vantages that the filter elements are relatively man-made fibers supported on a tubular metal
simple in construction and cheap to fabricate, core (Fig. 43 B). Slotted screens and wire-wound
and that the devices are adaptable to require- filters can also be employed. Such elements
ments imposed on separation efficiency and are used mainly to collect weakly-concentrated
throughput capacity. The elements are mounted solids from liquids such as oils and soap and
38 Filtration

Figure 43. A) Sectional view of candle filters and B) tubular filter elements (reproduced with permission of Faudi Filter)
a) Deaeration; b) Opening device; c) Filter candle d) Discharge; e) Tensioning plate

dyestuff solutions; mesh openings range from water filter element is the gravel-filled prepack
0.01 mm to 0.5 mm (down to 2 µm in special cartridge.
meshes). Backwashing is desirable for wire- A continuously operating gap-type cartridge
mesh elements. filter has several filter elements, charged on the
Disposable sleeves of paper or nonwoven inside, arranged on a rotating mount that brings
synthetics are used to retain finer solids. In part, them one after another to a stationary backwash
these filter media simultaneously act as deep bed device.
filters, the solids being deposited in the medium
itself. These simple filter elements offer com- Cartridge Filters. Cartridges are designed
paratively high flow rates. Available filter units for deep-bed filtration and are thus used mainly
cover the range from a few liters per minute to for fine filtration of dilute slurries, concentra-
several hundred cubic meters per hour. Enclosed tions of less than 0.01 % and particle sizes less
in pressure-tight vessels, they can be operated at than 20 µm. They usually comprise replaceable
absolute pressures of up to 10 MPa. The pressure cartridges made of a variety of materials such
drop across such a filter is around 10 kPa. as sintered metals (AISI 316 stainless steel), ce-
ramics (also usable at high temperatures), plas-
Gap-Type Candle Filters. Gap-type candle tics, cellulose or glass fiber (resistant to most liq-
filters can be made of disks, profiled wire, or uids). Wound cartridges of cotton, cellulose or
tubes (Fig. 44). Most are held together by straps. manmade polymer fibers, often combined with
In one design, the gap-forming elements are nonwovens, are distinguished by relatively large
slipped or welded onto a tube; filters of this type spaces (honeycomb) for retaining solids. The
are used as well strainers. A special drinking simple construction and low material costs open
 Filtration 39

up technically and economically interesting pos- For clarifying difficultly filterable liquids, such
sibilities. as some pharmaceutical and biological liquids
(blood, among others), elements made of fibrous
Large-Area Filters. Large-area filter ele- bases or materials coated with activated carbon
ments are made by folding the filter medium give satisfactory performance in the micrometer
along the direction of the cartridge (Fig. 45) or range (microfiltration).
by using pouch and disk constructions. The fil- A recently developed element is assembled
ter medium is again mounted on a center tube. from seven individual tubes having slots for the
Elements can also be built up in several layers. passage of filtrate (Fig. 46). A tube bundle is co-
Folded-paper cartridges of this type offer 170 m2 vered with a suitable high-pressure fabric, which
of filtration area per unit. Pouch- and disk-type fits tightly around the curved surfaces during fil-
filters have far less area per unit (up to 0.5 m2 ) tration. During the backwash cycle, the fabric
but can be cleaned and are therefore reusable. is lifted off the tubes; this movement causes the
Up to 3.45 m2 of filtration area per unit is avail- cake residue to be thrown off. The filter medium
able in pouch filters. A disk filter consists of has a tubular weave, that is, it forms a seamless
disks of pulp, metal screen, or membrane filter tube that can withstand several bars of backwash
medium slipped on a central support, alternating pressure. Therefore, its cleaning does not cause
with support disks, which have slots to admit the any concern. This large-area filter element is sta-
slurry into the elements. ble and can be used especially well as a back-
wash filter with a cake thickness between 3 and
50 mm. With up to 200 m2 of filtration area, this
candle-bag filter is suitable for thickening and
clarification of suspension as well as for solids
treatment, such as washing, extraction, or steam
drying. Finally, the cake can be reslurried or dis-
charged as dry solids. Typical applications are
catalyst or activated carbon removal, filtration
of pigments or impurities and treatment of poly-
mer intermediates.

Design and Selection. Candle filters are

generally designed to the flow capacity, filtra-
tion pressure and separating power stated by the
manufacturer. The selection of the filter medium
calls for some experience.
It can often be advantageous to use several
units with small filtration areas in place of one
larger-area unit. With several units in parallel,
for example, one element at a time can be cut
out of the line for washing while the remaining
ones stay in the filtration stage.

8.4. Deep-Bed Filters

Figure 44. Gap-type candle filter
A: a) Steel disk package (turned for solids discharge); This section deals only with depth filters having
b) Fixed gap cleaner beds of sand, gravel or similar loose materials.
B: a) Steel wire spiral (turned for solids discharge); b) Fixed A depth filter is usually a simple container
scraper
with a porous bottom, on which a bed of filter
medium between 0.5 and 1.5 m deep is placed.
Other Designs. A number of other cartridge If the bed material is gravel or sand, such a fil-
designs have been devised for special tasks. ter is also called a sand filter. Figure 47 shows
40 Filtration

Figure 45. Candle-type strainer filters (reproduced with permission of Mann & Hummel)
A) Radial fold filter; B) Disk filter; C) Multitube filter

a simple form of a gravity sand filter. The fil- fractions. In such multilayer filters, the liquid
ter bed (c) is supported by the screen (a), and can be introduced at different points. This ap-
the filtrate is discharged through pipe (e). Wa- proach gives a 70 % increase in flow velocity,
ter, steam or air can be admitted through pipes substantially longer service time, and enhanced
(g) for cleaning. Wash water overflows at (b), sludge capacity.
if at all. When agitation is used in cleaning, the When a depth filter is employed to clarify
wash liquor is discharged at (f ). The cooling or juices, solutions and similar valuable liquids, en-
heating coils (e) make it possible to temper the closed tanks are used instead of open vessels,
filter. Depth filters are also operated as pressure and higher pressures can also be applied. Pres-
filters, either in order to increase the throughput sure sand filters usually permit two to three times
or when they are installed in pressurized lines. as great a pressure drop as gravity filters, and so
To increase the filtration area of pressure sand finer-grained bed materials can be used as well.
filters, several beds can be arranged one above With a few exceptions, bed depths in such filters
another. are much less than the depths usually found in
Most filters of this type are used in the treat- water-treatment plants. In industry, depth filters
ment of drinking water and process water. Basin- with beds of special materials such as activated
type sand filters have been introduced where carbon or ion-exchange resins are often installed
quantities are very large, since these fixed struc- so that dissolved substances can be removed si-
tures offer relatively large areas and depths. multaneously.
Flow in a depth filter is usually from top to In a continuous process (Fig. 48), the influent
bottom. The flow is reversed in order to clean is initially in an unpacked internal space, whence
the bed. The basic operating modes differ little it enters the bed through conical internals. The
even though a variety of techniques are possible, clarified liquid (filtrate) drains from the bed into
especially for cleaning. an external space. The filter medium is hydrauli-
With finer-grained bed materials used to col- cally removed at the bottom and cleaned in a
lect finely dispersed solids, the topmost layer of regeneration tank at the top. The clean sand is
the bed tends to become plugged, so that clean- returned to the filter vessel.
ing may become necessary before the entire bed For smaller units (up to roughly 600 m3 /h),
is loaded with solids. In such cases, layers differ- a backwash-cleaning filter has been developed
ing in particle size can be used; a new cleaning for largely unattended operation. When solids
method is needed, however, to avoid mixing the deposited in the filter bed cause the differential
 Filtration 41

pressure to increase, the liquid level in the tank

will also rise until its hydrostatic pressure initi-
ates backwashing. Because the cross-sectional
area of the backwash pipe is larger than that
of the influent pipe, the flow velocity can be
roughly four times as great (44 m/h).

Figure 48. Continuous sand filter

a) Sludge; b) Sand and sludge; c) Slurry; d) Sand bed; e) Fil-
trate; f) Sand and sludge

8.5. Disk Filters

The element in a disk filter is a rotating verti-

cal disk (Fig. 49); one or more such disks are
arranged on a shaft, with roughly half of each
disk submerged in a slurry tank (Fig. 50). The
device allows continuous filtration. The disks
are made up of 8 – 10 individual sectors, each
of which is an independent filter. The interior
space of a sector is connected to the filtrate dis-
Figure 46. Candle-bag FUNDA-BAC filter (reproduced
charge by a rotary valve, so that a cake can form
with permission of Dr. Müller, Männedorf) on the outside when the sector is submerged in
a) Filtrate/blowback-air; b) Central tube; c) Concentric the tank. After the submersion part of the cycle,
tubes; d) Horizontal slots for filtrate entry–blowback; e) Fil- air is drawn or blown through the sector in order
ter medium; f) Slurry; g) Filter cake; h) Filtrate coming down
concentric tubes and rising in central tube
to effect dewatering; finally, the cake is removed
by simultaneous application of a scraper and an
air blast, or by spraying.
The disks are 1.2 – 3.6 m in diameter; in a
special design, disks up to 5 m in diameter were
used. Multi-disk filters have filtration areas of up
to 280 m2 . In devices with relatively large diam-
eters, hydrostatic effects may cause nonuniform
cake thickness.
When several disks are mounted in a single
tank, the tank is fitted with an agitator (usually a
paddle mixer) or an air turbulizer in order to pre-
vent sedimentation of the solids, which would
lead to uneven cakes and poor dewatering. If not
with an agitator, the multi-disk filter is built with
a divided tank. The slurry level in the tank dic-
tates the disk rotation speed.
Figure 47. Open “low” sand filter
The disk filter is commonly operated as a vac-
a) Screen; b) Effluent; c) Sand bed; d) Wash water; e) Heat- uum filter. The tank is open and readily accessi-
ing or cooling system; f) Filtrate; g) Cleaning pipes ble. If vapors generated at elevated temperatures
42 Filtration

Figure 49. Vacuum disk filter

must be kept from escaping into the environ- the drawback that cracks develop in the cake and
ment, the filter can be mounted in a pressure- cannot be smoothed.
tight housing and operated under pressure; for Applications center on high-tonnage prod-
hyperbaric operation, see also Section 4.1.4. ucts where large filtration areas are needed, e.g.,
iron ore slimes, flotation concentrates, white wa-
ter from papermaking machines, blast-furnace
dust from scrubbers, and aluminum hydrate
(groups M and S, Table 2).

8.6. Drum Filters

Wrapping the filtration surface around a cylin-
der yields significant advantages that have made
drum filters one of the most widely used types.
Their advantages are continuous operation, easy
charging, a choice of cake-removal methods,
low sensitivity to suspension variations, good
possibilities for washing in some cases, satisfac-
tory residual moisture, relatively simple designs,
Figure 50. Vacuum disk filter reliability, and economy.
a) Scraper; b) Filter disk; c) Trapezoidal sectors; d) Outlet
nipples ; e) Automatic valve; f) Filter tank; g) Overflow In one revolution, the drum passes through
the processing stages, thus allowing continuous
In principle, the filter cake in a vacuum disk movement of filter cake and filtrate. Filters can
filter can be washed, but it is certainly less effec- be operated as gravity, vacuum or pressure fil-
tive than in, e.g., belt filters. The basic advantage ters.
of the continuous vacuum filter is that it requires
little space per unit of filtration area. Another Gravity Drum Filters (Revolving Screens).
advantage is that the filter elements are readily Applications of gravity drum filters are limited
accessible. In some cases, this type of filter has to simple screening, where cake formation is not
 Filtration 43

crucial to the filtration operation, that is, where removed by an air blast from inside the drum,
the cake does not greatly increase the filtration falling through a chute into a collector.
resistance. Thus the nature of the solids gov- Single-cell vacuum drum filters are built with
erns the application: gravity drum filters are suit- filtration areas of up to 40 m2 . They are suit-
able for filtering coarse-grained or fibrous mix- able for all slurries that can be held suspended
tures, for example, treating surface waters, pa- in the tank, that is, slurries that do not contain
permaking wastewaters, and the like. They can readily sedimenting solids (group S in Table 2),
be charged on the inside or the outside. When and where the cake need not be washed. They
the filter is internally charged, the untreated liq- feature a high working vacuum, since there are
uid flows through a distributing channel to the no high losses; good dewatering, since relatively
inside of the drum. As the drum turns, the solids long blowing times are possible; and simple con-
collected by gravity move upward, separate and struction.
are removed, for example with a screw conveyor. Drum filters generally have continuously
The drum is covered with a screen fabric. variable drives so that they can accommodate a
With microscreens, it is possible to collect solids range of product properties. The filter medium (a
that are somewhat more difficult to filter, such finely-woven or fine-pored fabric) is supported
as occur in sewage treatment. on a widely spaced wire mesh.
A filter charged from outside is used in the Because of its simple design, the single-cell
treatment of recycle waters and wastewaters in drum filter is well-suited to precoat filtration (see
paper and pulp manufacturing. The drum is al- also page 65 and Chap. 11). In a special ver-
most completely submerged in the slurry. While sion where the common path of filtrate and air is
the solids are held up on the screen surface short, it is preferred in the processing of cloudy
(an easily removable cake forms in the case wine and beverages. Throughputs varies from
of fibrous solids), the virtually fiber-free filtrate 0.2 – 1.2 m3 m−2 h−1 , depending on the kind of
runs into the lowermost part of the drum. For a beverage. In order to produce a uniform pre-
drum roughly 2 m in diameter turning at a pe- coat, which may be 10 – 12 cm thick (this layer
ripheral speed of 3 – 15 m/min, throughputs of is continuously scraped off during filtration), the
0.5 – 5.0 m3 /min per meter of drum width are concentration of precoat material (diatomaceous
possible. Activated sludge flocs are collected earth) is low, the depth of submersion is slight,
with a drum 3 m in diameter and 3 m long, lined and the drum is rotated rapidly. If the drum shell
with a microscreen having a mesh opening of is divided into sections 50 – 60 mm wide and a
10 µm; the throughput is 630 m3 /h. tank is added to receive the wash liquor, cake
washing is also possible in single-cell drum fil-
Vacuum Drum Filters. In order to increase ters.
throughputs and extend the range of applica- A special variety of this filter is the suction
tions, the inside or outside of the drum is en- roll used in papermaking. It has a suction box,
closed in a housing connected to a vacuum which restricts the vacuum to a relatively narrow
pump. In the simplest case, the drum has heads zone at the top. Suction rolls make it possible
on either end, so that the entire inside space to increase the speed of the papermaking ma-
is under a uniform vacuum. Roughly 30 % of chine from 250 m/min with couch rolls to over
the drum is submerged in a tank, which fits 1000 m/min.
fairly closely around it. Slurry in the tank is Multi-compartment Drum Filters. Washing,
held at a constant level by means of an ad- as well as the separate recovery of filtrates
justable overflow. The feed is distributed by a from the several process steps, are made easier
stirrer, whose oscillating movement along the in multi-compartment drum filters. The filtra-
drum is intended to prevent partial settling of the tion surface in such a device is subdivided into
suspended solids. In the submerged part of the flat, closed cells, which have their filtrate sides
drum, the vacuum pulls liquid through the filter connected through separate pipes to vacuum
medium while a cake builds up on the outside. pump(s) (Fig. 51). The compartments usually
The cake exposed on the top part of the drum have perforated inserts bearing, for example,
is dewatered by air pulled through it. Shortly drainage channels on the cake side and filtrate
before the drum re-enters the tank, the cake is collection channels on the vacuum side. The
44 Filtration

Figure 51. A) Vacuum drum filter (reproduced with permission of Dorr – Oliver)
B) Vacuum drum filter
a) Agitator; b) Valve; c) Drum; d) Filter pipes; e) Division strips; f) Tank

compartment insert bears a fabric, which sup- bottom of the tank has the function of preventing
ports the actual filter medium. While this fabric the solids from settling in order to keep from up-
is installed separately for each compartment, setting the filtration. It is not always desirable to
the filter cloth itself covers as much of the drum start filtration immediately after the drum is sub-
periphery as possible. merged, since with sedimenting feeds this would
The filtrate pipes rotate with the drum and mean picking up the fine fraction first and thus
have a sliding seal connection (rotary valve) to impairing the permeability of the filter medium.
the fixed lines leading to the supply tanks and The cake emerging from the tank should first be
pumps. The valve also serves as control means, dewatered and then washed.
allotting the desired process stages to the sev- If cracks appear in the cake on dewatering,
eral sectors of the drum. The control arrange- they will interfere with uniform washing. The
ment makes it possible to set up any desired fil- cake surface can then be smoothed with pres-
tration cycle; this is an undisputed advantage of sure rolls. Washing should be spread over a large
the compartment filter. portion of the drum circumference, and so with
The slurry feed is on the ascending side of large quantities of wash liquor there is a dan-
the drum. An overflow pipe provides level con- ger that the cake will slip off. To prevent this,
trol and thus maintains steady filtration condi- washing belts are placed around the drum. Like
tions; the pipe can be adjustable. A stirrer in the the expressing belts described further on (see
 Filtration 45

page 36), these surround the drum and have the method (Fig. 51 B); it is best suited to rigid, non-
dual function of closing up cracks and effecting deformable cakes at least 4 mm thick. Lifting of
good distribution of the wash liquor. The wash the cake can be reinforced by an air blast sup-
liquor is usually delivered to the cake through plied below the filter medium through the filtrate
drip tubes, channels or nozzles. pipes.
In string and chain discharge, parallel strings
or chains are passed over the drum in the cir-
cumferential direction. After the last dewatering
step, these pass over a deflecting roll with a rel-
atively small diameter, and the cake then drops
off. Chain discharge is suitable for relatively
thick cakes such as are produced in the filtration
of coarsely crystalline materials. “Felted” cakes,
on the other hand, call for string discharge.
Roller Discharge. Thin filter cakes, down to
1 mm and thinner, can be taken up by rollers
(Fig. 52 A). Contact between roller and drum
should not be too firm. The roller turns at the
same speed or slightly (3 – 5 %) faster. The cake
is removed from the roller by a scraper, comb or
other means; part is left on the roller to promote
separation from the drum.

Figure 53. Combined vacuum drum pressure belt filter

(Dorr – Oliver, Germany)
a) Press belt drive; b) Filter cloth aligning assembly; c) Press
rolls; d) Press belt tensioning device; e) Vacuum drum filter
Figure 52. Cake discharge assemblies in vacuum filters
A) Roller discharge; a) Filter drum; b) Filtrate pipe; Belt discharge involves leading the filter
c) Scraper; d) Roller; e) Slurry tank;
B) Belt discharge; a) Filter cloth; b) Tensioning device;
cloth with the cake over small rollers (Fig. 52 B).
c) Cloth wash; d) Wash liquid receiver This method can be used for continuous filtration
of slurries containing fine solids that would gen-
A variety of devices and techniques are used erally block the filter cloth too quickly. Spray-
to remove various cakes from the filter medium. ing the cloth from both sides makes it possible
Scraper discharge is the earliest and simplest
46 Filtration

to handle finely-dispersed suspensions without do good service as laboratory filters. The filters
precoating. are irreplaceable for many continuous filtration
When filtrates are volatile or tend to produce jobs, being distinguished by reliability, low op-
vapors, or when an improvement in filter capac- erating costs, versatility and adaptability.
ity is desired (see page 48 and Fig. 58), it may Rotation speeds depend on filter size and
be useful to enclose the filter and pressurize the desired cake moisture content and range from
housing slightly. 0.1 – 3 revolutions per minute.
Expression devices have been added to drum
filters (Fig. 53). Besides lowering the cake mois-
ture by 20 – 200 %, compression also promotes
cake removal. The rubber expressing belt is held
against the drum with several pneumatically ad-
justable rollers; forces per unit length of up to
some 250 N/cm are used. The belt path is such
that the cake gradually enters the region of max-
imum pressure.
For the filtration of finely dispersed feeds, the
drum filter can also be operated as a precoat filter
(Chap. 11). Before filtration proper, a 5 – 6 cm
layer of filter aid is applied from a slurry. It may
be advantageous to smooth the precoat layer.
During filtration, the filter aid must remain ad-
hering to the filter cloth over the entire periphery
of the drum, so as to maintain the suction in all
the compartments of the drum. No air blast is
used to help in cake removal. During filtration,
the scraper is advanced 0.05 – 3 mm per drum
revolution until a permanent precoat thickness Figure 54. Inner face vacuum filter
of a few mm is reached. a) Dewatering zone; b) Rotary valve; c) Settling zone;
If the suspension is one that settles rapidly d) Suction zone
(group F of Table 2), it can be supplied to the
Sizing of Vacuum Drum Filters. The design
tank from a box located at the top of the drum
of such filters is normally directed to the
(top-feed filter). This arrangement creates seal-
throughput of solids as the significant compo-
ing problems with respect to the drum and the
nent of the feed not least of the fact that deliquor-
cake. In general, the lower tank is either elimi-
ing and washing of the produced cake herein are
nated or filled with wash liquor. The inner-face
more or less uncomplicated procedures.
vacuum drum filter (Fig. 54) is also suitable for
Based on the filtration equation (Eq. 15) (Sec-
this type of feed; sedimentation and filtration
tion 2.1.2) the material balance using mass ratios
in such a device are in the same direction, so
of the slurry, the cake and the filtrate and the sub-
that no stirring is needed. The filter medium is
stitution of the effective filtration time (s) by
on the inside of the drum shell, while the com-
a
partments are on the outside. The drum is open t = 60 (68)
n
at one end to allow slurry feeding and cake re-
where a is the submerged to the total drum area
moval; the closed end bears the filtrate pipes and
and n (min−1 ) the number of drum revolutions,
rotary valve. By virtue of gravity, the coarse frac-
lead to the available throughput of dry solids (kg)
tion of solids is deposited first on the filter cloth,
per unit filter area (m2 ) and unit time (h)
forming a more permeable ground layer, which
separates more easily from the cloth. aKn∆p
(MS )A = C (69)
Vacuum multi-compartment filters are made αm η
in standard series (about 30 sizes) with filtra- here (M S )A is the specific mass of solids
tion areas up to 100 m2 and drum diameters up 
−2 −1 60
to 4.2 m. The smaller sizes, roughly 0.25 m2 , (kg m h ), C = 3600 π a conversion fac-
 Filtration 47

Figure 55. Pressure drum filter (Fest-Filter for antibiotics production, 1 m2 filtration area (reproduced with permission of BHS
Sonthofen)

 
cM
tor (s1/2 min−1/2 h−1 ), K = 1 cM 1 − cMc
The annular space between drum and housing is
3 sealed with stuffing boxes and partitioned into
a concentration constant (kg/m ), 1 the density
four or five chambers. The drum shell consists of
of the liquid (kg/m3 ), cM and cMc the mass ra-
compartments (Figs. 56 and 57), which are con-
tios of solids in the slurry or in the cake after
nected to a rotary valve by filtrate pipes. Slurry
the filtration cycle, αm the average specific re-
under pressure is continuously pumped into the
sistance of the cake (m/kg), η the viscosity of the
filtration space. The cake builds up in the filter
liquid (Pa s) and ∆p the pressure drop through
compartments; as the drum rotates, the cake is
the cake (Pa). The specific flow resistance of the
mechanically compacted by passing through a
filter medium is disregarded because of the com-
wedge, then moves on to the washing chamber.
paratively low influence.
If no provision is made for multistage washing,
The equation gives a parabolic increase in
the next step is dewatering by blowing in a sepa-
cake production with increasing rotation speed;
rate chamber, which is followed by the cake re-
in other words, the maximum solids output cor-
moval section. In the unpressurized region, the
responds to the highest possible rotation speed.
cake is removed by back-blowing and pivoting
On the other hand, the cake thickness decreases
scrapers. Washing of the filter cloth can also take
exponentially thereby. Since this thickness is
place in this zone.
limited by the cake discharge device, the maxi-
The advantages are: continuous operation,
mum solids production is also limited. The limit
relatively high throughputs, filtrations up to
further depends on the material values contained
near the boiling point of the liquid, no vapor
in Equation (69).
losses, very good washing, countercurrent wash-
Table 3 presents some examples illustrating
ing when multistage arrangements are used, low
the performance range of the vacuum drum filter.
cake moisture, no cracking before washing, and
Pressure Drum Filters. To realize the ad- mechanical compaction. The filter is naturally
vantages of continuous drum operation in pres- more expensive than a conventional rotary drum
sure filtration, with its higher throughputs, and filter, so that additional filtration costs are cal-
to make the filtration of volatile liquids more culated as some 50 %. It finds use mainly in the
economical, Fest developed a drum filter with chemical industry (filtration of dyes, vitamins,
a pressure housing around the drum (Fig. 55). inorganic and organic chemicals, pesticides, in-
The drum turns at a continuously variable speed. secticides), in the production of pharmaceuticals
48 Filtration
Table 3. Performance of vacuum drum filters (Dorr–Oliver).

Material Feed concentration, Filtrate rate, Cake moisture, Discharge

% solids kg m−2 h−1 %

Calcium carbonate 20 34 – 50 40 – 50 scraper

Coal (flotation concentrate) 25 360 – 500 25 scraper
Coal (refuse) 30 120 – 145 25 – 30 scraper
Blast furnace flue dust 45 45 25 – 30 scraper
Iron oxide (pigment red) 13 17 30 roll
Corn starch 12 – 28 130 – 165 30 – 40 belt
Wine lees low 82 – 820 (L/m2 h) – precoat

(antibiotics), and in vegetable processing (ex- hyperbaric filters. Many such designs provide
traction). Table 4 gives some throughput figures, better dewatering than the straight vacuum fil-
which show substantial gains in some cases. Be- ter.
cause cleaning is more complicate, it is recom-
mended that the product not be changed.
Table 4. Some throughputs of pressure drum filters, kg m−2 h−1 ,
based on dry cake (BHS, Sonthofen, Germany)
Throughput Cake moisture, %

Antibiotics 385 14
Copper sulfate 525 24
Sodium hydrosulfite 700 20
Zinc stearate 45 – 160 60 – 70
PVC (suspension) 420 51
Titanium dioxide 150 45

Figure 57. Schematic operation of Fest-Filter

Figure 56. Sectional view of Fest-Filter (reproduced with

permission of BHS Sonthofen)
1) Filter drum; 2) Pressure tight housing; 3) Scraper; 4)
Partitioning element pressed by compressed air

Increased capacity sometimes results from

the use of pressure drum filters created by hous-
ing conventional vacuum drum filters in pres-
sure tanks (Fig. 58). These devices have long Figure 58. Pressurized drum filter – Hyperbar filter
been known and have recently come to be called
 Filtration 49

8.7. Leaf and Plate Filters

The element in a leaf or plate filter is essen-

tially a leaf-shaped structure covered with filter
medium on one or both sides. Slurry is supplied
to the leaf from the outside, and the filtrate can
drain through the void inside, while the cake col-
lects on the outside. Filter elements are usually
assembled into units of varying size. They can
be operated as open-tank devices, immersed in
the feed, with the filtrate being withdrawn by
suction (open-tank leaf filter, Moore filter). Be-
cause the cake often drops spontaneously into
the feed tank, these devices are also used as fil-
ter thickeners. Alternatively, the filter elements
are enclosed in pressure vessels (which may be
heatable) and operated as pressure filters, espe-
cially for influents of relatively low concentra-
tion (clarifying filtration). They are also well-
suited to precoat filtration.
The shape and arrangement of the filter leaves
or plates are adapted to the properties of the cake
and the filter operating requirements. If the cake
is easily detached from the filter medium, a ver-
tical leaf configuration can be chosen, so that
the cake falls off the medium by gravity (re-
moval can be promoted by an air blast or vibrat-
ing). Horizontal leaves are suitable for poorly- Figure 59. Wire filter leaf
a) Binding; b) Filter medium; c) Metal mesh; d) Wire mesh
adhering filter cakes. support (Chamber screen); e) Filtrate manifold
Possible element shapes are innumerable,
from simple perforated and mesh constructions Leaf filters are made in a smooth design with
to multi-layer designs with internal stiffening. up to 60 m2 of filtration area. In large plant units,
The design of Figure 59 is typical for bed ele- the leaf assemblies can be moved mechanically
ments which are preferred because of their pres- or hydraulically (Fig. 62), or the housings are de-
sure resistance. Each element consists of five signed for easy cake loosening and removal. Be-
fabric plies with graded mesh openings. The core cause the pressure on the cake is relieved when
ply, which allows the filtrate to drain, bears a the tank is opened, a vacuum is often pulled on
supporting fabric on either side, with the filter the filtrate pipes at this time so that the cake will
cloths proper on the outside. not drop off the leaves until the desired moment.
In another type, the effective filtration area in In the Kelly filter, vertical filter leaves were ar-
each element is made up of a base with perfo- ranged axially in the cylindrical pressure hous-
rated plates, which is inserted in a massive frame ing, so that the leaf size decreases to either side.
to withstand greater mechanical loads. The filter The leaves are vertical in smaller units or hori-
cloth or a wire mesh is placed over the base. zontal in larger ones (up to 140 m2 ). The cylin-
For clarifying filtration with filter beds, wo- drical housing of the Sweetland filter is divided;
ven fabrics, filter paper or membranes, the filter the lower half can be pivoted to the side to allow
media are placed right on the horizontal plate cake removal by hosing off.
structure. The stack of filter elements to retain Where process conditions do not allow the
solids down to some micrometers is placed about slurry heel (slurry remaining in the pressure
a cylindrical pipe enclosed within a pressure- housing after filtration is complete) to be recy-
tight vessel (see Figs. 60 and 61). cled to the filter feed or otherwise utilized, some
50 Filtration

designs have one or more filter leaves in the bot- tion; with vertical leaves as shown in Figure 63,
tom of the pressure space to filter this residual automatic removal is often a simple step.
feed. These leaves do not function during the
main part of the cycle. The heel is usually driven
through those filter leaves by pressurized gases
(compressed air).

Figure 62. Horizontal-tank pressure leaf filter (Niagara)

Figure 60. Horizontal plate filter (deep-bed filter) (repro-

duced with permission of Seitz-Filter-Werke)

Figure 63. Vertical pressure leaf filter

a) Valve security; b) Overflow

In horizontal systems, flowable and non-

flowable cakes must be distinguished. Flowable
cakes are the rule in precoat filtration for clar-
ification; here the cake is commonly discarded
as waste. The round filter leaves or plates, with
slurry feed from the top, are arranged on a hollow
Figure 61. Sectional view of horizontal plate filter shaft in a pressure vessel and positioned a few
centimeters apart with spacing disks (Fig. 64).
Many designs address the problem of cake re- Cake thickness is controlled through the filtra-
moval. Modern filtration systems are generally tion pressure or with special sensors. Cakes in
provided only with completely automatic opera- these devices are nearly always so loose that they
 Filtration 51

can be discharged by briefly spinning the stack Nonflowable cakes are generally obtained
of plates; separation can be helped by backwash- in cake filtration where filter aids must be
ing if necessary. Cake removal, required when avoided. Help in these instances comes only
leaves cease to function, is effected by vertical from mechanical cleaning devices. Washing in
vibration in addition to rotation. Filters of this these pressure filters usually involves some dif-
type are also called centrifugal-discharge filters ficulty, because the slurry heel must first be re-
up to 170 m2 . They are often classified as plate moved and the housing filled with wash liquor.
filters. Special devices have been developed to reduce
A further variation in operation of pressure the consumption of wash liquor.
plate filters is shown in Figure 64. If the cake In the pressure leaf filters described above,
does not flow off the rotating plates, it is dis- the feed is pumped into the housing, and its dis-
charged by fixed scrapers during cake formation tribution over the leaves is naturally somewhat
on the rotating plates. random. The slurry can also be supplied to the
leaves through a hollow center shaft, with the
filtrate draining into the housing. In this way,
uniform loading of the filter elements is ensured.

Figure 64. Continuous pressure plate-filter (reproduced

with permission of Schenk Filterbau)
1) Feed; 2) Scraper; 3) Plates; 4) Filtrate discharge; 5) Cake
discharge

To empty the filter completely before remov-

ing the cake, most filters of this group have
leaves at the bottom of the stack (scavenger fil-
tration elements) to allow separate filtration of Figure 65. Centrifugal-discharge pressure plate filter
the slurry heel. (STAWAG BIOTECH/Switzerland)
For relatively dry filter cakes, a conical dis- a) Filter drive; b) Upper bearing; c) Upper seal; d) Filter
plates; e) Lower bearing and seal assembly; f) Filter vessel
charge is preferred (Fig. 65, left). The stack of
plates in such a device must be driven from the
top of the tank, which, in addition facilitates the Range of Application. The applications of
sealing of the driving shaft. pressure leaf filters are extraordinarily broad,
52 Filtration

and extension to special filtration problems is with no change of apparatus when nutsches
relatively easy. As cake filters, these devices in process service are fitted with a variety
are employed for filtering all kinds of chem- of accessories (e.g., agitator, mixer, heating
ical products, such as glycerol, caustic soda and cooling devices); in this way operations
solution, phosphoric acid, or pharmaceuticals. such as mixing, stirring, reacting, crystalliza-
Run times between cleaning periods are sev- tion filtration, extraction and drying can be
eral hours, and throughputs of 1 – 4 m3 m−2 h−1 performed in sequence. Low equipment costs,
(up to 6 m3 m−2 h−1 in extreme cases) have non-polluting operation, and optimal techniques
been achieved. Pressure leaf filters are applied make these devices suitable for small product
in group S and D of Table 2. batches. Nutsches can be placed on pivots and
When used as precoat filters, these units are repositioned for the various process steps (Fig.
especially well-suited for the collection of rel- 66).
atively fine-grained solids from low-concentra-
tion feeds (beverages, cane syrup, or water). Av-
erage throughputs are 0.3 – 1 m3 m−2 h−1 . Run
times are strongly dependent on the level of im-
purities to be removed; in mixed and thick juices
in sugar refining, runs of 7 – 16 h (depending on,
e.g., the quantity of diatomaceous earth used as
filter aid) are achieved.
Centrifugal-discharge filters are available
with filtration areas of 1 – 60 m2 (up to
170 m2 from one manufacturer); the leaves are
420 – 1500 mm in diameter.

8.8. Nutsche (Pan) Filters

The simplest type of nutsche filter is an open
tank or box with a porous bottom, into which
the slurry is charged or flows continuously. Fil-
ters of this kind are common everywhere, espe- Figure 66. Pressure nutsche filter – multi purpose filter –
cially in laboratories. They do not impose strin- in the crystallization step (reproduced with permission of
gent requirements on suspension properties, and Schenk Filterbau)
they can function even without difficulty with
Nutsches are good candidates for filtration
highly-concentrated or rapidly-settling slurries.
with relatively thick cakes. To keep cracks from
As a rule, they are operated manually. For poorly
appearing, some filters have smoothing attach-
filterable feeds, suction can be applied to the fil-
ments, which can also provide advantageous
trate side.
mixing of wash liquor and cake and can assist in
Nutsches are widely applied in the chemical
cake discharge.
industry because all the steps in filtration, includ-
Tanks with internals such as agitators and
ing washing, dewatering, and drying if practiced
solids-discharge devices (plough) are more ver-
(with hot air), can be performed in a clean, dis-
satile nutsches. These accessories can homoge-
tinct manner. There has accordingly been no lack
nize the filter cake and render it especially wash-
of efforts to automate the operation of nutsches
able (Fig. 67).
or make it continuous.
In some advanced developments, intended
In order to increase filtrate flow rates, an
for comparatively high throughputs, a number
enclosed nutsche can also be pressurized with
of individual nutsches circulate on either a belt
air or inert gas. Pressure nutsches are espe-
or a carousel. (A system of the first type is usu-
cially good with volatile solvents. They can be
ally classed as a belt filter.) This kind of nutsche
drained mechanically through a retractable bot-
has proved useful especially in phosphoric acid
tom. Several process steps can be carried out
 Filtration 53

Figure 67. Pressure Nutsche filter

a) Agitator; b) Wash device; c) Screw conveyer; d) Heating pipes; e) Filter plate

manufacturing, where it is employed to remove 8.9. Pressure Plate Filters

gypsum in the sulfuric acid digestion of phos-
phate rocks. Careful countercurrent washing is The filter press is one the simplest of all pressure
practiced in order to attain a high degree of sep- filters; it allows relatively easy cake removal af-
aration. Equipment sizes range up to a filtration ter the individual filtration steps. It consists of a
area of some 200 m2 . number of flush plates, up to 100 or more, and
Automated nutsches share the advantages frames whose width (between 25 and 150 mm)
stated earlier: They are insensitive to slurry prop- can be matched to the service conditions. The
erties and thus suitable for groups F, M, and S plates and frames form rather flat pressure filtra-
in Table 2, and they provide a clear separation tion spaces with a relatively large filtration area
of the process steps and thus insure a uniform, (plate-and-frame filter press, Fig. 68 A). During
reliable filtrate composition. filtration, the plates and frames must be squeezed
For the filtration of slimy feeds, it is advan- by mechanical or hydraulic means in order to
tageous to keep the filter cake in motion, for ex- seal the filtration spaces (Fig. 69). The faces of
ample by mechanical vibration or an appropriate the plates are studded or grooved to permit fil-
slurry flow, so that the cake will remain perme- trate drainage.
able for a longer time.
54 Filtration

The plates can also be made with a raised edge

(recessed-plate filter press, Fig. 68 B). There are
several essential differences between the two
types: In the plate-and-frame press, slurry enters
through channels in the corners of the plates and
frames. The filter cloths can therefore be shaped
as flat strips and pulled over the plates; this ar-
rangement is advantageous when the cloths are
changed. In recessed-plate presses, slurry is in-
troduced into a center orifice of the plates. The
filter cloths must be made in two parts and in-
serted in the slurry feed channels; this arrange-
ment involves much more effort. Further, it is
harder to vary the cake thickness in recessed-
plate devices than in plate-and-frame presses,
where all that is necessary is to replace the
frames. The recessed-plate press has, however,
the advantage that only about half of the filter
elements need be moved to open the press; the
equipment also costs much less for a given filtra-
tion area. Because of the deflection of the filter
cloths at the edge of the recessed plate, thinner
cakes (up to about 35 mm) are generally pro-
duced than in plate-and-frame devices. With ei-
ther type of press, it must be noted that capillary
flow takes place despite the relatively high den-
sity of the filter cloths, and this flow – at least
in filtration with solvents – causes the undesir-
able escape of filtrate through the seals between
plates.
The filtrate is either discharged separately
Figure 68. Filter press – sectional view from each plate through cocks (open discharge)
A) Plate-and-frame filter press or collected in a channel (closed discharge),
a) Filter cloth; b) Filter plates; c) Hollow frames; d) Mov-
able end half plate; e) Fixed end half plate which is preferred when toxic or volatile ma-
B) Recessed-plate filter press terials are handled.
a) Fixed end half plate; b) Filter cloth fastening; c) Recessed
filter plates; d) Filter cloth; e) Movable end half plate

Figure 69. Filter press (reproduced with permission of Eberhard Hoesch & Söhne)
 Filtration 55

At cake washing time, valves are changed

over and special lines carry wash water only to tf =tk Z (70)
every other plate, so that the liquor can flow
transversely through the cake to the opposite where t f is the filtration time, t k is the time for
plate. Occasionally the wash water is also de- filling and emptying per chamber, and Z is the
livered through the slurry channel; this arrange- number of chambers.
ment is, of course, not as effective. After wash- On the basis of a cost calculation, the maxi-
ing, the cake can be dewatered by passing steam mum number of chambers is
or (possibly heated) air through it.  1
tf (CM −Cp ) 2
For cake discharge, the press is opened and Z= (71)
tk Cp
the plates are moved, one by one, through a pre-
determined distance. A variety of mechanical where C M is the cost of mechanical equipment
devices are now available for this purpose. If the (fixed and movable end plates, adjusting device)
cake is to drop out by itself, it should not adhere and C p is the cost per plate (chamber). For con-
too tightly to the filter cloth and should not be ventional designs, Z is found to be around 60.
too densely filtered. Cake separation can be as- To determine t f , the total cycle time includ-
sisted by rapping, pulling out the filter cloth, or ing washing and other steps, experimental data
other means. An automatic filter press for high must be used. Unfortunately, experience has
throughputs has more than 100 chambers with a shown that measurements in laboratory-scale fil-
filtration area of 1000 m2 and more. ter presses cannot generally be extended to arbi-
Filter presses are generally insensitive to trary sizes, since there may be discrepancies in
slurry filtration properties, with perhaps one ex- the filling of the filtration chambers and thus in
ception: In large presses with long slurry chan- the pressure relationships.
nels, varying sedimentation may cause a slurry Filter presses are commonly charged at pres-
of group S (see Table 2) to fill the filtration spaces sures of up to 2 MPa, more in special cases. Cen-
unevenly. Under some conditions, an undesired trifugal or diaphragm pumps are preferred for
classification occurs, with a detrimental effect the cake filtration of highly-concentrated slur-
on washing, and may even lead to pressure dif- ries. The possibility of employing relatively high
ferences between chambers, causing the plates filtration pressures, along with the mechanical
to deform or break. In such cases, it is desirable advantages in charging and discharging, lend fil-
to provide a hole for pressure equalization or a ter presses some advantages over other types of
supporting button. pressure filter, even though these devices are al-
In addition to filter presses with vertical ways operated batchwise:
plates, some designs also feature horizontal 1) Insensitivity to feed fluctuations
plates. 2) Relatively high throughputs, even with dif-
ficultly filterable slurries, so that far smaller
Filtration Cycle (see Chap. 5). Cake filtra- amounts of filter aids are needed
tion in filter presses involves two indistinctly 3) Low cake moisture
separated stages. At the start of filtration there 4) Denser cakes that are easier to handle
is no cake, and the hydraulic resistance is there- 5) Clear filtrate
fore very low, so that the filtration pressure can- 6) Good separation of different filtrates (wash
not rise very high at this point. The process is liquor, etc.)
similar to constant-volume filtration (see Sec- 7) Arbitrary filtration steps (washing, steam or
tion 2.1.2). The pressure increases as the cake air blowing, etc.)
thickness grows, until the rated pressure (of the 8) Low maintenance costs, few spare parts, low
pump) is reached. Constant-pressure filtration depreciation
then begins, with a declining quantity of filtrate. 9) Simple operation
The exact sequence of filtration in filter presses 10) Comparable equipment costs per square me-
is still unclear and cannot be calculated, because ter of filtration area
not enough research has been done, but a rough
estimate suggests that the highest throughput is The drawbacks are obvious: Batch operation;
achieved if personnel requirements in cases where cake does
56 Filtration

not drop off by itself; relatively long cleaning cake filtration is applied chiefly to groups M and
times. S of Table 2. Slurry feed rates in these fields de-
pend on the widely varying slurry composition
Applications. Even though they are batch and range from 0.2 – 1 m3 m−2 h−1 on the aver-
devices, the good washing and low cake mois- age.
ture available in filter presses have kept them in
wide use. Contributing factors, along with com-
paratively long service times and good reliabil-
ity, include mechanical plate movement, used al-
most exclusively for the opening and discharge
of large units; automatic filter-cloth cleaning
with high-pressure water sprays; and the avail-
ability of special plate designs. Plates up to 2.6 m
on a side give far more than 1000 m2 of filtration
area in one press. The design of the plates and
the use of polypropylene as the main plate mate-
rial have remedied many of the shortcomings of
filter presses, such as plate fractures, corrosion,
and plate mass.
Filter presses can be employed almost any- Figure 70. Filter press for sheet filtration – deep bed
where, even if the mode of operation and the pressure filter (reproduced with permission of Seitz-Filter-
Werke)
equipment must be adapted to the feeds in ques-
tion. Filter presses are used successfully in ei- Clarification is carried out in sheet filter
ther cake or clarifying filtration, depending on presses, which resemble plate-and-frame filter
the concentration and properties of the solids; in presses in design (Figs 70, 71, and 72). Because
the latter case, filter aids are usually added, or of the very much lower solids concentration, ser-
filter beds are employed instead of cloth media. vice times are much longer (several hours). For
In the production of chemicals (e.g., dyes), this reason, automation is commonly dispensed
ceramics and raw materials, and in wastewater with. Filtersheets include ordinary precoats and
treatment, nuclear technology and other fields, special papers (see page 64 and Chap. 11).

Figure 71. Sheet filter press opened (reproduced with permission of Seitz-Filter-Werke)
 Filtration 57

Figure 72. Clarifying filter press – schematic operation

Top: Filtration with filter aids; Bottom: Sheet filtration

The most important applications of clari- Membrane filter presses can be operated at up
fying filtration include beer, wort, wine, fruit to 2 MPa; they produce a uniformly dewatered
juices, pharmaceutical liquids, or water steriliza- cake.
tion (group D of Table 2). Here too, filter loading
varies widely, depending both on the properties Plate Press with Belt Discharge (Auto-
of the solids being removed and their concentra- matic Press). This type of filter press, orig-
tion in the feed and on the nature of the liquid. inally developed in Russia, combines positive
They range from 0.05 m3 m−2 h−1 for viscous automatic cake discharge with cake compres-
varnishes up to 10 m3 m−2 h−1 for dilute sus- sion. The horizontal filter plates are stacked and,
pensions, such as beverages. with the filter frames, combined into a three-
chamber system: filtrate chamber, cake cham-
Membrane Filter Presses. In a membrane ber, and high-pressure water space. The water
press, the filter plate is coated with an elastic ma- space is separated from the cake by a membrane.
terial (rubber). After filtration, the membranes For cake discharge, a cloth belt on the frame is
are pressurized so that they mechanically com- advanced until the cake from each plate is com-
press the filter cake. In this way the cake mois- pletely stripped off as the belt is deflected into
ture is reduced by ca. 1 % – 20 %, depending on the next lower plate (Figs. 74 and 75).
the cake compressibility. Figure 73 shows an ex-
ample of a recessed-plate membrane press. A Filter Press with Stationary and Rotating
similar expedient is also possible in a plate-and- Plates. This filter contains alternating station-
frame press. The pressing either shortens filtra- ary and rotating plates on a shaft (Fig. 76). A
tion time or the filtration pressure can be made velocity difference is produced in the cake bet-
smaller, which is an eminent practical advan- ween the plates, leading to breakdown of the
tage. cake. A thin layer of filter cake, whose thick-
58 Filtration

ness depends on the filter medium employed, is 8.10. Tubular Filters

left on the filtration surface. In the extreme case
where cake formation is totally prevented, this is Tubes as filter elements are similar in structure to
pure cross-flow filtration (see Section 2.4). The cartridges. This section deals only with tubular
intermediate states are referred to as dynamic filters whose dimensions do not usually corre-
filtration. spond to the concept of a filter cartridge (diam-
eter either too large or too small). This group
includes, on the one hand, tubular pressure fil-
ters and, on the other, tubular membranes used
in cross-flow filtration.

Tube Filters. The tubular pressure

filter – the tube press – developed in England,
consists of a pressure tube with a filter tube in-
serted in it. After cake filtration in the annular
space, a membrane placed inside the pressure
tube compresses the cake. A pressure of up to
10 MPa can be applied. Next (or immediately
after filtration), the cake can be washed. For cake
discharge, the filter tube is swung downward and
the cake is loosened from the filtration surface
with compressed air. This filter has the advan-
tage of the cylindrical filtration chamber, which
is economical for relatively high pressures.
In another type of tubular pressure filter, fil-
tration and compaction are similar but the tube
is positioned horizontally, so that the cake can
be scraped out of the filter tube.
A third type of tubular pressure filter has a
cylindrical rotor inside the filter tube. Slurry is
continuously compacted in the annular space.
The solids are retained in the annular space on
the filtration surfaces of the tube and the rotor,
where they are subjected to shear. In this way,
the cake is caused to move downward to the dis-
charge. As in the filter press with rotating plates
(see preceding section), the filter cake must re-
Figure 73. Membrane filter press plate assembly main flowable after substantial dewatering; that
a) Filter cloth; b) Slurry corner feed; c) Recessed plate; is, it must be thixotropic. In one or more washing
d) Membrane recessed plate; e) Press medium; f) Cake; zones, wash liquor can be fed radially through
g) Filtrate; h) Air or water inlet (Pressuring membranes)
the filter tube. Several filter sizes with filtration
areas from 0.25 – 1.6 m2 are tested.
If the filter cake is thixotropic, the shearing
makes it flowable, so that it can be conveyed by Cross-Flow Tubular Filters. The filter ele-
pressure through the system of plates. Accord- ments in the tubular cross-flow filter are small
ing to studies of some dye suspensions, this filter tubes or hoses, a few millimeters in diameter,
can collect the same quantity of solids as a con- which are bundled into systems of tubes carry-
ventional filter press with roughly 20 times as ing parallel flows (Fig. 77). The filtrate passes
large a filtration area. the system through walls of the tubes whereas
the suspension flows tangentially to them drag-
ging the retained particles, see Chapter 2.4. The
 Filtration 59

Figure 74. Automatic filter press – systemic processing

a) Cloth drive; b) Cloth wash; c) Cake removal; d) Pressure control; e) Filter cloth; f) Filter cloth aligning assembly; g) Ten-
sioning device; h) Yoke plate; i) Yoke anchor; j) Filter plate with inflatable membrane; k) Lifting table; l) Hydraulic closure
device; m) Filter preframe

tubes can be made of various porous materi- Figure 78 shows an example of a complete
als, preferably polymers or ceramics, and have microfiltration unit including cross-flow ele-
quite narrow pore-size ranges, from a few mi- ments and the programmed control unit for batch
crometers down to hundredths of a micrometer. and continous operation.
They are, above all, microfilters for the concen-
tration of dilute suspensions and for clarifying
and sterilizing filtration. Such filter systems with 8.11. Special Filter Types
the finest membrane pore sizes are also suitable
for ultrafiltration and reverse osmosis; multi- Coarsely-dispersed systems with relatively high
layer or asymmetric membranes are used in them solids contents are dewatered with conventional
(→ Membranes and Membrane Separation Pro- screens like the vibrating screens used for classi-
cesses). fication. One such filter is the vertical sieve con-
Throughput rates range up to taining a bent screen plate, which is employed
3000 L m−2 h−1 , depending on pore size and fil- to separate coarse and fibrous solids at lower
tration pressure. The possible applications vary concentrations from process waters and waste-
with capacity. The principal users are chemical, waters with screen filtration. The sieve, which
pharmaceutical and foodstuffs producers and, is equipped with an adjustable screen slope, is
increasingly, bioengineering concerns. charged from the top, so that the slurry flows
60 Filtration

Figure 75. Automatic filter press (reproduced with permission of Eberhard Hoesch & Söhne)

downward by gravity. The screen, with slots filter media, where the electrolytic filtrate is dis-
varying from 0.125 – 2.5 mm wide, retains the charged [45]. Several separating chambers form
solids, which drop downward. The simple, in- filter systems similar to filter presses.
expensive design has made this device a widely- Difficultly filterable suspensions are also
used one in food preparation, the textile and filtered by high-gradient magnetic separation
manmade fiber industry, paper and pulp man- (HGMS) (→ Magnetic Separation). This type
ufacturing, and the chemical industry. of filter employs a steel wool medium. In a
Several new filtration mechanisms are very strong magnetic field, high field gradients
being explored with an eye to filtration are generated at the individual filaments. These
problems that have not yet been solved. gradients attract fine magnetic particles. This
These include, in particular, the dewatering HGMS filter thus resembles a depth filter. Suc-
of suspensions having relatively high con- cesses have been achieved in the purification of
centrations of extremely fine solids (below kaolin and wastewaters.
10 µm down to colloidal sizes). The conven-
tional separation techniques – flocculation and
microfiltration – generally yield filter cakes or
concentrates that require considerable energy for
complete phase separation (e.g., by drying). Re-
search on ionized phases has shown that the elec-
trokinetic effects of electro-osmosis for liquid
transport and electrophoresis for solids transport
along an electric field allow separation, even of
difficultly filterable suspensions. Both these ef-
fects have been known for a long time.
A filter based on the above processes con-
Figure 76. The dynamic filter press
sists of separating chambers with anodes, where a) Filtrate discharge pipe; b) Main shaft; c) Filter plate;
the ionized solids collect, and cathodes made as d) Agitating disk; e) Cake discharge valve
 Filtration 61

cles, the sensitivity of the product to impurities,

corrosion problems, the sensitivity of the equip-
ment to sedimentation and to product fluctua-
tions, the cost of operation, and so on. Table 5
can be used in the selection of special vacuum
filter types under a number of criteria. The tabu-
lated data should, however, be regarded only as
rough guidelines. Filter types are shown in Fig-
ure 79 together with the particle sizes for which
they can be used.
Figure 77. Schematic of tubular membrane filter
a) Tube bundle; b) Cross section

Figure 79. Filter selection as a function of solids particle

sizes

The higher cost of pressure filtration in com-

parison with vacuum filtration is usually not
justified except when the cake has a resistance
of 3.5 · 1011 m/kg. Flocculated solids, which
should not lose their structure since it is advan-
tageous for filtration, require careful handling,
especially in feeding to the filter. Because most
such solids are somewhat compressible, not too
much pressure should be applied, and so vac-
uum filtration is commonly preferred for these
Figure 78. Microfiltration equipment (Seitz-Microflow, re- materials.
produced with permission of Seitz-Filter-Werke) A safe selection without trials or appropri-
ate experience is possible only in the rarest in-
stances.
9. Filter Selection Little general information and few computa-
tional formulas can be given in the field of fil-
Because certain qualities, largely related to de-
tration, which is one of the oldest operations in
sign, characterize the ranges of application of
process engineering. Regrettably, filtration (like
filters, some guidelines can be set forth. These
other essential processes involving the handling
together with a few other points can provide a
of bulk solids, dumped and packed beds, etc.)
basis for filter selection. In general, a good se-
must deal with the effects of material proper-
lection takes account of factors such as slurry
ties that can be determined only with difficulty
properties, throughput, or cake formation rate
or cannot be measured in a predictable way, and
(see Table 2). Other points to be considered are
these effects are so large and pervasive that there
the density and viscosity of the liquid, the size,
is no comprehensive, unified way of allowing for
size distribution and shape of the solids parti-
62 Filtration
Table 5. Applicability of filters

Filter type Suspension of Operation

fine particles Pressure Washing Compression Continuous (c)

automatic (a)

Belt × c
Belt with compression × × × c+a
Nutsche × × × × a
Tilting pan × c
Leaf/plate × × a
Drum × c
Pressure drum × × × c
Membrane filter press × × × × a
Twin-belt pressure filters × × × × c
Tube press × × × a

them. There is no doubt, however, that selection slurries having a very broad particle-size spec-
criteria exist and that they imply at least certain trum. In such cases, some concession nearly al-
filter categories, so that in many cases the num- ways has to be made in terms of separation ef-
ber of open options is not very large. ficiency, or further operating practices, such as
careful cleaning or frequent replacement of the
filter medium, have to be introduced.
10. Filter Media Filter media can be characterized in terms of
the following overall criteria:
The outcome of filtration, that is, the degree to
1) Cut size, that is, the particle size that just
which the filter separates the two phases, is gov-
passes through the filter medium.
erned above all by the filter medium. Where the
2) Permeability; high permeability means low
available filter media are not suited to the prop-
pressure drop.
erties of the phase (solid) being separated, filter
3) Chemical stability with respect to the filtrate.
aids can close the gap.
4) Blocking tendency, particularly for fabrics in
The filter medium should be selected to pro-
cake filtration.
vide the desired separating effect and to fit the
5) Mechanical strength in relation to loads im-
special properties of the suspension (such as the
posed in back-blowing or the movement of
particle size of the solids and the viscosity of
filter cloths.
the liquid). The selection of a medium should
6) Smooth surface to promote cake removal.
also take account of service conditions such
as cleaning, washing, reaction to back-blowing, As is appropriate after many years’ experi-
and chemical and mechanical stability, which ence in filtration, a great many types of filter
are no less important than the slurry properties. media have been introduced in practice. New
In cake filtration, cake removal must also be con- materials and processing methods continue to
sidered. offer a wide range of improvements. The diver-
In line with the multiple purposes of filtra- sity of filter-media properties has led to a number
tion, media must perform the following tasks: of classifications in the literature. The following
seems to be an advantageous one:
1) Optimal retention of all solid particles out-
side the filter medium Perforated plates, screens, slotted screens
2) Retention of the solid particles, mainly in- Fabrics
side the filter medium, by virtue of effects Beds, felts and other nonwoven materials
generally lumped together as “entrapment,” Packed beds and precoat layers
which essentially have to do with adhesion Porous materials
forces and electrical forces. Membranes
Often these functions cannot be unambigu- Within these groups, there are differences in
ously separated; this is particularly the case with properties, especially with regard to chemical
 Filtration 63

stability (including aging). However, often phys- the medium, thus effecting some reduction in
ical and biological requirements are also im- pore size and also promoting bridge formation
posed, such as high-temperature stability, wa- on the medium. The ease of working with fabrics
ter uptake, swelling capacity, weathering behav- is an incomparable advantage, of course.
ior (stability to light), and resistance to insects The fabric weave is important for filtration
(moths) and bacteria (rotting). proper as well as service properties. Another es-
Aside from material properties, the overall sential factor is the structure of the fiber, which
filtration qualities can be represented only in an varies widely in natural and synthetic materials.
approximate way, because they depend heavily Where particularly high strengths are needed,
on the properties of the suspension being fil- as in twin-belt pressure filters, monofilament-
tered. Even the often-used permeability and/or yarn fabrics are preferred. High precision in fab-
mean pore size figures should be considered – at rication allows mesh openings in the micrometer
best – rough reference values for the behavior range, especially with metal fibers.
during filtration. A reliable assessment is usu- Within some limits it is possible to start with
ally possible only if practical tests or, within typical fabric data, such as weight per unit area,
limits, laboratory trials (e.g., with the test leaf numbers of warp and filling yarns, fiber diame-
filter, Chap. 7) are performed. ter, fabric thickness and fiber density, and calcu-
late the pore size and hydraulic resistance. The
Perforated Plates, Screens, Slotted resistance calculation is based on the pore radii
Screens. Aside from screens used in screen of the fabric and the yarn, and Poiseuille’s law
filtration, filter media in this group serve mainly is used as a first approximation.
to support filter cloths or papers, which as a rule The permeability of a clean, unused fabric
have finer pores. can be calculated (with about the same reliabil-
With perforated plates, the largest possible ity) from Kozeny’s equation (66); the starting
free surface area is usually desired so that the data are the densities and porosities of the yarn
pressure differences to be overcome in filtra- and the fabric. But empirical relations should
tion will be small. Free areas range from some give better agreement with experimental values.
20 – 30 % for ordinary plates with circular holes However, it is vital to know how the fab-
to over 90 % for high-quality screens with square ric influences cake formation and the narrowing
openings in the millimeter range. The free area and possible blocking of the pores. The result-
drops to less than 10 % for very fine sieves with ing change in hydraulic properties of the filter
openings a few micrometers across. medium is described in Section 2.2.
Slotted screens with very small openings,
used chiefly as strainers and candle filters (see Nonwovens, Papers, and Felts. These fil-
Section 8.3), are made by stacking plates, rings ter media consist of relatively short fibers (sta-
or other elements around a permeable cylinder. ple fibers a few centimeters long) formed into a
The fine gaps between the elements allow only random layer and then compacted in some way.
the liquid to pass. Strainers can be fabricated Nonwoven media are usually fabricated in fairly
more simply by winding profiled (wedge) wires thick layers and therefore function as depth fil-
or strings on a core. These units have little free ters (→ Nonwoven Fabrics).
area, roughly 10 %. As a result, they are eco- Papers made of cellulose fibers are available
nomic only when solids concentrations are very in a bewildering range of grades for use in lab-
low. oratories, small plants, and daily life (→ Paper
and Pulp). Heavier papers and paperboards (2 – 6
Fabrics. By far the most widely used filter mm thick) can also be fabricated from mixed
media are woven fabrics. Manmade fibers dom- materials, such as cellulose plus diatomaceous
inate, but fibers of glass, minerals, and metals earth or activated carbon. These filter materials
are also used to an increasing extent, especially meet a wide range of requirements and are em-
in view of their good chemical stabilities. ployed in large quantities for the clarification of
The advantages of multifilament-yarn fabrics beer, wine, or juices, and in the dyes and coat-
include the depth action of the filter medium, ings, food, and cosmetics industries. By virtue of
which permits slight penetration of solids into the raw materials and fabrication processes, one-
64 Filtration

time use of the filter medium is often economic; may not adequately remove them. Materials for
this feature is especially desirable in sterile fil- porous filters include minerals, diatomaceous
tration. earth, porcelain, clay, coal, graphite, corundum,
Conventional felts of relatively short natural rubber, plastics, and metals, including highly re-
and manmade fibers are usually not adequate to sistant nickel – chromium – molybdenum alloys.
the filtration and service loads in plant equip- The most important criterion for selection is
ment. Felts that incorporate woven-fabric rein- chemical and thermal stability.
forcement are often preferred for this reason. Porous materials made from equal-sized par-
Some loss in terms of the basic advantage of felt ticles are distinguished by uniform porosity. In
must be accepted when these composite materi- order to reduce the blocking tendency, layers
als are used. As a rule, needled felts have lower with differing particle sizes can be superimposed
resistances than woven fabrics. They have now with the fine-pored layer toward the filter cake;
become the most commonly employed nonwo- thus only the topmost layer need be cleaned, and
vens (→ Felts). the filter offers better service qualities.
Porcelain filters are available with pore radii
Packed Beds and Precoat Layers. Loose from 0.08 to 6 µm and porosities of 30 – 70 %.
beds of granular materials can also be used Sintered metal filters range from 1 to over 100
in clarifying and some cake filtrations. For eco- µm in pore size and from 30 to 60 % in poros-
nomic reasons, cheap natural products such as ity. Plastic filter media with about the same pore
sand, gravel, or coal are used, but it is desirable spectra can easily be fitted to the equipment.
to remove the excessively fine-grained fractions Their relatively poor temperature stability, how-
from them by washing. Common particle sizes ever, restricts their use. Besides poly(vinyl chlo-
are 3 – 50 mm for gravel, 0.35 – 0.45 mm for fine ride) and polyethylene, porous masses can also
sand, 0.45 – 0.55 mm for medium sands, and be fabricated from polytetrafluoroethylene, with
over 0.55 mm for coarse sands. Other candidate its excellent stability.
materials include minerals (quartz, limestone),
coke, anthracite, slag, wood pulp, glass beads, Membranes. At present a great number of
wadding, or fibers. distinct membranes are on the market, not just
The hydraulic properties are calculated with for ultrafiltration and reverse osmosis, but also
the relations developed in the theory section, for microfiltration (→ Membranes and Mem-
in particular Darcy’s law, Section 2.1.1, or – if brane Separation Processes). They are made of
the appropriate material data are known – the plastics and are suitable for clarifying as well
Kozeny equation (66). as pure surface filtration. If very small pores are
needed, membranes are assembled from two lay-
Rigid Porous Materials. Porous materials, ers, a coarse-pored supporting layer (with, e.g.,
which are fundamentally similar in structure, 15 – 20 µm pore openings) topped with a filter
are suitable for any kind of filtration. Their layer (0.2 µm pores). All membranes have a rel-
mechanical stability allows their use as filter me- atively narrow range of pore sizes.
dia without supporting structures (up to pres- A special form of membrane filtration em-
sures of 2 MPa and more). They are preferably ploys hollow fibers made of, e.g., polyamides,
employed as filter cartridges or in the form of with diameters of 50 µm and wall thicknesses
sheets and more recently, honeycomb and other of 13 µm. The solution being separated is intro-
three-dimensional shapes. Because they are gen- duced into the hollow fibers under an appropriate
erally too valuable to use just once, and be- pressure. Pure liquid escapes through the wall of
cause they can withstand vigorous backwash- the fiber, while the dissolved material remains
ing without special preparation, solids should behind and can easily be carried out of the fiber.
be collected mainly by surface filtration. Deep-
bed filtration is recommended only when the
particles are very small in comparison with the 11. Filter Aids
pores and are collected by an adsorptive mecha-
nism. In the intermediate region, solid particles Some suspensions contain solids that quickly fill
block the pores too quickly, and backwashing or block the openings in the filter medium. This
 Filtration 65

group includes suspensions substantially made ter aid, is filtered onto the medium (base layer)
up of relatively fine, soft (especially gelatinous), so that a clear filtrate can be obtained right from
compressible solids. Such feeds can still be fil- the start of filtration. Filter aid is also added to
tered well if the blocking of the filter medium is the slurry continuously during filtration. In batch
prevented by the inclusion of inert, readily fil- operation, this is done by stirring in the slurry
terable granular materials. These filter aids form tank; in continuous filtration, dry or wet filter
a layer permeable to the filtrate, and at the same aid can be metered into the slurry delivery line.
time they carry out the functions of a loose filter No generally valid rules exist for the proper ra-
cake. The particles being retained are deposited tio of filter aid to solids concentration. A variety
on the filter aid. This process must still leave of empirical values are available for some pro-
sufficiently free openings through which the fil- cesses and solids types. If there is too little filter
trate can pass. The main candidates for filter aids aid, the filtration goes badly; if too much, the
are thus highly porous materials. Diatomaceous filtrate flow rate drops off too sharply.
earths are very economical examples; their fine- The main applications for filtration with filter
ness is characterized by 10 % > 40 µm at the aids are the precoat technique for poorly filter-
high end and between 1 and 7 µm at the low able slimes of chemical and mineral products
end. Also used are perlites and, for special jobs, and the clarifying filtration of beverages (beer,
Fuller’s earths, powdered glass, coal prepara- wine, juices) containing soft, gelatinous impuri-
tions, cellulose fibers, wood pulp, paper stock, ties, as well as the clarification of gelatins, cane
bagasse (a sugar cane residue), talc, or plastics, juice, or edible oils.
although these products are less effective than
diatomaceous earths and perlites. The require-
ments for a good filter aid are uniform quality, 12. References
correct particle size and shape, and the highest
possible wet volume (specific volume in the wet 1. H. Darcy: “Les fontaines publiques de la ville
condition, usually greater than the wet volume de Dijon”, Paris 1856.
2. VDI-Richtlinie “Filtrierbarkeit von
per mass of filter aid).
Suspensionen” VDI 2762, 1997.
In diatomaceous earths, particles consist-
3. L. Svarovsky: Solid – Liquid Separation,
ing of needle-shaped diatoms have proved ad- Butterworths, London 1977, p. 175.
vantageous; disk-shaped particles filter poorly 4. M. Tiller, T. Cleveland, R. Lu, Ind. Eng. Chem.
and produce too dense a cake. Unsuitable con- Res. 38 (1999) 590 – 595.
stituents such as clay, or sand must be removed 5. P. H. Hermans, H. L. Bredée, Rec. Trav. Chim.
from the raw materials, because they hinder fil- 54 (1935) 680 – 700.
tration by blocking the pores. 6. A. Rushton, A. S. Ward, R. G. Holdich:
A synthetic filter aid is manufactured from Solid – Liquid Filtration and Separation
volcanic rocks. The raw material, bound with Technology, VCH Verlagsgesellschaft,
some water, is ground, then suddenly heated to Weinheim 1996, pp. 64 ff.
a high temperature; the grains inflate to form 7. K. Luckert, Wiss. Z. Techn. Univ. Magdeburg
spheres. Regrinding yields half-shell-shaped 36 (1992) no. 5/6, 74 – 80.
fragments, whose large surface area makes them 8. P. L. Boucher, J. Proc. Inst. Civ. Eng.
(1946 – 1947) 415 – 445.
suitable as a filter aid once the fines are screened
9. A. Rushton, A. S. Ward, R. G. Holdich:
out. Their action in filtration is somewhat worse Solid – Liquid Filtration and Separation
than that of diatomaceous earth, with a porosity Technology, VCH Verlagsgesellschaft,
20 – 40 % lower. Weinheim 1996, pp. 177 ff.
In precoating, a layer of filter aid several mil- 10. K. J. Ives, in A. Rushton (ed.): Mathematical
limeters thick is deposited on the filter medium Models and Design Methods in Solid-Liquid
before filtration proper. After the filtration is Separation, NATO ASI series E No. 88,
completed, the filter aid is often discarded along Martinus Nijhoff, Dordrecht 1985, pp. 90 ff.
with the collected solids. 11. A. Rushton, A. S. Ward, R. G. Holdich:
Several steps take advantage of the effect of Solid – Liquid Filtration and Separation
the loosened filter cake. First, a precoat some Technology, VCH Verlagsgesellschaft,
1 – 2 mm thick, containing 200 – 800 g/m2 of fil- Weinheim 1996, p. 198.
66 Filtration

12. G. Dierckx in: La Filtration Industrielle des 30. D. Leclerc, S. Rebouillat, in A. Rushton (ed.):
Liquides, Tome III, Société Belge de Mathematical Models and Design Methods in
Filtration, Liège 1978, pp. 295 – 314. Solid – Liquid Separation, NATO ASI series E
13. A. Palinski, W. Uhl, R. Gimbel, Vom Wasser No. 88, Martinus Nijhoff, Dordrecht 1985, pp.
89 (1997) 175 – 189. 356 ff.
14. J. Altmann, S. Ripperger, J. Membrane Sci. 31. J. Kozeny, Ber. Math.-naturwiss. Abt. Akad.
124 (1997) 119 – 128. Wien. (1927) 271 – 306.
15. S. Ripperger, J. Altmann, Filtrieren Separieren 32. A. E. Scheidegger: The Physics of Flow
11 (1997) no. 3, 109 – 113. Through Porous Media, 3rd ed., University of
16. W. Bender, Chem. Ing. Tech. 55 (1983) no. 11, Toronto Press, Toronto 1974, pp. 137 ff.
823 – 829. 33. H. Rumpf, A. R. Gupte, Chem. Ing. Tech. 43
17. K.-H. Steiner, Chem. Ing. Tech. 61 (1989) no.
(1971) no. 6, 367 – 375.
1, 1 – 8.
34. J. Gregory in K. J. Ives (ed.): The Scientific
18. H. Anlauf, Fortschrittsber. VDI, Reihe 3, 114
Basis of Flocculation, Sijdhoff & Noordhoff
(1986).
19. H. Schubert: Kapillarität in porösen Alphen aan de Rijn 1978, p. 91.
Feststoffsystemen, Springer Verlag, 35. H.-J. Jacobasch, P. Weidenhammer, Chem.
Heidelberg 1982, p. 184. Ing. Tech. 68 (1996) 1590 – 1594.
20. H. Anlauf, Maschinenmarkt 95 (1989) no. 8, 36. D. Houi, R. Lenormand, in F. Family, D. P.
26 – 30. Landau (eds.): Kinetics of Aggregation and
21. R. J. Wakeman: “Cake Dewatering,” in L. Gelation, Elsevier, Amsterdam 1984.
Svarovsky (ed.): Solid – Liquid Separation, 37. P. Schmitz, B. Wandelt, D. Houi, M.
Butterworths, London 1977, p. 300. Hildenbrand, J. Membrane. Sci. 84 (1993)
22. R. J. Wakeman, Filtr. Sep. 16 (1979) no. 6, 171 – 183.
655 – 669. 38. W. Höflinger, C. Stöckelmayer, A. Hackl, Filtr.
23. A. Rushton, A. S. Ward, R. G. Holdich: Sep. (1994) Dec., 807 – 811.
Solid – Liquid Filtration and Separation 39. W. Höflinger, C. Stöckelmayer, Staub
Technology, VCH Verlagsgesellschaft, Reinhalt. Luft 55 (1995) 423 – 428.
Weinheim 1996, pp. 348 ff. 40. W.-M. Lu, C. C. Lai, K.-J. Hwang, Sep.
24. D. Redeker, K.-H. Steiner, U. Esser, Chem. Technol. 5 (1995) 45 – 53.
Ing. Tech. 55 (1983) no. 11, 829 – 839. 41. “Filtrierbarkeit von Suspensionen,”
25. I. Nicolaou, W. Stahl, Aufbereit. Tech. 33 VDI-Richtlinie 2762 (1997).
(1992) no. 6, 328 – 338. 42. H. Anlauf, Filtrieren Separieren 8 (1994) no.
26. J. Walker, Spektrum Wissensch. 12 (1986) 2, 63 – 66, 69 – 70.
188 – 197. 43. H. Anlauf, Filtrieren Separieren 8 (1994) no.
27. W. Tiedemann, Fortschrittsber. VDI, Reihe 3, 3, 116 – 118, 121 – 126.
453 (1996). 44. W. Gösele, Filtrieren Separieren 9 (1995) no.
28. M. Shirato, T. Murase, E. Iritani, S. Nakatsuka,
1, 14 – 22.
Filtr. Sep. 24 (1987) no. 2, 115 – 119.
29. A. Rushton, A. S. Ward, R. G. Holdich: 45. F. M. Tiller, C. S. Yeh in H. S. Muralidhara
Solid – Liquid Filtration and Separation (ed.): Advances in Solid – Liquid Separation,
Technology, VCH Verlagsgesellschaft, Batelle Press, Columbus OH 1986, pp. 1 – 37.
Weinheim 1996, pp. 455 ff.
 Fire Extinguishing Agents 1

Fire Extinguishing Agents

Orville M. Slye, Jr., Loss Control Associates, Levittown, Pennsylvania 19056, United States

1. Introduction . . . . . . . . . . . . . . . . . 1 4. Dry Chemical Extinguishing Agents . 6

2. Water as an Extinguishing Agent . . . 1 5. Inerting Gas Extinguishing Agents . . 7
3. Fire-Fighting Foams . . . . . . . . . . . 3
6. Halogenated Extinguishing Agents . . 8
3.1. Limitations and Uses . . . . . . . . . . . 4
3.2. Foam Concentrates . . . . . . . . . . . . 4 7. Extinguishing Agents for Combustible
3.3. Guidelines for Using Fire-Fighting Metal Fires . . . . . . . . . . . . . . . . . . 9
Foams . . . . . . . . . . . . . . . . . . . . . 6 8. References . . . . . . . . . . . . . . . . . . 10

1. Introduction fire. Because water is generally plentiful, its use

is relatively inexpensive and effective. The ef-
Fire extinguishing agents include water, water ficiency of water for extinguishing fire is pri-
plus additives, “dry chemicals,” inerting gases, marily due to the change in physical state from
and halogenated compounds, each specifically liquid to vapor. The heat of vaporization, which
suited for certain types of fires. Water is the old- is 2260 kJ/kg, removes heat from the combus-
est means of extinguishing fire, and chemicals tion process. As an example of the heat removal
are used as additives to enhance its characteris- capability of water, a typical fire-fighting nozzle
tics for fire control. Dry chemical agents are mix- applying water at 380 L/min (100 US gal/min)
tures of powders applied from portable devices directed into a fire removes nearly 1000 MJ/min.
or from fixed systems. Inerting systems using In comparison with the complete combustion of
nitrogen, carbon dioxide, or flue gas have long 1 L of gasoline, which produces >36 MJ/kg, the
been used in fire control, especially in marine extinguishing efficiency of water can be fully
applications. Use of halogenated agents, with appreciated [2].
superior flame extinguishing properties, was in- Additional advantages of water as an extin-
creasing worldwide in the 1980s. guishing agent include the following:
The type of extinguishing agent depends on
the class of the combustible material. Various 1) Has the ability to dissolve and wash away
systems are used to classify combustibles and to many products of combustion so that the seat
determine the most effective type of extinguish- of the fire may be reached
ing agent [1]. 2) Can be easily pumped through hoses and
Table 1 illustrates three major systems for fire pipes because of the small change in vis-
classification. Some of these systems catego- cosity with temperature in the liquid phase
rize fire control agents according to the class or between 1 and 99 ◦ C
classes of fire for which they are most effective 3) Expands to steam, which has ca. 1700 times
and applicable. Although separation into classes the volume of the liquid; makes confined
of fire is often difficult in actual fire situations, spaces inert by displacing air and oxygen,
the classification systems allow an accurate de- aiding in fire extinguishment
scription of a fire situation and identify some 4) Has high surface tension (0.073 N/m), which
of the hazards associated with the fire-fighting enables water to be issued in a consolidated
activity. stream or in discrete water droplets from
spraying devices or “fog” nozzles
5) Has a density high enough to provide a phys-
2. Water as an Extinguishing Agent ical mass to a nozzle stream, which assists in
physical penetration
Water is the single most useful and efficient ma-
terial for controlling and halting combustion and

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11 113
2 Fire Extinguishing Agents
Table 1. Classification of fire-extinguishing agents

Classification United States United Kingdom Federal Republic of Germany

Class A fire normal combustibles: wood, solid materials (organic matter): ∗

cloth, paper, rubber, and plastics fire occurs with formation of
glowing embers
Class B fire flammable and combustible liquids or liquefiable solids ∗
liquids, gases, and greases
Class C fire energized electrical equipment gases or liquefied gases from a ∗
that may be harmed by the liquid spill or a liquid or gas leak
extinguishing media
Class D fire combustible metals, such as combustible metals ∗
magnesium, titanium,
zirconium, sodium, or potassium
Electrical fire see Class C no separate classification; see Class E
de-energize and use appropriate
agent for class of fire remaining
Class E see Class C see Electrical fire extinguishing agent chosen for fire
of surrounding material: foam
should not be used; water should
be used only in the form of a fog
and at a safe distance (>5 m),
depending on the voltage

∗ Identical to United Kingdom classification.

6) Has molecular stability; does not break down developed and extend the capability of water as
or dissociate appreciably at <1650 ◦ C, which an extinguishing agent.
exceeds ordinary flame temperature Inorganic freezing point depressants pre-
Although water is the most useful and effi- vent water from crystallizing at low tempera-
cient heat-removing agent for fire-fighting pur- ture. Calcium chloride [10043-52-4], used in
poses, some physical properties restrict use un- 94 % pelleted grade, depresses the freezing point
der certain conditions, including the following: of water to as low as −40 ◦ C; sodium chro-
mate [10034-82-9] is added (0.5 wt % of the
1) When frozen, water cannot be transported or calcium chloride used) for corrosion protec-
applied easily to a fire. tion. Other antifreeze materials, such as ethylene
2) High surface tension restricts ability to pene- glycol [107-21-1], propylene glycol [57-55-6],
trate and wet below the surface area of com- and glycerol [56-81-5], are also used for cold-
bustibles to extinguish deeply sourced fires. weather protection, primarily in automatic sprin-
3) Water readily runs off surfaces, leaving a kler systems. However, care must be taken to
coating too thin for heat removal or surface prevent contamination of public water supplies.
protection. The use of these materials in portable extin-
4) Transportation through hoses or pipes results guishers is not recommended because residual
in loss of pressure because of friction. antifreeze is flammable after the fire evaporates
5) Density and immiscibility reduce effective the water.
control of hydrocarbon fires; water sinks be- Wetting agents lower the surface tension of
low the fuel even when used in a fine spray. water from a normal level of 0.073 N/m to ca.
6) Water vapor explosion may occur if spon- 0.025 N/m, which allows water to penetrate solid
taneous vaporization is possible, e.g., in the materials and extinguish fires below the surface.
case of molten salts, bitumen, or other prod- Wetting agent solutions are most useful when
ucts with a temperature >120 ◦ C. used on tightly consolidated Class A fire hazard
7) Use of water to fight fires of lower molecular materials, such as straw, mattresses, or cotton
mass metals may be dangerous. bales, where the water, with a lower surface ten-
Chemicals that change water’s characteris- sion, reaches the deep-seated fire by capillary
tics by depressing freezing point, reducing sur- action more quickly and with better efficiency
face tension, increasing viscosity, and modify- than water without a wetting agent.
ing flow properties or water density have been
 Fire Extinguishing Agents 3

Viscosity-enhancing materials or “thicken- be temporary, fires involving fuels with a high

ers” increase the viscosity of water so that it may flash point require only a short interruption of
be applied to nonhorizontal surfaces. Two prin- combustion to halt reignition.
cipal types of water thickeners are used: those
that produce an organic gel and those that give a
slurry. Gels either coat the material that is burn- 3. Fire-Fighting Foams
ing or prevent the material from igniting. Ben-
tonite [1302-78-9], a powdered mineral, yields Fire-fighting foam is a mass of gas-filled bub-
a water slurry, as does ammonium phosphate bles formed from aqueous solutions of specially
[7783-28-0] or ammonium sulfate [7783-20-2]. formulated, concentrated liquid foaming agents.
Ammonium sulfate gives a thick slurry, which is The gas normally is air, but may be an inert gas.
used particularly in combating forest fires. These Because the density of the resulting foam
slurry-type mixtures retard flames because of is so low, it floats on the surface of flamma-
their solids content and the capability of ammo- ble and combustible liquids, producing an air-
nium salts to halt flaming and glowing ignition. excluding, cooling, continuous layer of vapor-
Flow property modifiers reduce friction re- sealing, water-bearing materials that halts or
sulting from water flowing at high velocity in prevents combustion [3]. Various methods and
a hose. Water pumped at high velocity through types of equipment are available to generate and
the small-diameter hose that is commonly used apply foam.
for fire fighting loses pressure because of fric- Formulation. Fire-fighting foams are formu-
tion between the water and the hose walls and lated in several ways for fire extinguishing ac-
because of turbulent flow within the hose. Dilute tion. Foams are produced by mixing an appro-
solutions of poly(ethylene oxide) [25322-68-3] priate amount of foam concentrate with water
can yield nonturbulent water flow in a fire hose. and then aerating and agitating the solution to
Flow increases of 55 – 70 % can be achieved in form the bubble structure.
a 3.8-cm fire hose when 0.017 vol % poly(ethyl- Some foams are thick and viscous, forming a
ene oxide) is added. Nozzle pressure at the end tough heat-resistant blanket over a burning liq-
of the hose is doubled when the flow modifier uid or on a vertical surface; others are thinner
is used. An added benefit from the water stream and spread more rapidly. Foams that produce
modifer is the ability to use small and more man- a vapor-sealing film of surface-active water so-
ageable hose sizes without loss of nozzle pres- lution on a liquid surface are available. Some
sure or flow volume. foams are used as large volumes of wet gas cells
Water density modification for fire-fighting for filling cavities and inundating surfaces.
purposes is achieved by adding air to water to Foams are defined by their expansion ratio,
form a semistable air foam that is lighter than which is the ratio of final foam volume to original
most flammable and combustible liquids or to solution volume before the air is added. Foams
emulsify the top layer of a burning liquid to ob- are arbitrarily subdivided into three ranges:
tain a nonflammable floating emulsion of water
1) low-expansion foam: expansion up to 20 : 1
and fuel. As do wetting agents, synthetic deter-
2) medium-expansion foam: expansion range
gents lower the water’s surface tension. Deter-
from 20 : 1 to 100 : 1
gents are chosen for their emulsification action.
3) high-expansion foam: expansion range from
When they are sprayed or directed into flamma-
200 : 1 to 1000 : 1
ble or combustible fuels, detergents mix rapidly
to produce a suspension of the fuel in the deter-
gent solution. Emulsification lowers the fuel’s
vapor pressure, which reduces the vapor concen- 3.1. Limitations and Uses
tration to below the lower flammable limit in air;
thus, the fuel no longer burns. Synthetic deter- Low-expansion foam develops a cooling, coher-
gent emulsifying agents are used at a concentra- ent blanket and is used primarily to extinguish
tion of 0.5 – 2.0 vol % yielding a fuel – solution – burning flammable or combustible liquid fires,
air emulsion with a lower density than that of such as in spills or in storage tanks. Foam ex-
either water or fuel. Although the emulsion may tinguishes fires progressively by first providing
4 Fire Extinguishing Agents

a cover on the surface of the liquid, such as in a improve foam formation and uniformity, as well
storage tank, to prevent vapor transmission and as to control viscosity at lower temperature.
then by cooling hot surfaces adjacent to the burn- Protein-type concentrates are available for
ing liquid to prevent reignition. Foams are also use with either fresh water or saltwater at 3
able to diminish or halt the generation of flam- or 6 vol % concentrations. The resulting foam
mable vapors from liquids or solids. Medium ex- is dense, viscous, and highly stabile; its resis-
pansion foam is used primarily to control spill tance to high heat and burnback is superior to
fires and to fill cavities where toxic or flammable that of other foaming agents. These foams cling
vapors may collect. to vertical surfaces and insulate them if the pro-
Use of medium- or high-expansion foam that portioning rate is increased or the water content
has air in the bubbles may be dangerous in a reduced.
small room. If the vapor concentration in the
room is higher than the explosive limit, the air Fluoroprotein Foaming Agents. These
from the foam may be enough to cause an ex- agents contain an additional fluorinated, surface-
plosion. Such accidents have occurred. active compound that provides a fuel-shedding
When attacked by heat and flame, foam property to the resulting foam. These foams
breaks down and the water content vaporizes. are particularly effective for fire-fighting situa-
Foam must be applied to a burning liquid sur- tions in which the foam becomes coated with
face in sufficient volume and rate to compensate fuel, such as when subsurface or base-injected
for evaporation, with additional foam required foam is used for fires in storage tanks or for foam
to establish a residual layer over any exposed streams applied from hose nozzles where falling
fuel. Foam is an unstable “air – water emulsion” foam may plunge into the burning fuel pool. In
that is easily dissipated by mechanical or phys- addition, the resulting foam has a greater com-
ical forces, by some chemical vapors or fluids, patibility with dry chemical agents than that of
and by incompatible extinguishing agents. Tur- protein foam. As with protein foam, the concen-
bulent air or a violent uplift of combustion gases trate is used with either fresh water or saltwater
can also divert light foam from the burning area. at concentrations of 3 or 6 vol %.
Foam solutions are conductive and are not
recommended for use on electrical fires. If foam Aqueous Film-Forming Foaming Agents
is used near electrical equipment, precautions (AFFF). The AFFF agents are synthetic com-
should be taken to minimize chances of electri- pounds that form air foams similar to those pro-
cal shock. duced by the protein-based materials. In addi-
tion, these foaming agents are capable of form-
ing water solution films on the surface of flam-
3.2. Foam Concentrates mable liquids from which the term aqueous film-
forming foam is derived. The AFFF concentrates
Some foam concentrates are available for spe- are used at either 3 or 6 vol % with fresh water
cific applications, whereas others are more suit- or seawater.
able for extinguishing fires in all types of The air foams generated from AFFF solutions
flammable liquids, including water-soluble and possess low viscosity, have fast spreading and
foam-destructive liquids. leveling characteristics, and, like other foams,
act as surface barriers to exclude air and halt fuel
Protein Foaming Agents. Concentrates of vaporization. The unique feature of these foams
these foaming agents consist of protein frag- is the continuous aqueous layer that forms under
ments derived from chemical digestion and the foam. This floating film on the hydrocarbon
hydrolysis of natural protein solids. The material fuel surface helps suppress combustible vapors
gives elasticity, mechanical strength, and water and cools the fuel substrate. The film is capable
retention capability to the resulting foams. of spreading over fuel surfaces not fully covered
The concentrates also contain dissolved poly- by foam; it is self-healing when mechanically
valent metallic salts, which strengthen the bub- disrupted and continues to spread as long as a
bles when the foam is exposed to heat and flame. reservoir of nearby foam remains. Hot surfaces
Organic solvents are added to the concentrates to can reduce foam effectiveness as can aromatic
 Fire Extinguishing Agents 5

hydrocarbons. The insulating effect in protect- and acrylonitrile. Relatively small amounts of
ing flammable or combustible liquids against ra- these substances rapidly deteriorate ordinary
diant heat is lower with these foams compared fire-fighting foams.
to protein foams. Proprietary compositions of several alcohol-
Concentrates of AFFF agents contain flu- type concentrates, based on concentrate bases
orinated, long-chain synthetic hydrocarbons of protein, fluoroprotein, or AFFF foams, have
with particular surface-active properties. Vari- been developed. The most common are usually
ous water-soluble, high-molecular mass, syn- described as polymeric alcohol-resistant AFFF
thetic polymers are added to aid in strengthening concentrates, which produce foams suitable for
the bubble wall and in retarding breakdown. application to either flammable hydrocarbons or
As used, these foams are nontoxic and water-miscible liquids. These substances exhibit
biodegradable in diluted form. Because of the AFFF characteristics when used on hydrocar-
low surface tension of solutions draining from bons and produce a floating gel-like mass for
AFFF, the foams may be useful under mixed foam buildup on water-miscible fuels.
class fire situations (Class A and B), where deep
penetration of water is needed to extinguish High-Expansion Foaming Agents. High-
deeply sourced fires in Class A materials. The expansion foaming agents are used to control
AFFF concentrates must not be mixed with other and extinguish Class A and Class B fires and
types of foam concentrates; however, the foam are particularly well suited for flooding con-
itself does not break down other types of foams fined spaces. Applications are generally indoor
in fire-fighting operations. The AFFF agents are because out-door use is limited by the weather.
compatible with dry chemical fire-fighting com- Liquid concentrates for producing high-
pounds. expansion foam consist of a synthetic hydro-
carbon surfactant that will foam copiously with
Synthetic Hydrocarbon Surfactant Foam- a small input of turbulent action. Normally 1 –
ing Agents. These hydrocarbons are syntheti- 2 vol % of concentrate in water is used. The air
cally produced surface-active compounds that supply for foam generation should be outside the
foam copiously in water solution; however, their fire area because combustion products have an
use for fire fighting requires some care. These adverse effect on the resulting foam volume and
compounds are also used at concentrations of 3 stability. Tests have shown that expansion ratios
or 6 vol % in water. of ca. 500 : 1 are the most effective for control-
Fire-fighting characteristics depend on the ling fires and reducing vaporization from liq-
volume of foam layer on the burning surface uefied natural gas (LNG) spills. As water drains
that restricts air and controls combustible vapor from the foam, a thin ice layer is formed. This ice
production. In addition, a minor cooling effect layer floats on the LNG and supports the high-
comes from the water contained in the foam, expansion foam blanket, retarding vapor gener-
which is a function of the rapid drain time of the ation and possibly building a shield to protect
water from the foam mass. This drain time leaves the LNG surface from radiated heat.
a bubble mass that is highly vulnerable to heat
or mechanical disruption. A rate of application Chemical Foaming Agents and Powders.
higher than that used with ordinary fire-fighting These materials have become obsolete because
foams is required to gain control and extinguish- of the superior economics and ease of handling
ment. The foams from these agents are some- of liquid foam-forming concentrates. Chemical
times destructive to normal fire-fighting foams. foam is formed by the aqueous reaction of alu-
minum sulfate [10043-01-3] and sodium hydro-
Alcohol-Type Foaming Agents. Alcohol - gen carbonate [144-55-8]; the foam also con-
compatible agents are used on fires involving tains proteinaceous stabilizers. The carbon diox-
fuels that are water soluble, water miscible, or ide [124-38-9] gas that results is trapped in the
are polar solvents. They can also be applied to foam.
normal flammable liquids, but are most effec-
tive when used on fires in alcohols, enamel and
lacquer thinners, methyl ethyl ketone, acetone,
6 Fire Extinguishing Agents

3.3. Guidelines for Using Fire-Fighting combustion zone. Dry chemicals, known as dry
Foams powders in the United Kingdom, do not extin-
guish fire by cooling, smothering, or emitting an
Foams are effective for fire control if the follow- inert gas, but instead provide instantaneous and
ing general rules are applied: momentary flame extinction [1, p. 199], [4].
Extinguishers for applying dry chemicals
1) Foam application should be gentle because onto fires evolved from hand-held tubes of
agitated application increases the time to ex- sodium hydrogen carbonate to a variety of
tinguish the fire and the amount of foam con- portable and fixed fire extinguishing systems
centrate used. using dry chemical pressurized-gas propellant.
2) Successful use of foam depends on the rate Particle size range of the mixture is 5 – 75 µm,
of application. Rates are expressed in terms with most in the range of 20 – 25 µm.
of the amount of foam solution (by volume) In 1959 the U.S. Navy developed the potas-
reaching the total area of fuel surface each sium hydrogen carbonate [298-14-6] formula
minute. Thus, an expansion rate of 1 : 8 with for dry chemicals. This material has twice the
an application rate of 4.1 L min−1 m−2 pro- flame-quenching capacity per unit mass as the
vides 32.8 L min−1 m−2 of finished foam. sodium compound. The material is called Pur-
Increasing foam application rate over the ple K because it exhibits a purple flame when it
minimum generally reduces time to extin- encounters a flame. Purple K is compatible with
guish the fire. If application rates fall below AFFF when applied in twined nozzle systems
the minimum, extinguishment is improbable. and provides rapid control of burning spilled
Application rates are determined by vendors flammable liquids, such as during an airplane
or approval laboratories. crash.
3) Foams are more stable when generated with Ammonium dihydrogen phosphate
water at an ambient temperature of 2 – 27 ◦ C; [7722-76-1]has an extinguishing action on flam-
either fresh water or seawater can be used. mable liquid fires similar to that of sodium
Foam contaminants, such as detergents, oil hydrogen carbonate. However, ammonium di-
residues, or certain corrosion inhibitors, may hydrogen phosphate also decomposes when
adversely affect foam quality. heated to yield a glassy coating of metaphos-
4) The location of foam-making device air in- phoric acid [37267-86-0], HPO3 , which may
lets is important because combustion prod- halt further combustion of Class A fuels such
ucts can adversely affect foam quality. as wood. This extinguishing agent is useful for
5) The pressure of water in foam-making de- fires in either Class A or Class B fuels. Electrical
vices affects foam quality; high or low limits fires, Class C, can also be extinguished by dry
should not be exceeded. chemicals because the powder is not electrically
6) Some fire-fighting chemicals, such as va- conductive. Extinguishers containing this agent
porizing liquid extinguishing agents and dry are “multipurpose” because they can be used on
chemicals, can adversely reduce the effec- Class A, B, or C fires.
tiveness of foam. A potassium-based dry chemical consisting
of potassium chloride [7447-40-7] or Super
K has been developed for fire fighting. This
agent exhibits a flame-extinction efficiency that
4. Dry Chemical Extinguishing is slightly less than that of potassium hydrogen
Agents carbonate.
Monnex, an extinguishing agent developed
Dry chemical agents, which are mixtures of by ICI (United Kingdom), consists of the ad-
powdered chemical compounds of varying dition product of urea and potassium hydrogen
composition, have the most efficient flame- carbonate and is unique in its mode of reac-
halting capability. The compounds are stored tion. Urea [57-13-6] can form adducts, or inclu-
in moisture-proof containers and are pneumati- sion complexes, under certain processing condi-
cally blown into a fire by a pressurized gas dis- tions. These complexes are crystalline mixtures
charge that conveys the solid powder into the in which the molecules of one of the components
 Fire Extinguishing Agents 7

are contained within the crystal lattice frame- ity and is ideal for use on energized electrical
work of the other compound; the original com- equipment.
ponents separate when the mixture is heated. In Carbon dioxide is the only inerting gas of
Monnex, urea is contained in the potassium hy- which large volumes can be liquefied and main-
drogen carbonate lattice. tained in that state in a small container volume
A finely powdered dry chemical is a more at ordinary temperature and at moderate pres-
efficient flame-quenching agent than the same sure. Carbon dioxide vapor is more dense than
powder with a coarser particle-size distribution. air, so the gas sinks to the base of the flames, re-
Fine powders cannot be projected great dis- placing air and oxygen and maintaining a flame-
tances, however, which makes them impracti- smothering atmosphere. Carbon dioxide extin-
cal for fire extinguishing purposes. The urea – guishes flammable and combustible liquid and
potassium hydrogen carbonate particles are of gas fires at concentrations of ca. 30 – 38 vol %
normal and customary size distribution and can carbon dioxide; however, a higher concentration
be projected efficiently through a nozzle under may be necessary to extinguish certain gases that
gas pressure. However, when heated, the crys- have wide flammable limits. Specific require-
tals shatter, yielding fine particles and resulting ments of the vendor, regulatory standards, or fire
in more efficient flame-quenching than is nor- codes should be consulted for particular appli-
mally obtained. cations.
Reignition is possible once the carbon diox-
ide dissipates and air (oxygen) contacts the com-
5. Inerting Gas Extinguishing Agents bustible material before the material has cooled
below its ignition temperature or fire point. Deep
Inerting gases extinguish or prevent fire by seated fires may continue in Class A materials
partial exclusion of oxygen from contact with after flame control has been achieved with car-
the combustible material. Inerting gases in- bon dioxide application. The gas diffuses slowly
clude gases that do not react with combustible through materials that are difficult to penetrate.
materials and can dilute oxygen or air atmo- Therefore, cooling of these materials is neces-
spheres to the point where oxidation (or com- sary and is normally accomplished by maintain-
bustion) either cannot start or cannot continue. ing an atmosphere of ca. 38 % carbon dioxide
Helium [7440-59-7], argon [7440-37-7], kryp- for a period of time.
ton [7439-90-9], nitrogen [7727-37-9], carbon Two principal types of storage units are used
dioxide [124-38-9], and sometimes water va- to contain carbon dioxide for fire-protection ap-
por are used to produce inert atmospheres. Flue plications. In the high-pressure method, the liq-
gases or products of combustion gases, such as uid and gas phase are at equilibrium in a steel
those from oil burners, are also inerting gases container at ca. 6 MPa pressure. The familiar
because of their high carbon dioxide and nitro- portable CO2 extinguisher is an example of the
gen content and low (ca. 5 %) oxygen content. high-pressure container. The low-pressure stor-
Applications for flue gas inerting include ma- age unit is maintained at ca. 2 MPa and kept at
rine petroleum tankers where flue gases are used −18 ◦ C by a refrigeration unit. This method al-
for storage tank inerting. Carbon dioxide and ni- lows large amounts of CO2 , mostly in the liquid
trogen are the principal inerting gases currently state, to be stored in light, steel-walled contain-
used. ers. Larger systems generally incorporate fire de-
tectors and automatic or remote manual activa-
Carbon dioxide gas has long been used as an tion devices. An alarm, sounding 15 – 20 s be-
inerting agent for fire extinguishment and pre- fore gas release, is required for confined spaces
vention [5]. Carbon dioxide is noncombustible to avoid asphyxiation of any personnel that may
and does not react with most substances. The be present.
gas provides its own pressure for discharge from
Nitrogen is used as an oxygen diluent to halt
storage containers used for fire-protection appli-
combustion and produce an inert atmosphere [1,
cations. As a gas or as a finely divided solid (dry
p. 191], [6]. However, nitrogen is not easily con-
ice), carbon dioxide does not conduct electric-
densed. The gas must be stored at high pressure
8 Fire Extinguishing Agents

(ca. 14 MPa) in heavy cylinders, which limits are indicated by the second digit; chlorine atoms
its application as a fire extinguishing material or are represented by the third digit; the fourth digit
inerting gas. In addition, because it is slightly indicates the number of bromine atoms; and the
lighter than air, nitrogen is difficult to direct or fifth indicates the number of iodine atoms, if any.
maintain near the base of flames or seat of the Hydrogen atoms are not numbered.
fire, where it is needed to be the most effective. Some common halogenated extinguishing
Applications in liquid form have been attempted, agents are listed in Table 2. Most countries al-
but the extensive quantities that are needed are low use of Halon 1211 and 1301 for fire control;
not currently practical. Halon 2402, which is highly toxic, has limited
applications where humans are not present, e.g.,
Water vapor can be used, in special cases, as for fuel tank or engine compartment inerting [7].
an extinguishing agent or inerting gas. However, Halons are effective flame extinguishing
high-pressure steam can generate static electric- agents because their density causes flames to
ity, which can ignite flammable vapors, unless sink and stay in the region of the base of the
special precautions are taken. flames. Knowledge is limited about combus-
tion kinetics and the influence of the actions
and reactions of halogenated material. Evidence
6. Halogenated Extinguishing Agents has shown that Halon agents remove the active
chemical species involved in the chain reactions
Although elemental halogens are vigorous ox- of flame propagation. In fire situations, Halons
idizing agents when reacted with metallic and decompose at flame temperature and the result-
nonmetallic elements with one or more atoms of ing products have an affinity for the highly ac-
oxygen, the resulting ionic halogens chemically tive free radicals (· O, · H, and · OH) produced
combine with and reduce many compounds. Re- by burning fuels, subsequently removing them
action of elemental halogens with highly oxidiz- from further flame propagation. Halogenated
able hydrocarbons, such as methane [74-82-8], agent efficiency occurs because of the follow-
ethane [74-84-0], or propane [74-98-6], using ing reactions:
special high-temperature methods in the absence
1) Capture of active atomic hydrogen by halo-
of oxygen, yields a gaseous or liquid organic
gen, removing hydrogen from further heat-
compound that is capable of decomposition and
producing reactions 2) Reaction of active
is an efficient fire-extinguishing agent. Early
free-radical hydroxyl groups from oxidation
halogenated extinguishing agents included car-
of fuels, followed by a halogen hydride reac-
bon tetrachloride [56-23-5] and methyl bromide
tion that results in water
[74-83-9].
2) Regeneration of active atomic halogen by
Halons. In 1946 it became obvious that of the preceding reaction so that the processes
all of the halogenated compounds, the lower of capture and removal of atomic and free-
aliphatic hydrocarbons substituted with bromine radical groups may be repeated
resulted in powerful extinguishing agents. How- The flame-extinguishing performance of
ever, the materials were toxic. The fluorine bond Halon 1301 is slightly superior to that of Halon
to carbon was known to be very stable, and if a 1211. In general, ca. 5 vol % of Halon 1301 ex-
compound containing some new ratio of fluo- tinguishes fires in most hydrocarbon fuels, com-
rine : bromine : carbon could be synthesized, pared with, e.g., 6 vol % of Halon 1211. Individ-
perhaps the result would be less toxic. This the- ual fuels should be tested or reference made to
ory led to the development of the halogenated standard tables to predict the actual extinguish-
fire extinguishing agents known as Halons [1, ing concentration. An 8 – 9 vol % concentration
p. 192]. is required to prevent flame propagation in com-
Nomenclature for the Halons has been sim- bustible mixtures of ordinary fuels in air. Halon
plified. Integers are used to represent the various 1301 is ca. 2.5 times more effective than carbon
constituents in the material: the first digit repre- dioxide.
sents the number of carbon atoms in the com- Solid combustibles can sometimes be extin-
pound molecule; the number of fluorine atoms guished by using Halons; however, soaking time
 Fire Extinguishing Agents 9
Table 2. Halogenated extinguishing agents

Chemical name CAS Trade Molecular

registry name formula
number

Bromomethane [74-83-9] Halon 1001 CH3 Br

Bromochlorodifluoromethane [74-97-5] Halon 1211 CBrClF2
Bromotrifluoromethane [75-63-8] Halon 1301 CF3 Br
1,2-Dibromo-1,1,2,2-tetrafluoroethane [124-73-2] Halon 2402 C2 F4 Br2

is required to allow the Halon to reach the seat of are being used. Many of these metals require
the fire in a mass of material. Soaking time varies extensive heat exposure before reaching ignition
with the solid combustible material composition temperature, whereas others may ignite sponta-
and geometry. neously.
Metals burn at extremely high temperature
Toxicology and Occupational Health. and are highly reactive. No extinguishing agent
When Halons are used in occupied areas, tox- is known that will halt the oxidation reactions of
icity, characterized by anesthetic or narcotic burning metals. Dry sand, cement, and special
effects, must be considered. High Halon con- powders are possible materials. Combustible
centration can lead to dizziness, impaired co- metal fires can be extinguished by removing the
ordination, and reduced mental acuity. At high metal’s contact with air or oxygen, by smother-
concentration, prolonged exposure can result in ing, by inerting, or by cooling the surrounding
unconsciousness or even death. area to lower the temperature of the mass below
Halon 1301 is the least toxic and, for most its ignition point [10].
applications, can be discharged into occupied One proprietary mixture consists of graphite
spaces. Its TLV-TWA values and MAK are and foundry coke, carefully sized to facili-
1000 ppm and 6100 mg/m3 , respectively [8], [9]. tate easy handling, packing, and application to
System designs exceeding 7 vol % concentra- the burning metal surface by scoop or shovel.
tion have induced light-headedness and have re- Graphite is difficult to ignite and is a good heat
duced dexterity. Above 10 vol % toxic effects conductor; i.e., it absorbs heat and radiates it
are considered potentially serious and these lev- from the burning area. An organic phosphate
els should be avoided. Halon 1211 has a lower added to the mixture decomposes to yield a non-
threshold limit than Halon 1301 (TLVs and combustible smoke that penetrates the spaces
MAKs have not been established), and the ef- between graphite particles to exclude oxygen.
fects at concentrations required for fire extin- The mixture is a reducing agent and is moder-
guishment are comparable to those of carbon ately effective for all metal fires.
dioxide. Another proprietary mixture consists largely
In general, application from portable extin- of carefully sized sodium chloride [7647-14-5]
guishers in typical rooms is considered safe, but with tricalcium phosphate [7758-87-4] powder,
fixed systems should be restricted to unoccupied and zinc stearate [557-05-1] added to facili-
areas. Concentrations up to 4 vol % have been tate discharge from a pressurized extinguisher
shown to be tolerable for a 1-min maximum ex- through a delivery nozzle. A small amount of
posure, which compares with the same exposure powdered thermoplastic material is added to
time for a 10 vol % concentration of Halon 1301. the mixture to melt and hold the sodium chlo-
ride particles together for efficient cooling and
smothering of the burning metal. This material
7. Extinguishing Agents for is suitable for all metal fires. A powder specially
Combustible Metal Fires formulated for sodium fires contains sodium car-
bonate [497-19-8] instead of sodium chloride [1,
Class D combustible metal fires are an impor- p. 205].
tant consideration when materials that burn in
air, such as elemental metals and their alloys,
10 Fire Extinguishing Agents

Inert gas blanketing of burning metals, e.g., 2. R. M. Hodnut in A. E. Cote (ed.): Fire
with argon, helium, and neon [7440-01-9], is an Protection Handbook, 16th ed., Chapter 1,
effective extinguishing method where feasible. Section 17, Chapter 6, Section 21, National
Ternary eutectic chloride powder contains Fire Protection Association, Boston 1986.
potassium chloride [7447-40-7], sodium chlo- 3. Reference 2, N. R. Lockwood, Chapter 4,
ride, and barium chloride [10361-37-2]. This Section 19, p. 32.
mixture, when exposed to burning metals, melts 4. Reference 2, W. Haessler, Chapter 3,
and can cover the burning surface, thus exclud- Section 19, p. 24.
ing oxygen. Water, applied judiciously from a 5. Reference 2, H. V. Williamson, Chapter 1,
Section 19, p. 2.
safe distance, can be used for burning magne-
6. Reference 2, P. F. Johnson, Chapter 6,
sium or titanium. Water dissociates to hydrogen
Section 19, p. 55.
and oxygen at the burning metal surface, thus 7. Reference 2, D. W. Moore, Chapter 2,
it may increase the burning rate. Water is not Section 19, p. 11.
safe to use on burning sodium and other alkali 8. ACGIH (ed.): Threshold Limit Values (TLV)
metals. and Biological Exposure Indices, ACGIH,
Cincinnati, Ohio, 1986 – 1987.
9. DFG (ed.): Maximum Concentrations at the
8. References Workplace (MAK) , VCH Verlagsgesellschaft,
1. R. L. Tuve: Principals of Fire Protection Weinheim 1986.
Chemistry, National Fire Protection 10. Reference 2, A. S. Prokopovitsh, Chapter 5,
Association, Boston 1976, p. 143. Section 19, p. 49.

Fire Resistance → Flame Retardants

Fireworks → Pyrotechnics
Fischer – Tropsch Synthesis → Coal Liquefaction
Fish Oils → Fats and Fatty Oils
 Fixed-Bed Reactors 1

Fixed-Bed Reactors
For other industrial reactors and their applications, see → Stirred-Tank and Loop Reactors, → Tubular
Reactors, → Fluidized-Bed Reactors, → Bubble Columns, → Three-Phase Trickle-Bed Reactors, → Reaction
Columns, → Thin-Film Reactors, → Metallurgical Furnaces, and → Biochemical Engineering.
Gerhart Eigenberger, Institut für Chemische Verfahrenstechnik, Universität Stuttgart, Stuttgart, Federal
Republic of Germany

1. Introduction . . . . . . . . . . . . . . . 2 4.2. Adiabatic Multistage Reactors with

2. Catalyst Forms for Fixed-Bed Reac- Interstage Heat Transfer . . . . . . . 17
tors . . . . . . . . . . . . . . . . . . . . . 4 4.3. Reactors with Heat Exchange Inte-
2.1. Gas – Catalyst Mass and Heat grated in the Fixed Bed . . . . . . . . 19
Transfer . . . . . . . . . . . . . . . . . . 6 4.3.1. Heat Transfer Media for Fixed-Bed
2.1.1. Random Packings . . . . . . . . . . . . 6 Reactors . . . . . . . . . . . . . . . . . . 19
2.1.2. Monolith Structures . . . . . . . . . . . 7 4.3.2. Reactor Designs . . . . . . . . . . . . . 22
4.3.3. Influencing the Course of the Reaction 24
2.2. Flow and Pressure Loss in Fixed
Beds . . . . . . . . . . . . . . . . . . . . . 8 5. Autothermal Reaction Control . . . 27
5.1. Introduction . . . . . . . . . . . . . . . 27
2.3. Heat Transport Transverse to the
5.2. Reaction Control with Periodic Flow
Flow Direction . . . . . . . . . . . . . . 9
Reversal . . . . . . . . . . . . . . . . . . 28
2.4. Comparison and Evaluation of Dif- 5.3. Reactor Behavior . . . . . . . . . . . . 29
ferent Catalyst Forms . . . . . . . . . 9 6. Stability, Dynamics, and Control of
2.4.1. Catalyst Forms for Adiabatic Opera- Industrial Fixed-Bed Reactors . . . 32
tion . . . . . . . . . . . . . . . . . . . . . 10 6.1. Introduction . . . . . . . . . . . . . . . 32
2.4.2. Catalyst Forms for Isothermal Opera- 6.2. Parametric Sensitivity . . . . . . . . . 32
tion . . . . . . . . . . . . . . . . . . . . . 11 6.3. Multiple Stationary States . . . . . . 34
3. Adiabatic Reaction Control . . . . . 13 6.4. Migrating Reaction Zones . . . . . . 36
4. Reaction Control with Supply or Re- 6.5. Safety Aspects . . . . . . . . . . . . . . 38
moval of Heat in the Reactor . . . . 15 6.6. Control of Fixed-Bed Reactors . . . 39
4.1. Introduction . . . . . . . . . . . . . . . 15 7. References . . . . . . . . . . . . . . . . . 40

Symbols (see also → Principles of Chemi- L length of catalyst bed, m

cal Reaction Engineering and → Model Reac- Ṅ energy required for coolant circulation,
tors and Their Design Equations) kW
Nu Nusselt number
ap specific outer surface area of catalyst,
Q̇ heat flow to be transferred, kW
m2 /m3 packing
Re Reynolds number
A flow cross-sectional area, m2
Sc Schmidt number
c molar concentration, mol/m3
Sh Sherwood number (Eq. 2.10)
c0 feed concentration, mol/m3
T temperature, K
c pG specific heat of reaction gas, kJ kg−1 K−1
T0 feed gas temperature, K
cs specific heat of catalyst, kJ kg−1 K−1
U circumference, m
D diffusion coefficient, m2 /s
Uw gas – catalyst heat-transfer coefficient,
dp catalyst particle diameter, m
W m−2 K−1
dh hydraulic diameter (d h = 4 A/U ), m
vG interparticle velocity, m/s
f 1,2 Ergun coefficients (Eqs. 2.4, 2.5)
V̇ volume flow rate, m3 /s
Gz mass-flow velocity, kg m−2 s−1
VR reactor volume, m3
kG gas – catalyst mass-transfer coefficient,
w migration velocity of reaction zone, m/s
m/s
z space coordinate, m

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b04 199
2 Fixed-Bed Reactors

ZL reactor length, m selectivity or yield due to the adiabatic temper-

αW wall heat-transfer coefficient, ature development are expected. The character-
W m−2 K−1 istic feature of adiabatic reaction control is that
ε void fraction, m3 free space/m3 packing the catalyst is present in the form of a uniform
η dynamic viscosity, N s m−2 fixed bed that is surrounded by an outer insulat-
∆hR reaction enthalpy, kJ/mol ing jacket (Fig. 1 A). Adiabatic reactor designs
∆p pressure drop, N/m2 are discussed in Chapter 3.
∆T ad adiabatic temperature change, K
∆T c cooling temperature change between in-
let and outlet, K
∆x molar conversion, mol/mol
λeff effective axial thermal conductivity,
W m−1 K−1
λG molecular gas thermal conductivity,
W m−1 K−1
λr effective radial thermal conductivity,
W m−1 K−1
 density, kg/m3
G gas density, kg/m3
S density of catalyst particle, kg/m3
ξ pressure drop coefficient

1. Introduction
Catalytic fixed-bed reactors are the most impor-
tant type of reactor for the synthesis of large-
scale basic chemicals and intermediates. In these
reactors, the reaction takes place in the form of
a heterogeneously catalyzed gas reaction on the
surface of catalysts that are arranged as a so-
called fixed bed in the reactor. In addition to the
synthesis of valuable chemicals, fixed-bed reac-
tors have been increasingly used to treat harmful
and toxic substances. For example, the reaction
chambers used to remove nitrogen oxides from
power station flue gases constitute the largest
type of fixed-bed reactors as regards reactor vol-
ume and throughput, while automobile exhaust
purification represents by far the most widely
employed application of fixed-bed reactors.
With regard to application and construction,
it is convenient to differentiate between fixed- Figure 1. Basic types of catalytic fixed-bed reactors
bed reactors for adiabatic operation and those A) Adiabatic fixed-bed reactor; B) Multitubular fixed-bed
reactor
for nonadiabatic operation. Since temperature
control is one of the most important methods Since the incoming reaction gases in most
of influencing a chemical reaction, adiabatic re- cases must be heated to the ignition temperature
actors are used only where the heat of reaction is of the catalytic reaction, adiabatic reaction con-
small, or where there is only one major reaction trol is often coupled with heat exchange between
pathway; in these cases no adverse effects on the incoming and exiting reaction gas resulting
 Fixed-Bed Reactors 3

in so-called autothermal reaction control. This 1) For product separation

type of reaction control offers certain specific 2) For recycle compression
features and development perspectives, which 3) For repeated heating and cooling of the cir-
are discussed in Chapter 5. culating material to the reaction temperature
Reactions with a large heat of reaction as and the temperature of the separating device
well as reactions that are extremely tempera- 4) Due to loss of product resulting from the
ture-sensitive are carried out in reactors in which need to remove part of the circulating ma-
indirect heat exchange occurs via a circulating terial to limit the amount of inert substances
heat transfer medium integrated in the fixed bed. or byproducts in the recycle stream (bleed
Since in most cases the task of the heat-trans- stream).
fer cycle is to maintain the temperature in the To minimize these costs it is therefore nec-
fixed bed within a specific range, this concept is essary to maximize the conversion in the reac-
frequently described as an “isothermal fixed-bed tor and avoid as far as possible inert accompa-
reactor”. However, isothermal reaction control nying substances in the reaction mixture. With
does not provide optimum selectivity or yield in irreversible reactions (e.g., partial oxidations)
all cases, and for this reason the concept of heat the trend is therefore towards a highly concen-
exchangers integrated in the fixed bed is also be- trated, approximately stoichiometric feed com-
ing increasingly used to achieve nonisothermal position, which may occasionally be in the ex-
temperature profiles. plosive range. The resulting problems are dis-
The most common arrangement is the mul- cussed in Chapters 4 and 6.
titubular fixed-bed reactor, in which the cata-
lyst is arranged in the tubes, and the heat carrier
circulates externally around the tubes (Fig. 1 B). 2. Catalyst Forms for Fixed-Bed
Fixed-bed reactors with an integrated heat sup-
ply or removal are discussed in Chapter 4.
Reactors
Fixed-bed reactors for industrial syntheses The heart of a fixed-bed reactor and the site of
are generally operated in a stationary mode (i.e., the chemical reaction is the catalyst. The pro-
under constant operating conditions) over pro- cesses taking place on the catalyst may formally
longed production runs, and design therefore be subdivided into the following separate steps:
concentrates on achieving an optimum station-
1) Diffusion of the reactants from the gas space
ary operation. However, the nonstationary dy-
through the outer gas – particle boundary
namic operating mode is also of great impor-
layer, macropores, and micropores
tance for industrial operation control. In partic-
2) Chemisorption on active centers
ular, fixed-bed reactors with a strongly exother-
3) Surface reactions
mic reaction exhibit an, at times, surprising op-
4) Desorption of the products
erational behavior which is discussed in more
5) Back-diffusion of the products into the gas
detail in Chapter 6.
space
Within a production plant the reactor may jus-
tifiably be regarded as the central item of appa- Since most reactions take place with a con-
ratus. However, compared to the remaining parts siderable heat of reaction, a corresponding heat
of the plant for preparing the feed and for sep- transport is superimposed on the mass transport.
arating and working-up the products, often it is The control of the microkinetics, consisting
by no means the largest and most cost-intensive of micropore diffusion, chemisorption, surface
component. In many cases the achievable con- reaction, and desorption, is the task of the cata-
version in the reactor is limited for thermody- lyst developer and is not discussed further here.
namic (equilibrium) and kinetic reasons (selec- If the catalyst is specified together with its mi-
tivity). It is then usual to separate the material crokinetic properties, then reaction conditions
discharged from the reactor into products and (feedstock concentrations, pressure, tempera-
unreacted feed components (see Fig. 2), which ture profile, and residence time) can be found
are recycled to the feedstock. This recycling pro- that lead to optimum yields. The reaction engi-
cedure involves costs neer must determine these conditions and ensure
that they are maintained in an industrial reactor.
4 Fixed-Bed Reactors

Figure 2. Reaction cycle for synthesis reactions with incomplete conversion

a) Fixed-bed reactor; b) Feed preheater; c) Exit cooler; d) Recirculation compressor; e) Separation column

In the case of selectivity-sensitive multistep ranged in the fixed bed in such a way as to ensure
reactions, any deviation from the optimum val- good heat transport to the heat-transfer medium.
ues inevitably leads to a decrease in yield. This A further requirement placed on the catalyst
applies to deviations from the uniform residence is a low flow pressure loss. This applies par-
time distribution due to flow dispersion and flow ticularly if the reaction conversion in a single
bypass phenomena in the fixed bed, as well as throughput is low, so that the reaction has to
to deviations from uniform reaction conditions be carried out with a large circulating gas ra-
in the catalyst as a result of mass-transport re- tio (Fig. 2), as well as to off-gas purification,
sistance in the particles and the outer boundary in which large off-gas streams must be handled
layer [1]. with minimal additional cost.
The influence of mass-transport resistance in Finally, the catalyst should be available in a
the particles can only be excluded if the critical sufficiently high concentration in order to keep
reaction rate is substantially lower than the mass the construction volume of the reactor low. The
transport velocity. This leads on the one hand to decisive parameters here are the specific external
the need for good external mass transfer (i.e. to catalyst surface ap (= square meters of catalyst
reasonable flow conditions in the packed bed), surface per cubic meter reactor volume) for re-
as well as to short diffusion paths in catalyst par- actions controlled by external mass transfer, the
ticles and sufficiently large pores. On the other catalyst fraction 1 − ε, where ε = cubic meters of
hand (in the case of exothermic reactions) the lo- free gas space per cubic meter of reactor volume,
cal reaction rate must be controlled and limited describing the void fraction of the fixed bed.
by the packed-bed temperature. The above requirements are to some ex-
Temperature control thus plays a predomi- tent contradictory, which has led to the propo-
nant role in selective reaction control in general, sition of a large number of different catalyst
and in particular in the case of exothermic mul- forms and arrangements. However, only a few
tistep reactions. Under nonadiabatic conditions, of these have proved really effective in prac-
catalysts must therefore be assembled and ar- tical operation. Suitable catalyst forms and ar-
rangements include random packings of spheres,
 Fixed-Bed Reactors 5

solid cylinders, and hollow cylinders, as well 2.1. Gas – Catalyst Mass and Heat
as uniformly structured catalyst packings in the Transfer
form of monoliths with parallel channels, paral-
lel stacked plates, and crossed, corrugated-plate 2.1.1. Random Packings
packets (Fig. 3).
Industrial fixed-bed reactors are generally oper-
ated with a cross-sectional loading G z ≥ 1 kg gas
per square meter of reactor cross section per sec-
ond. This loading produces a sufficiently strong
turbulence in random packing. As a result the
external gas – catalyst mass-transfer resistance
is small compared to the transport resistance in
the catalyst pores.
However, generally the thermal conductivity
of the catalyst matrix is larger than of the gas.
This means that the external gas – catalyst heat
transport resistance exceeds the thermal con-
duction resistance in the catalyst particles. The
temperature and concentration conditions estab-
lished in a spherical catalyst are illustrated for a
partial oxidation reaction in Figure 4. The condi-
tions can be calculated from the model equations
given in → Model Reactors and Their Design
Figure 3. Usual shapes of monolith catalysts
A) Square-channel monolith; B) Parallel-plate monolith; C)
Equations, Chap. 4.1.1. under the assumptions
Corrugated-plate monolith made there. An essential precondition is that the
catalyst particle is uniformly exposed over its
entire surface to a flow with uniform tempera-
ture and concentration. This is, of course, never
the case in random packings. Figure 5 shows
the local mass-transfer distribution, providing an
insight into the overall highly inhomogeneous
conditions. The visualization technique is based
on the reaction of traces of ammonia in the gas
stream with a catalyst surface impregnated with
manganese chloride solution. The conversion to
manganese dioxide is already so fast under am-
bient conditions that it practically depends only
on the external mass-transfer resistance of the
gas boundary layer. The intensity of the dark col-
oration is thus directly proportional to the local
reaction rate of the surface reaction. At a con-
stant ammonia concentration in the gas flow it
is thus also proportional to the local mass trans-
fer, and if the mass transfer and heat transfer are
equivalent, also to the local heat transfer [2].
Figure 5 shows that the local conditions in
random packings are much more complex than
assumed in current conventional models. Nev-
Figure 4. Temperature and concentration profiles for a par- ertheless, the models for fixed beds containing a
tial oxidation reaction in a spherical catalyst pellet larger number of catalyst particles over the cross
section can provide reliable information if it is
6 Fixed-Bed Reactors

borne in mind that they only describe the mean tiation between the gas temperature and catalyst
value of a process that varies greatly as regards temperature difficult.
detail. For the same reason, it is inappropriate
to compare model predictions with a few local
temperature or concentration measurements. In- 2.1.2. Monolith Structures
deed, a certain degree of averaging is also neces-
sary in the measurement procedure (see Section In contrast to random packings, the external heat
2.2). transfer and mass transfer in monolith catalysts
is much more uniform, but they can also be-
come limiting factors at high reaction rates. This
applies in particular to channel-type monoliths
with narrow parallel channels, where the flow
is generally laminar under industrial operating
conditions. Examples include monolith catalysts
with a square-channel cross section for automo-
bile exhaust purification and for the removal of
nitrogen oxides from flue gases.
Figure 6 shows results of the visualiza-
tion of the local mass transfer by using the
ammonia – manganese chloride reaction (Sec-
tion 2.1.1). The marked decrease in coloration
in the flow direction is mainly the result of the
increasing consumption of ammonia in the wall
boundary layer, so that the reactants diffusing to
the wall have to travel an ever increasing dis-
tance from the flow core (build up of the lam-
inar boundary layer). The depletion is particu-
larly pronounced in the corners, since two re-
action surfaces meet here. The more acute their
enclosed angle, the greater is the depletion in the
corner region and the smaller is the contribution
of the wall surface to further heat transfer and
mass transfer. The efficiency of channel mono-
liths of equal cross-sectional area but different
shape therefore decreases in the sequence: cir-
cle, hexagon, rectangle, triangle. This is illus-
Figure 5. Local mass-transfer distribution at the surface trated in Table 1, which gives the asymptotic di-
of individual cylindrical or ring-shaped catalyst pellets in a mensionless mass-transfer and heat-transfer co-
fixed-bed packing efficients for tubes of the above cross sections.
As Figure 7 shows, the asymptotic limiting value
The literature contains a number of correla-
is established after a flow length roughly corre-
tion equations for the mean gas – catalyst mass
sponding to 10 times the hydraulic channel di-
transfer and heat transfer as a function of gas
ameter. The asymptotic limiting value from Ta-
properties, catalyst geometry, and flow condi-
ble 1 can therefore be used to perform estimation
tions [3], [4]. However, in practice they play only
calculations in conventional industrial mono-
a minor role for catalyst packings since design
lith catalysts with a large length-to-diameter ra-
and simulation calculations are frequently per-
tio. For more accurate calculations the radially
formed with a model that is quasi-homogeneous,
and axially variable velocity, concentration, and
at least with regard to temperature (→ Model Re-
temperature profiles must also be taken into ac-
actors and Their Design Equations, Chap. 4.).
count [7].
The reason for this are the above-mentioned
strong local fluctuations, which make differen-
 Fixed-Bed Reactors 7

Table 1. Asymptotic dimensionless laminar flow heat or mass-trans-

2.2. Flow and Pressure Loss in Fixed
fer coefficients Nu = αw · dh /λG (constant wall conditions) and Beds
fanning friction factor f for pressure drop ∆p = 2 f (ηZL /d2h ) · vG
for ducts of different cross section [6]
Conventional industrial catalyst forms differ
considerably as regards pressure loss. For ex-
ample, for equal mean dimensions and the same
proportion of empty space, random packings
generally have a considerably higher pressure
loss than monolith structures, and among these,
corrugated structures have a higher pressure loss
than monoliths with straight parallel channels.
Mass transfer and heat transfer are strongly cor-
related with the pressure loss. For reasons of
energy demand, the catalyst form for a given
process is chosen to combine the required mass
transport and heat transport with the lowest pres-
sure loss. However, it should be borne in mind
that the flow into the fixed-bed reactor (Fig. 1) is
generally achieved by means of a feed pipe and a
distribution hood. These must therefore be con-
structed so that the fixed bed or tube bundle is
uniformly traversed, and the gas residence time
in each tube or each flow filament of the fixed
bed is the same. This requirement can always be
met simply if the pressure loss in the fixed bed
or tube bundle is substantially greater than in the
entrance hood. In this case it need only be en-
sured that the fixed bed is packed so uniformly
that no flow bypass is formed or, in the case of a
multitube reactor, the pressure loss is equalized
in all the individual tubes of the bundle. Because
the pressure loss increases with the square of the
Figure 6. Visualization of mass transfer in monolith struc- flow velocity, a uniform distribution of the flow
tures (flow from left to right) then occurs automatically.
A) Square duct; B) Corrugated monolith [5]
Obtaining a uniform flow distribution is sub-
stantially more difficult if the pressure loss of the
In contrast to the monolith types discussed fixed bed is small. This holds in particular for
so far, the flow conditions in corrugated-plate monolith reactors with straight, laminarly tra-
monoliths (Fig. 3 C) are turbulent under normal versed channels (see Section 2.3).
industrial velocities. The uniformity of the mass- The Hagen – Poiseuille equation is used to
transfer distribution [8] depends on geometrical calculate the pressure loss in laminarly traversed
parameters (wave form, amplitude, wavelength, monolith channels
angle of incidence). The transfer coefficients
are considerably higher than those of laminarly 32ηZL vG
∆p= (2.1)
traversed channel monoliths (Fig. 6 B), but the d2h
pressure loss is also high. These structures of- The pressure loss of packed tubes can be de-
fer considerable advantages for convective heat scribed either by means of a pressure loss coef-
transport transverse to the flow direction and for ficient and the pressure drop equation
transverse mixing, which are discussed in more
 2
detail in the following sections. ∆p=ζ · ·vG (2.2)
2
or by the Ergun equation:
8 Fixed-Bed Reactors

Figure 7. Behavior of the dimensionless heat-transfer and mass-transfer coefficients over the dimensionless tube length
Nu = αW · d h /λG , Sh = k G · d h /D

2.3. Heat Transport Transverse to the

2
∆p=f1 vG +f2 vG (2.3) Flow Direction
where for spherical packings: With nonadiabatic reaction control, heat must
(1−ε)2 be transported perpendicular to the flow di-
f1 = 150·η· 3 2 (2.4) rection through the fixed bed to the heat ex-
ε ·dp
change surfaces. At the usual mass flow rates
of G z = 1 kg m−2 s−1 , this heat transport takes
(1−ε) place mainly by convection, i.e., the fixed bed
f2 = 1.75·· (2.5)
ε3 ·dp must be constructed so that flow components
Thus the pressure drop depends very strongly on transverse to the main flow direction occur lo-
the void fraction ε of the packing. Of the standard cally. Monolith structures with straight parallel
forms for packed catalysts, hollow cylinders of channels are thus unsuitable for nonadiabatic re-
thin wall thickness (ε ≈ 0.6 – 0.8) are therefore action control.
preferred to spheres (ε ≈ 0.37 – 0.4) and solid In catalyst packings transverse flow compo-
cylinders (ε ≈ 0.35). nents are automatically established as a result
The strong dependence of the pressure loss of the nonuniform arrangement and the twisted
on the void fraction underlines the importance of flow around the pellets. Hollow and full cylin-
packing catalyst beds carefully to avoid bypass ders with a length-to-diameter ratio of 1 to 3 are
flow due to local variations in the packing den- particularly effective in this respect.
sity. For the same reason the tubes of multitubu- Despite the fact that radial heat transport in
lar reactors for highly exothermic, selectivity- the form of twisted flow takes place mainly by
sensitive reactions are often filled uniformly by convection, it is formally described by means
means of special devices and if necessary indi- of a so-called effective thermal conductivity λr
vidually compensated for pressure loss. transverse to the flow direction.
The pressure loss coefficient ζ (Eq. 2.2) can
be determined for typical packing forms, for ex-
ample, according to [9].
 Fixed-Bed Reactors 9

In addition to heat transport through the fixed

bed perpendicular to the main flow direction,
the heat transport at the boundary between the
fixed bed and heat exchange surface is also deci-
sive for the heat exchange. The latter heat trans-
port is generally described by a wall heat-trans-
fer coefficient αW , in which the complex inter-
play between convective flow at the tube wall
and conduction transport by contact between the
fixed bed and the heat exchange surface is de-
scribed in overall terms. Heat transport in packed
tubes has been investigated and discussed in de-
tail [4], [10]. However, the correlations for αW
and λr given in the literature do not adequately
take account of the actual velocity distribution
in packed tubes. Plug flow was generally as-
sumed, although the actual velocity profile is
nonuniform with a pronounced slip at the wall.
This is due to the fact that the pellets make only
point contact with the wall, whereas they overlap
and cross over one another inside the packing,
thereby reducing the free volume and hence the
velocity. The conditions for a spherical packing
are illustrated schematically in Figure 8. The ra-
dially varying empty space distribution and ve-
locity distribution must be taken into account in
detailed reactor calculations, as well as in the
determination of accurate heat-transport param-
eters [12], [13].
Existing correlation equations for calculat-
ing the heat-transport parameters were obtained
from heating or cooling experiments without re-
actions and assuming plug flow; they therefore
permit only a semiquantitative evaluation. How-
ever, this is adequate for qualitative comparison
of catalyst structures.

2.4. Comparison and Evaluation of

Different Catalyst Forms

The choice of a suitable catalyst form is always

an optimization problem that can be completely
specified only for a specific process. Even then, Figure 8. Radial distribution of the void fraction and axial
however, weighting the performance function flow velocity in a tube packed with spheres
is not easy since, for example, small pressure
losses, uniform flow through the reactor, and
good mass- and heat-transfer properties gener- 2.4.1. Catalyst Forms for Adiabatic
ally represent opposing requirements. The fol- Operation
lowing assessment is therefore only a rough
guide. Decisive parameters for adiabatic operation in-
clude:
10 Fixed-Bed Reactors

1) The active catalyst surface available per unit limiting value given in Table 1 (Section 2.1) for
reactor volume the square channel
2) The quality of the mass and heat transfer bet-
kG ·dh
ween the flowing gas and the active catalyst Sh= ≈3 (2.9)
D
surface
3) The flow pressure loss gives, with aP = dh4·ε ,
4) The uniformity of the flow through the reac-
12D
tor and thus the degree of utilization of the kG ·ap ≈ (2.10)
fixed bed d2h ·ε

The major proportion of the active catalyst and

surface is located in the interior of the porous V̇ ·d2h ·ε
catalyst structure. However, if it is assumed that, VR = 0.38 (2.11)
D
in the case of sufficiently fast reactions, the re-
action site is restricted to a thin layer underneath If Equation (2.1) is used for the pressure loss,
the external surface, then the active catalyst sur- then for the laminarly traversed monolith chan-
face area can be taken as proportional to the spe- nel, from Equations (2.7) and (2.10)
cific external catalyst surface area ap . If the uni- 12.28·η 2 2
form distribution of the flow entering the fixed ∆p= ·vG ·ε (2.12)
D
bed is regarded as a separate problem, then for
given kinetic conditions the evaluation may be Using the above equations, reactor variants for
restricted to three parameters: specific external catalytic off-gas purification with a given vol-
surface area ap , gas – solid mass-transfer coeffi- ume flow V̇ were calculated in [11]. The result is
cient k G , and the flow pressure loss. The evalu- shown in Figure 9. The pressure drop of the fixed
ation becomes particularly simple if, with a sin- bed over the required reactor length is plotted;
gle dominant reaction, the external gas – solid the curve parameter is the hydraulic diameter
mass transfer limits the reaction, since in this d h of the monolith channel or packing body for
case the specific reaction kinetics have no in- different empty-tube gas velocities v e = ε · v G .
fluence. The relationships for a concentration According to Equation (2.11) the required fixed
c of a key component A and a simple reac- bed volume V R with square monolith catalysts
tion A + . . . → products are outlined in [2.11]. and a given throughput V̇ depends only on d h ,
Assuming mass-transfer limitation, the material whereas the geometric arrangement (small bed
balance for the key component along the flow cross section A and long bed length Z L , or large
path is bed cross section and short bed) has no influence
on V R . However, the bed cross-sectional area A
∂c for a given gas throughput V̇ determines via
ε·vG · = −kG ·ap ·c (2.6)
∂z
If the reaction has a conversion of 99 %, i.e., an V̇ =A·vG ·ε (2.13)
outflow concentration of 1 % of the inflow con- the interparticle velocity v G , and according to
centration, the length of the fixed bed Z L is, by Equation (2.12) this then appears as a quadratic
integration, term in the pressure loss.
ln0.01·ε·vG 4.6·ε·vG In conclusion, a minimum catalyst volume
ZL = − = (2.7) with minimum pressure loss is obtained by using
kG ·ap kG ·ap
a very flat bed with a large flow cross-sectional
For the required reactor volume V R with the area A and small hydraulic channel diameter or
cross-sectional area A: particle diameter d h . This result applies in gen-
eral to all catalyst forms. The main difficulty
V̇
VR =ZL ·A= 4.6· (2.8) with this arrangement is the uniform distribu-
kG ·ap
tion of the flow velocity. Figure 9 shows the im-
Correlations for k G can be found in [3], [4]. The provement in pressure loss that can be achieved
computation is particularly simple for straight, by channel monoliths as compared to spherical
laminarly traversed channels. The asymptotic packings. Other catalyst forms such as Raschig
 Fixed-Bed Reactors 11

rings or corrugated-plate packets lie between radial thermal conductivity, since the former can
these boundary curves. be compensated by an appropriate temperature
profile of the heat-transfer medium, whereas the
radial thermal conductivity directly influences
the uniformity of the reaction conditions over
the tube cross section. On the other hand, solid
cylinders with a large length-to-diameter ratio
have good heat transport values, but at the cost
of a very high pressure loss.
Despite its poor heat transport properties, a
monolith with straight, parallel channels, such
as used for automobile exhaust control, is in-
cluded in the comparison.
Monolith forms have very high specific sur-
faces combined with a very low pressure loss.
Figure 9. Pressure drop over the fixed-bed length for a cat- Crossed corrugated structures are considerably
alytic combustion reactor with given throughput and 99 %
conversion as a function of the hydraulic catalyst diameter
more favorable for isothermal reaction control.
d h for different gas empty-tube velocities v G [11] They have a very high radial thermal conduc-
tivity that is almost independent of the specific
surface area; the latter can be varied over a wide
range by means of the channel dimensions. The
2.4.2. Catalyst Forms for Isothermal catalyst of a reaction tube can thus be structured
Operation so that wide packings of small specific surface
area can be used in the region of the main re-
In addition to the previously discussed quan- action zone, while packings of increasingly nar-
tities, the lateral heat-transport parameters of rower structure, i.e., large specific surface area,
the fixed bed are further decisive parameters in are used downstream. In this way a more uni-
isothermal reaction control. As shown in Section form reaction rate and temperature profile can
2.3, heat transport can be characterized by the ef- be achieved over the tube length (see Section
fective thermal conductivity perpendicular to the 4.3.3).
main flow direction λr and the wall heat transfer However, it must be remembered that with
coefficient αW . Both quantities are strongly de- crossed corrugated structures, convective radial
pendent on the filling or packing form. Since heat transport occurs only in one plane perpen-
transport in the industrially interesting region dicular to the main flow direction. In addition,
mainly occurs by convection, they are approxi- the flow behavior in tubes of circular cross sec-
mately proportional to the mass throughput. tion is rather nonuniform over the circumfer-
For the purposes of overall comparison, ence, which is why it is advantageous to arrange
the corresponding characteristic parameters are short packing sections in series, each section be-
given in Figure 10 for some industrially impor- ing displaced by 90 ◦ . The heat transport param-
tant filling and packing forms in a tube of 50 mm eters in Figure 10 were determined for structures
internal diameter with a mass-flow velocity of arranged in this way.
Gz = 1 kg m−2 s−1 . A general problem in the use of monolith
The dimensions of the packing bodies were structures in reaction tubes is incomplete wall
chosen so that their specific external surface area contact. Since individual tubes of multitubular
ap is ca. 500 m2 /m3 . Under these conditions hol- reactors always have a diameter tolerance of ca.
low, thin-walled cylinders have clear advantages 1 mm and interlocking of the structure with the
over other packing forms, exhibiting the lowest tube wall must be avoided, the bypass of flow at
pressure loss and the highest thermal conductiv- the wall is even greater than with random pack-
ity. Only as regards wall heat transfer are they ings. Up to now there have been no specific in-
inferior to spheres or cylinders. However, good vestigations of the magnitude and effects of this
wall heat transfer is apparently less decisive phenomenon.
from a reaction engineering viewpoint than good
12 Fixed-Bed Reactors

Figure 10. Specific outer surface area ap , void fraction ε, effective radial heat conductivity λr , wall heat-transfer coeffi-
cient αW , and pressure drop ∆p for different packings in a tube of 50 mm internal diameter and an air mass-flow velocity
G z = 1 kg m−2 s−1 at ambient conditions
a) Glass spheres, d p = 5 mm; b) Glass spheres, d p = 10 mm; c) Raschig rings, ceramic, d a = 10 mm, d i = 6 mm, l = 11 mm;
d) Raschig rings, stainless steel, d a = 10 mm, d i = 9 mm, l = 11 mm; e) Hollow ceramic cylinders of irregular length, d a = 9 mm,
d i = 4.5 mm, l ≈ 15 mm; f) Full ceramic cylinders of irregular length, d a = 5 mm, l = 11 mm; g) Crossed corrugated metal-plate
packing (Sulzer Katapak) wide channels; h) Crossed corrugated metal-plate packing, narrow channels; i) Automotive exhaust
monolith, Cordirith, square channels, d = 0.9 mm

3. Adiabatic Reaction Control in nitric acid production (→ Nitric Acid, Ni-

trous Acid, and Nitrogen Oxides, Chap. 1.3.) and
Adiabatic fixed-bed reactors are the oldest fixed- oxidative dehydrogenation on silver catalysts
bed reactor configuration. In the simplest case (e.g., synthesis of formaldehyde by dehydrogen-
they consist of a cylindrical jacket in which the ation of methanol,→ Formaldehyde, Chap. 4.1.,
catalyst is loosely packed on a screen and is tra- → Formaldehyde, Chap. 4.2.). In the first case
versed in the axial direction (Fig. 11 A). To avoid the “fixed bed” consists of several layers of plat-
catalyst abrasion by partial fluidization, catalyst inum wire gauzes, and in the second case, of a
packings are always traversed from top to bot- porous silver layer several centimeters in height.
tom. If fixed beds composed of monolith catalyst The bed diameters can be up to several meters.
sections are used, the flow direction is arbitrary. On account of the difficulties involved with
As discussed in Section 2.4.1, the require- obtaining uniform flow as well as for structural
ment for a low pressure loss leads to a fixed reasons, the disk concept is limited to small cata-
bed of large diameter and low height (Fig. 11 B). lyst volumes. The radial flow concept (Fig. 11 C)
Such an arrangement (disk concept) is used par- is used where large amounts of catalyst are in-
ticularly when very short residence times, fol- volved. The catalyst packing is accommodated
lowed by direct quenching of the reaction, are in the space between two concentric screen rings
required. Examples include ammonia oxidation or perforated plate rings, and is traversed radi-
 Fixed-Bed Reactors 13

ally, either from the inside to the outside or from

the outside to the inside. This design is particu-
larly suitable for large catalyst volumes as well
as for operation at elevated pressure, since at
moderate reactor diameters the catalyst volume
can be varied over a wide range by altering the re-
actor length, without affecting the flow-through
length of the packing.

Figure 12. Upper bed closure in a radial-flow reactor [14]

Figure 11. Main design concepts for adiabatic reactors

A) Adiabatic packed-bed reactor; B) Disk reactor;
C) Radial-flow reactor

A critical feature of packed radial-flow reac-

tors is the shape of the upper bed closure. A sim-
ple horizontal covering is not practicable since a
gap through which unreacted gas can pass is then
formed due to the unavoidable settling of the
packing. The arrangement shown in Figure 12
has proved effective since it produces mixed ax-
ial and radial flow through the bed in the up-
per bed closure. The required geometrical shape
must be determined by simulation of the local Figure 13. Reaction chamber for removal of nitrogen ox-
ides from power station flue gas [15]
two-dimensional flow through the packing [14].
14 Fixed-Bed Reactors

vorable flow conditions in the outflow hood may

also affect the flow behavior through the catalyst
bed.
Figure 14 shows the velocity distribution in
front of the monolith inlet for an industrially
housed automobile catalyst [11]. Since the flow
cannot follow the sudden widening of the inlet
funnel, one third of the total cross section is tra-
versed at a velocity that is roughly three times the
mean velocity. It can be estimated that, with uni-
form flow through the catalyst, half the catalyst
volume would be sufficient for the same mean
conversion. Also, bends in the feedpipe can lead
to swirl-type components and thus contribute to
nonuniform flow.
Purely adiabatic fixed-bed reactors are used
mainly for reactions with a small heat of reac-
tion. Such reactions are primarily involved in gas
purification, in which small amounts of interfer-
ing components are converted to noninterfering
compounds. The chambers used to remove NOx
from power station flue gases, with a catalyst
volume of more than 1000 m3 , are the largest
adiabatic reactors, and the exhaust catalysts for
internal combustion engines, with a catalyst vol-
ume of ca. 1 L, the smallest. Typical chemical
applications include the methanation of CO and
Figure 14. Velocity distribution in an industrially housed CO2 residues in NH3 synthesis gas, as well as
automobile catalyst [11] the hydrogenation of small amounts of unsat-
The advantages of monolith catalysts with urated compounds in hydrocarbon streams. The
straight, parallel channels for adiabatic reac- latter case requires accurate monitoring and reg-
tors have already been referred to in Section ulation when hydrogen is in excess, in order to
2.4.1. Since monolith catalysts are usually pro- prevent complete methanation due to an uncon-
duced with a rectangular cross section, the fixed trolled rise in temperature, a so-called runaway
bed is constructed by arranging these individual (see Chap. 6).
monoliths in rows in the form of a large “box”.
Conventional DENOX reactors for removing
NOx from power station flue gases are there- 4. Reaction Control with Supply or
fore designed as rectangular chambers (Fig. 13). Removal of Heat in the Reactor
The catalyst is often arranged in the form of sev-
eral layers in series, the spaces between the in- 4.1. Introduction
dividual layers permitting cross-mixing, so that
In the majority of fixed-bed reactors for indus-
the influence of nonuniform flow as well as any
trial synthesis reactions, direct or indirect supply
possible local blockage of the next layer can be
or removal of heat in the catalyst bed is utilized
compensated to some extent.
to adapt the temperature profile over the flow
Reference is made in Section 2.2 to the impor-
path as far as possible to the requirements of an
tance of uniform flow into and through adiabatic
optimal reaction pathway. Here a clear devel-
fixed-bed reactors. This is not easy to achieve,
opmental trend can be observed, which is illus-
particularly with low-pressure-loss monolith re-
trated schematically in Figure 15.
actors, and requires a careful design of the inflow
Development started with the adiabatic reac-
hood. On account of the low pressure loss, unfa-
tor (Fig. 15 A), which on account of the adiabatic
 Fixed-Bed Reactors 15

Figure 15. Development of fixed-bed reactors

A) Single-bed adiabatic packed-bed reactor; B) Adiabatic reactor with interstage gas feed (ICI concept); C) Multibed adiabatic
fixed-bed reactor with interstage heat exchange; D) Multitubular fixed-bed reactor; E) Multitubular fixed-bed reactor with two
cooling circuits and nonisothermal cooling temperature (the temperature profile shown is for a strongly exothermic reaction)

temperature change could only be operated to The next development was the replacement
give a limited conversion. Higher conversions of injection cooling by interstage heat exchang-
were achieved at the same mean temperature ers, through which the required or released heat
level when several adiabatic stages were intro- of reaction is supplied or removed (Fig. 15 C).
duced, with intermediate heating or cooling after The development of reactors in which the
each stage. The simplest form involves injecting heat-exchange surfaces are integrated in the
hot or cold gas between the stages (Fig. 15 B). fixed bed to supply or remove the heat of reac-
For a constant tube diameter, the main disad- tion as close as possible to the reaction site oc-
vantages of this temperature control strategy are curred in parallel with the development of multi-
cross-sectional loading, which increases from stage adiabatic reactors with intermediate heat-
stage to stage, and the mixing of hot and cold ing or cooling. The multitubular fixed-bed re-
streams, which is energetically unfavorable. The actor (Fig. 15 D) constitutes the oldest and still
composition is changed by injection, which can predominant representative of this class of fixed-
have a positive or negative effect on the desired bed reactors. Here the catalyst packing is located
reaction. in the individual tubes of the tube bundle. The
heat-transfer medium is circulated around the
16 Fixed-Bed Reactors

tube bundle and through an external heat ex- actors with circulating gas heating, and strictly
changer, in which the heat of reaction is sup- isothermal designs with multitubular reactors
plied or removed. Whereas with endothermic heated with molten salt are currently used for
reactions, circulating gas can be used as heat- the endothermic synthesis of styrene from ethyl-
transfer medium, for strongly exothermic reac- benzene. Also, exothermic, equilibrium-limited
tions exclusively liquid or boiling heat-transfer reactions such as methanol synthesis are carried
media are used. Only in this way can the catalyst out in multistage adiabatic reactors with inter-
temperature (e.g., in the case of partial oxida- stage cooling as well as in multitubular reac-
tions) be held in the narrow temperature range tors. Overall, however, there is a trend towards
necessary for selective reaction control. the more highly integrated designs, which will
Initially, the integration of heat exchange in accelerate with rising energy and raw material
the fixed bed was utilized to ensure as isother- prices. Adiabatic multistage designs and reac-
mal a reaction control as possible, which is tors with heat exchange integrated in the fixed
why reactors of the type shown in Figure 15 D bed are discussed in the following sections. Au-
are also commonly termed “isothermal reac- tothermal reaction control, in which the heat of
tors”. They are characterized by reaction tubes reaction of moderately exothermic reactions is
of 20 – 80 mm internal diameter and a carefully utilized to heat the incoming feedstock, is dis-
designed flow control of the liquid heat-trans- cussed separately in Chapter 5.
fer medium, with largely constant heat-transfer
conditions throughout the tube bundle and max-
imum temperature changes of the heat-transfer 4.2. Adiabatic Multistage Reactors with
medium in the tube bundle of a few degrees. Interstage Heat Transfer
The latest concepts are aimed at establish-
ing a freely selectable (within limits) optimum Adiabatic multistage fixed-bed reactors with in-
temperature profile over the tube length. This termediate cooling or heating are nowadays used
requires complex heat-transfer medium control particularly where the reaction proceeds selec-
with several sections and temperature levels tively to give a single product but is limited by
(Fig. 15 E). the equilibrium conditions. Intermediate cooling
The stimulus for the developments outlined or heating is used to displace the gas tempera-
in Figure 15 was the need for total raw material ture in the direction of higher equilibrium con-
utilization as regards both mass and energy. This version. Typical examples include the synthesis
involves as main criteria the yield of primary of ammonia, sulfur trioxide, and methanol. In
end products (maximum), the yield of byprod- these exothermic reactions the equilibrium con-
ucts that must be removed and eliminated (min- version to the target product decreases with in-
imum), the thermal energy consumption or re- creasing temperature, as shown in Figure 16 A.
covery, and the mechanical energy requirements For a given conversion x a temperature can there-
(gas compression, circulation of heat-transfer fore be found at which the reaction rate, with re-
medium). In addition to the running costs, which spect to the target product, becomes a maximum.
are determined by the above criteria, the invest- This temperature must be below the equilibrium
ment costs are decisive in an investment deci- temperature but not so low that the reaction be-
sion, and naturally rise sharply with increasing comes too slow for kinetic reasons. The points
complexity of the reaction cycle. obtained in this way can be joined to form a
On account of cost degression the projected maximum reaction rate curve (Fig. 16 B).
plant size and the subsequent degree of utiliza- Since, in the case of adiabatic reaction con-
tion as well as the technological sophistication trol the temperature increases linearly with the
are decisive in calculating the product price. Sev- achieved conversion ∆x according to the equa-
eral of the fixed-bed reactor variants illustrated tion,
in Figure 15 can, depending on the location of
the production site and the estimated output, be ∆hR ·c0
∆T = − ·∆x (4.1)
used for the same process. For example, multi- G ·cpG
stage adiabatic reaction systems with interme-
diate superheated steam feed, multitubular re-
 Fixed-Bed Reactors 17

Figure 16. Equilibrium limitation of exothermic reactions

A) Equilibrium conversion as a function of temperature; B) Optimum reaction rate curve; C) Improvement of conversion by
interstage cooling

each adiabatic reaction pathway of an exother- ample, radially instead of axially traversed beds
mic reaction lies on a straight line of gradient can achieve a smaller pressure loss with a more
∆T /∆ x (see Fig. 16 A). favorable structural arrangement; heat exchange
A practicable reaction pathway for a multi- with the cold feedstock can be effected by heat
stage adiabatic reaction can thus be derived from exchange surfaces integrated in the first catalyst
Figure 16 by joining straight-line sections for the bed; or a cold gas quench can be used to achieve
adiabatic reaction to vertical lines for the tem- additional temperature regulation.
perature reduction due to indirect intermediate Modern, adiabatic multistage reactors may
cooling (Fig. 16 C). thus become so complex that the question arises
The kinetically optimum reaction pathway whether a multitubular design according to Fig-
with the smallest required catalyst volume re- ure 15 D or E does not represent the more fa-
sults when the trajectory follows, in a large num- vorable alternative. The required heat-exchange
ber of small steps, the line of maximum reac- surface area in the case where heat exchange is
tion rate. In practice, the apparatus and equip- integrated in the fixed bed is smaller than in the
ment expenditure involved in a large number of case of free gas flow on account of the posi-
stages must be weighed up against the savings tive effect of the catalyst packing. Furthermore,
in catalyst. Conventional multistage reactors for it does not involve any additional pressure loss,
this class of reaction therefore have three to five and the optimum reaction rate curve (Fig. 16 B)
stages. Figure 17 shows the layout of an ammo- can be better approximated by controlling the
nia synthesis reactor designed on this basis. For cooling temperature profile (see Section 4.3.2.)
structural reasons the heat exchanger is incorpo- than by a stepwise temperature reduction.
rated between the inflow and outflow in the low- On the other hand, a multistage arrangement
est part of the pressure casing. The reaction gas may be considered for structural, operating tech-
then flows upward in the annular gap between nology, or kinetic reasons in the following cases:
the pressure casing and the fixed beds, whereby
it is further heated and at the same time pro- 1) If, in the case of large single-train plants, sub-
tects the pressure-bearing structural components division into several individual items of ap-
against excessively high fixed-bed temperatures. paratus is necessary for reasons of transport
The three adiabatic fixed-beds are traversed from or construction
top to bottom, part of the heat of reaction being 2) If a catalyst must be replaced in individual
utilized to generate steam in the two intermedi- stages at different times on account of differ-
ate heat exchangers. To start up the cold reactor, ent catalyst compositions and/or aging
hot gas must be added to the uppermost bed, for 3) If a gradual addition of a reactant has kinetic
example through an external start-up preheater. advantages compared to the total addition to
Industrial adiabatic multistage reactors often the feed (here a suitably designed interme-
differ in many details from Figure 17, although diate heat exchanger ensures a uniform dis-
they are of a comparable basic design. For ex-
18 Fixed-Bed Reactors

Figure 17. Schematic of a multistage reactor for ammonia synthesis

tribution and mixing with the reaction gas 3) A sufficiently large mass flow velocity of the
stream) reaction gases ensures good heat transport
4) If the intermediate stages are used to extract from the packing to the heat-exchange sur-
a limiting product in the case of equilibrium- face
limited reactions; an example is the interme-
diate absorption of SO3 before the last stage With exothermic equilibrium reactions and
of the SO3 synthesis endothermic reactions these requirements are
5) With reaction temperatures above 300 ◦ C in- less stringent since these reactions cannot run-
termediate cooling can be performed directly away, although here too it is beginning to be
with boiling water, whereas in a fixed bed recognized that a tight and uniform temperature
a high-temperature heat-transfer medium control over the reactor cross section is advan-
must be used as coolant (see Section 4.3.1) tageous.

4.3.1. Heat Transfer Media for Fixed-Bed

4.3. Reactors with Heat Exchange Reactors
Integrated in the Fixed Bed
The first of the above requirements presupposes
The aim of reaction control with heat exchange an assortment of heat-transfer media that covers
integrated in the fixed bed using a circulating the whole temperature range of interest for gas-
heat-transfer medium is to maintain the catalyst phase reactions in fixed-bed reactors. It is conve-
temperature in a narrow optimum range under all nient to distinguish between gaseous, liquid, and
operating conditions. With strongly exothermic vaporizing heat-transfer media. Gaseous heat-
successive reactions, such as partial oxidations transfer media in the form of hot flue gases are
and partial hydrogenations, on account of the used in the temperature range above 500 ◦ C ex-
danger of a runaway reaction (see Section 6.2) clusively to supply heat for endothermic reac-
this requirement can be met only if tions.
1) The temperature of the heat-transfer medium Conversely, vaporizing heat-transfer media
is close to the desired catalyst temperature are used exclusively to remove heat from
2) Large heat- exchange surfaces are available exothermic reactions. Whereas formerly petro-
per unit catalyst volume leum fractions such as kerosene (e.g., in ethylene
 Fixed-Bed Reactors 19

oxide synthesis) were more widely used, they η 0.25 /c2.75

p · 2 , which depends only on the
have now been largely replaced by boiling wa- physical properties of the heat-transfer medium,
ter on account of their flammability, lower heat is plotted as a function of temperature in Fig-
of vaporization, and the need to produce steam ure 19. This shows the exceptional heat-transfer
in a downstream condenser/heat exchanger. De- properties of water that result from its density
pending on the saturated vapor pressure, the tem- and, in particular, its high specific heat, as well
perature range from 100 to 310 ◦ C (100 bar) can as the properties of gases (air) and vapors (water
be covered with boiling water. In this range it is vapor), which are about seven orders of mag-
the preferred heat-transfer medium for evapora- nitude worse. Common heat-transfer oils and
tive cooling if an isothermal cooling temperature salt melts (sodium nitrate) lie close together, but
is required. about an order of magnitude above water. The
Locally variable cooling temperature profiles poor performance of molten sodium compared
can be established most easily with liquid heat- to heat-transfer oils and salt melts is noteworthy.
transfer media that do not vaporize in the in-
tended operating range. In order to avoid cavi- To test Equation 4.3 on a more realistic ex-
tation, pressurized water should be used only up ample of the cooling of a multitubular reactor, a
to ca. 220 ◦ C; heat-transfer oils cover the tem- quadratic tube bundle (cross section 1.5×1.5 m)
perature range up to 300 ◦ C, while above this with fourfold passage of the coolant was de-
temperature salt melts are now used exclusively signed by using detailed equations for pressure
in reaction technology [16]. Compared to heat- drop and heat transfer [27] for various heat-
transfer oils they have the advantage that they are transfer media. The heat release of 1650 kW in
incombustible and stable, although they have the 1591 (37×43) tubes of 30 mm external diam-
disadvantage that they solidify at about 200 ◦ C eter and 4 m length corresponds to the condi-
(nitrate melts) or 400 ◦ C (carbonate melts). The tions in a partial oxidation reaction. A tempera-
temperature ranges of possible heat-transfer me- ture rise between feed and outlet of ∆T c = 5 K
dia are compared in Figure 18. In addition to the was assumed for the heat-transfer medium (ad-
thermal stability, the energy Ṅ per unit amount ditionally 150 K for air and water vapor). Ta-
of transported heat Q̇ required to circulate a ble 2 lists as results the required pump power
heat-transfer medium is an important criterion Ṅ, the pressure drop in the cooling circuit ∆p
of choice. (whereby p = 1 bar exit pressure was assumed
The following equation has been derived for for water vapor and air), and the excess temper-
the evaluation of heat-transfer media without ature of the reactor wall above the heat-transfer
phase change [26]: medium temperature ∆T W , assuming constant
Q̇
wall temperature along the length of the tube.
∆Tc 0.73 ·cp It was shown that the results of these more pre-
∼ (4.2)
Ṅ 0.36 η 0.09 cise design equations for the liquid heat-transfer
where Q̇ is the heat flow transferred by the media can be correlated with the equation

2.73
heat-transfer medium while its temperature in- Q̇ η 0.27
creases by exactly ∆T c , Ṅ is the required pump Ṅ = 7800 (4.4)
∆Tc c2.73
p ·2
power, and , cp , and η are the density, spe-
This represents a good confirmation of Equation
cific heat capacity, and viscosity of the heat-
(4.3).
transfer medium. For liquid heat-transfer media,
Water is thus the ideal heat-transfer medium
the equation is derived from the pressure drop
within its temperature range. For higher temper-
in a turbulently traversed, hydraulically smooth
atures molten salts have increasingly replaced
pipe. It is practical to solve Equation (4.2) for
the previously more commonly used heat-trans-
the pump power:
fer oils. Salt melts cover a larger temperature

2.75
Q̇ η 0.25 range and have the particular advantage over oils
Ṅ ∼ · (4.3) that they are incombustible. The potential danger
∆Tc c2.75
p ·2
of a relatively large amount of hot salt melt ob-
Thus the required power varies as almost viously exists, but is reliably dealt with by expe-
the third power of Q̇/∆T c . The component rienced reactor construction companies. Special
20 Fixed-Bed Reactors

Figure 18. Application ranges for common heat-transfer media

Figure 19. The material-specific factor F = η 0.25 /c2.75

p · 2 for various heat-transfer media as a function of temperature

Table 2. Results of the example calculation

Heat-transfer Producer Pump power Pressure drop Mean temperature Permitted cooling
medium Ṅ, kW ∆p, bar difference temperature increase
∆T w , K ∆T c , K
Water 0.060 0.008 0.75 5
Transcal N BP 0.629 0.042 2.32 5
Diphyl THT Bayer 0.862 0.054 2.35 5
Sodium 4.54 0.150 0.04 5
HT salt 1.31 0.105 1.45 5
Water vapor 0.119×106 8.759 1.30 5
Water vapor 0.254×103 0.175 14.22 150
Air 0.229×106 18.001 1.08 5
Air 0.456×103 0.341 12.29 150
 Fixed-Bed Reactors 21

nitrate melts (HITEC) can be used in the tem- liquid heat-transfer medium surrounds the sta-
perature range 200 – 500 ◦ C. Gradual decompo- tionary tube bundle. The rising vapor bubbles
sition begins above this temperature, which can escape through the ascending pipe into a vapor
accelerate violently above 600 ◦ C. Access of or- drum, where they are separated from the liquid.
ganic components to the melt (nitrate decom- A circulation flow is established due to the dif-
position) and of water (steam explosion) must ference in density in the downpipe (pure liquid)
be excluded [16]. New salt melts, for example, and in the reactor jacket, which means that cir-
based on carbonates, are being developed for the culating pumps are generally not required. The
temperature range 400 – 800 ◦ C. In this case it is heat-transfer medium temperature is regulated
not so much the thermal stability of the molten via the saturated vapor valve. Specific details of
salt but rather the corrosion of the reactor mate- this regulation are discussed in Section 6.6.
rials that presents problems.
Gases are the only heat transfer media usable
over the entire temperature range, but because of
their low density they have an unfavorable heat
transport behavior (Fig. 19). They are therefore
used exclusively as flue gases to supply heat at
high temperatures. However, large temperature
differences between the heat-transfer medium
and the reactor wall, with possible adverse ef-
fects on the uniformity of the heat supply, must
then be accepted.

4.3.2. Reactor Designs

As with adiabatic reactors, a principal task of

reactor development is to produce uniform reac-
tion conditions over the whole reactor and main-
tain such conditions during the entire operating
time. This involves the conditions in the cata-
lyst packing (residence time, catalyst concentra- Figure 20. Multitubular reactor with boiling water cooling
tion and activity, heat transport) and in the heat- If uniform supply and removal of heat-trans-
transfer medium circuit (throughput, tempera- fer medium via annular channels is ensured, this
ture, heat transfer). When liquid or vaporizing arrangement provides reliable isothermal reac-
heat-transfer media are used, the heat-transfer tion control. Since a steam cushion can form un-
coefficients are usually one order of magnitude der the upper tube floor, the active catalyst layer
greater than those on the catalyst side, which should begin only at a deeper level.
facilitates the task as regards the heat-trans- Apart from the type of multitubular reactor
fer medium. On the other hand, with strongly shown in Figure 20, other multitubular reactors
exothermic, selectivity-sensitive reactions (es- are sometimes used in which the catalyst bed
pecially partial oxidations), a temperature con- is arranged around the tubes and the heat-trans-
stancy of the heat-transfer medium of ca. 1 ◦ C fer medium flows through the tubes (Fig. 21 B).
is often required. This leads to a high energy re- An interesting new development has been intro-
quirement for circulation (according to Eq. 4.4) duced by Linde (Fig. 21 A): the tube bundle is
and necessitates extremely careful design and composed of counterwound spirals in which up-
control of the heat-transfer medium circuit. wardly flowing water is evaporated. The tubes
Tubular reactors of the type shown in Fig- run into a vertical vapor drum located at the
ure 15 D have been in use longest and have been reactor head. The tube bundle is connected to
furthest developed. In the case of a vaporizing a central downpipe at the bottom so that, as in
heat-transfer medium an arrangement as shown the arrangement in Figure 20, a natural circula-
in Figure 20 is generally chosen, in which the
22 Fixed-Bed Reactors

tion of the evaporating water is established. Ad- Circulation systems with parallel and crossed
vantages in construction and in the heat transfer cocurrent or countercurrent flow of the heat-
from the reaction gas to the tubes of the bundle transfer medium (Fig. 22) are commonly em-
are claimed for this design [28]. ployed for liquid heat-transfer media. The main
part of the heat-transfer medium is generally
circulated with a high-capacity pump in order
to achieve uniform heat-exchange conditions,
while a partial stream is passed through a heat
exchanger for supplying or removing the heat
of reaction. The desired heat-transfer medium
temperature is attained by regulating this par-
tial stream. With exothermic reactions the heat
exchanger is normally a steam generator which
produces saturated steam at a pressure corre-
sponding to a boiling point of 30 – 80 ◦ C below
the maximum cooling temperature.
A superheater fed with a further partial stream
of the heat-transfer medium can if necessary be
connected downstream of the steam generator.
The arrangement with separate external units,
shown schematically in Figure 22 has structural
and maintenance advantages over a common ar-
rangement in the tube-free interior of the reactor
[29].
Apparatus construction companies specializ-
ing in these reactors have developed a detailed
and comprehensive know-how as regards flow
control of the heat-transfer medium [30]. This
concerns the uniform supply and removal of
the heat-transfer medium, which generally takes
place via external annular channels, as well as
the flow control within the reactor. Here a dis-
tinction is made between parallel flow control
and crossed flow control. Parallel flow control
(Fig. 22 B) is achieved by two rectifier plates
with narrow bores. On account of the pressure
loss through the bores suitably arranged over the
reactor radius, a uniform flow profile is produced
over the cross section with uniform heat removal
conditions between the distributor plates. The
advantage of this arrangement is that the whole
reactor can be equipped with tubes.
However, due to the nonuniform flow con-
ditions in the inflow and outflow region of the
heat-transfer medium, only the region between
the distributor plates should be filled with active
catalyst. Heat transfer is low because of the par-
Figure 21. A) Design concept of the Linde isothermal reac- allel flow of the heat transfer medium, and the
tor for methanol synthesis; B) Cut through the tube bundle pressure loss in the distributor plates does not
surrounded by catalyst pellets (from [31])
contribute to improving the heat transport. For
this reason this arrangement is preferably used
for reactions with a moderate heat of reaction.
 Fixed-Bed Reactors 23

Figure 22. Heat-transfer medium control in tube-bundle fixed-bed reactors

A) Cross flow; B) Parallel flow

In reactions with a large heat of reaction, es-

pecially partial oxidations, transverse flow con-
trol is more widely used, generally in a radially
symmetrical arrangement with baffle plates, as
illustrated in Figure 22 A. Since the heat removal
conditions are poorly defined in the region of the
flow deflection, with the change from a trans-
verse stream to a parallel stream and back to
a transverse stream, this region should be free
of tubes. A difficulty arises from the constant
change of the flow cross section in the radial
direction. However, this can be alleviated, for
example, by providing pressure-relief bores in
the baffle plates, increasing in number towards
the reactor axis. In this way constant heat-trans-
fer conditions should be achieved over the reac-
tor radius. In summary, ensuring uniform heat
transfer conditions as regards the heat-transfer
medium thus requires a considerable flow tech-
nology know-how. Some publications illustrate
the major differences in the behavior of different
tube sections that can arise due to an inadequate
design and layout of the heat-transfer medium
circuit [17–19].

4.3.3. Influencing the Course of the Reaction

The course of the reaction (i.e., the conversion

and selectivity or yield) can be decisively influ-
Figure 23. Influence of the coolant flow direction and flow enced by the arrangements made for controlling
velocity v s on the reaction temperature profile the heat-transfer medium. The most obvious, al-
A) Isothermal; B) Cocurrent flow; C) Countercurrent flow
though technically most complex solution, is to
24 Fixed-Bed Reactors

arrange different heat-transfer medium circuits involving exothermic reactions should therefore
so as to achieve a stepwise approximation of be chosen only in particular cases.
an optimum temperature profile. The purposeful
utilization of the temperature change of the heat-
transfer medium flowing through the reactor is,
however, technically simpler, and is discussed
here in connection with cocurrent or counter-
current cooling of a fixed-bed reactor involving
an exothermic reaction.
Figure 23 shows temperature profiles for
three different ways of controlling the cooling
stream in a partial oxidation reaction. If the
coolant is circulated so fast that its tempera-
ture in the reactor scarcely alters, then its flow
direction is irrelevant and a temperature pro-
file with a pronounced temperature maximum
becomes established; this is typical of strongly
exothermic reactions (Fig. 23 A). If the coolant
is circulated in cocurrent and its velocity is cho-
sen so that it becomes noticeably hotter over its
path, an almost isothermal temperature behav-
ior can be achieved (Fig. 23 B). This is because
the reactive gas at the inlet is in contact with
the coldest coolant and the cooling temperature
rises in step with the consumption of the reac-
tants, so that the reaction rate remains virtually
constant over a fairly long section [20–22]. This
stabilizing effect of cocurrent cooling has hardly
been exploited up to now in industrial reactors.
This may be due to the fear that, at the required
low flow velocity (in the example of Fig. 23 B,
v s = 0.01 m/s), heat transfer will be inadequate
and natural convection will occur in the cooling
jacket. However, v s describes the mean coolant
velocity parallel to the tube axis. With a cross-
cocurrent flow of the coolant, the actual flow
velocity may in fact be substantially larger, de-
pending on the number of deflections, with the
result that the aforementioned problems do not
arise.
Compared to cocurrent flow, countercurrent
flow has a markedly destabilizing effect at low
flow velocities (Fig. 23 C). Since the incoming
reaction mixture in this case is in contact with
the warm coolant outflow, the maximum tem-
perature rises to much higher values. Counter-
current cooling can even lead to the occurrence
of several stationary states, and in general fa- Figure 24. Influence of the heating agent flow direction on
vors the runaway of a strongly exothermic, irre- the temperature profile in styrene synthesis
A) Adiabatic; B) Isothermal; C) Countercurrent
versible reaction (see Section 6.3). In contrast to EB = ethylbenzene; St = styrene
heat exchange without a reaction, countercurrent
control of the heat-transfer medium in reactors
 Fixed-Bed Reactors 25

Figure 25. Influence of activity profiles on the temperature profile of a strongly exothermic reaction
A) Catalyst with 66 % activity in the front section of the tube and 100 % activity in the rear section of the tube [23]; B) Linear
(broken line) and optimal catalyst activity distribution (full line) for limiting the maximum temperature to 370 ◦ C (simulation
result); C) Experimental verification of B [25]

The temperature control of an exothermic sibilities of establishing optimum temperature

equilibrium reaction can constitute such a case. profiles for a given reaction, and of counteract-
As illustrated in Figure 16 B, the optimum tem- ing any changes in activity that occur during the
perature profile should in this case decrease operating life of the catalyst by altering the tem-
with increasing conversion, i.e., along the tube perature profiles.
length. On account of the equilibrium inhibi- A further possibility of influencing the course
tion of the reaction, it is not possible for the of the reaction is to use catalysts of different ac-
reaction to runaway in the front region. Coun- tivities over the reactor length. Particularly with
tercurrent flow of the heat-transfer medium is strongly exothermic reactions that are liable to
also advantageous for endothermic equilibrium runaway, such as partial oxidations, a less active
reactions. Figure 24 shows the calculated tem- catalyst is occasionally used in the front part of
perature and concentration profiles with differ- the reactor in order to avoid too high a max-
ent heating conditions in the synthesis of styrene imum temperature. Figure 25 A illustrates the
(dehydrogenation of ethylbenzene). With adia- use of two catalysts of differing activity in se-
batic and isothermal reaction control, styrene ries. The resulting temperature profiles have a
formation decreases with increasing tube length, typical double-hump shape [23], [24]. This can
whereas it remains roughly constant with coun- be avoided if an activity profile is established by
tercurrent control. using a continuously varying mixture of cata-
A significant advantage of nonisothermal lysts with different activities (Fig. 25 B, C) [25].
control of the heat-transfer medium in cocur- In these cases the fully active entry region (rel-
rent or countercurrent flow is the saving in cir- ative activity 1) is designed so that the temper-
culation energy, since much smaller heat trans- ature rises to a preselected maximum value. In
fer-medium streams must be circulated. Overall, order to maintain the temperature at this value,
the combination of several heat-transfer medium the activity in the following region is sharply de-
circuits (Fig. 15 E) and the purposeful utilization creased and is then raised to a relative activity of
of the temperature change of the heat-transfer 1 as the reaction rate drops due to the depletion
medium in the reactor offer a wide range of pos- of the reactants. A smooth temperature profile
26 Fixed-Bed Reactors

can be achieved even if the optimized activity

profile in Figure 25 B is only approximately re-
alized (Fig. 25 C).
The control of the maximum temperature
by using locally differing catalyst activities
presents problems if the main reaction zone
moves into the region of high catalyst activity
due to changes in the operating conditions. For
example, in the case of Figures 25 B and C, a
decrease in the throughput may already result in
reaction runaway in the short, fully active front
region. This can be counteracted by reducing
the activity of this zone. Catalyst deactivation
occurring during operation may have more seri-
ous effects. If, for example, the catalyst is poi-
soned in a front migrating from the entrance to
the rear, the main reaction zone finally migrates
to the highly active rear catalyst region, which
may lead to excessively high temperatures that
can no longer be controlled.
In general, influencing the reaction course via
control of the cooling stream is more flexible
than incorporating catalysts of different activi-
ties. Particularly with nonisothermal control of
the heat-transfer media, the reaction course can
be influenced over a wide range by means of the
inflow temperature of the heat-transfer medium
as well as by its volumetric flow rate.

5. Autothermal Reaction Control

5.1. Introduction
Figure 26. Reactor circuits for autothermal reaction control
The expression autothermal reaction control is with indirect heat exchange
used with fixed-bed reactors if the heat of reac- A) External heat exchange; B) Internal heat exchange
tion is utilized to heat the reactor feed to the ig-
If the conversion is not limited by the reac-
nition temperature of the catalyst. Then, neither
tion equilibrium, then ∆ x = 1 and ∆T ad de-
addition nor removal of heat occurs during sta-
pends only on the inflow concentration c0 of
tionary operation of the reactor. It thus follows
a key component. Autothermal reaction control
that autothermal reaction control is restricted
is used in practice if the adiabatic temperature
to exothermic reactions in which a moderately
increase is in the range 20 K ≤ ∆T ad ≤ 300 K.
large amount of heat is produced. As a measure
Autothermal reaction control can be realized in
of the heat release, the adiabatic temperature in-
several ways, the simplest being to couple an
crease ∆T ad is usually used. This characterizes
adiabatic reactor with a countercurrent heat ex-
the temperature increase that the reaction mix-
changer in which the hot outflow heats the cold
ture would experience at the maximum possible
inflow (Fig. 26 A). If the heat exchanger is not
conversion ∆ x if no heat were released. As al-
to become impracticably large, this arrangement
ready given in Equation (4.1):
is suitable only for an adiabatic temperature in-
∆T = −
∆hR ·c0
·∆x
crease > ca. 200 K. If the heat exchange is in-
G ·cpG
 Fixed-Bed Reactors 27

Figure 27. Autothermal reaction control with direct (regenerative) heat exchange for an irreversible reaction [11]
A) Basic arrangement; B) Local concentration and temperature profiles prior to flow reversal in steady state; C) Variation of
outlet temperature with time in steady state

tegrated in the reactor (Fig. 26 B), then a better direction is reversed by valves, so that the tem-
heat transfer can be achieved inside the catalyst- perature front moves back again and heats the
filled tubes as well as around the tubes as a result cooled part of the packing. In this way a periodic
of the transverse flow, so that also gases with a steady state is finally established, in which the
somewhat lower adiabatic temperature rise can temperature profile moves up a certain amount
be reacted autothermally. Overall, however, in- in one half cycle, and moves down by the same
direct gas – gas heat exchange is a weakness of amount in the next half cycle. The upper and
this reactor concept. lower ends of the packing each serve as a re-
generative heat exchanger, the hot reaction zone
being maintained in each case in the interior of
5.2. Reaction Control with Periodic the packing.
Flow Reversal If the fixed bed is adiabatically insulated, the
heat of reaction can leave the reactor only via the
A major improvement was the autothermal re- outflow. This leads to the saw-toothed course of
action control with direct, regenerative heat ex- the outflow temperature T  with time shown in
change, developed by Matros et al., in which Figure 27 C. From the total energy balance it
the catalyst packing simultaneously acts as can easily be seen that the time-average value of
the regenerative heat exchanger [32–34]. Fig- the outflow temperature must lie exactly ∆T ad
ure 27 A shows the basic arrangement. After the above the inflow temperature. Nevertheless, the
catalyst fixed bed has been heated to the reaction temperature peaks shown in Fig. 27 C may con-
temperature, for example, with a pilot burner, the siderably exceed this mean value.
cold reaction gas flows into the packing, where it The main advantage of this form of reaction
is heated by the hot catalyst packing and then re- control is the very effective regenerative heat
acts. At the same time the inflow part of the pack- exchange in the catalyst packing, which does
ing is cooled, so that the reaction front migrates not require any additional built-in components
into the packing (Fig. 27 B). Before the reaction and permits autothermal reaction of gas mixtures
front has reached the end of the bed, the flow with an adiabatic temperature increase of less
28 Fixed-Bed Reactors

than 20 K. The main application of autothermal with a stationary inlet, outlet, and flushing seg-
reaction control with periodically varying flow ment leads to a periodic change in the direction
direction is catalytic off-gas purification, in par- of flow through the bed, which can be either axial
ticular catalytic oxidation of small amounts of (Fig. 29 A) or radial (Fig. 29 B).
combustible substances in exhaust air [11]. In
addition this form of reaction control has been
tested by Matros et al. for equilibriumlimited
exothermic reactions such as SO3 , methanol,
and ammonia synthesis, and has in some cases
been employed on an industrial scale [32–34].

Figure 29. Schematic of flow control with a rotating cata-

lyst bed [11]
A) Axial-flow reactor; B) Radial-flow reactor
The flushing segment is shaded.

5.3. Reactor Behavior

Due to the direct coupling of the reaction with
Figure 28. Alternative arrangements for autothermal reac- the heat exchange, autothermal reaction control
tor design with regenerative heat exchange exhibits some specific features as regards reac-
A) Radial flow concept; B) Multiple-bed arrangement tor behavior that distinguish it from the behav-
ior of conventionally operated fixed-bed reac-
In addition to the standard variants shown in
tors. Firstly, the autothermal procedure presup-
Figure 27, a number of modifications have been
poses the existence of several stationary operat-
proposed and applied (Fig. 28). For example, the
ing states (see Section 6.3). The “ignited” oper-
bed shown in Figure 28 A can be designed as
ating state is the desired state, for only then is
a radial flow system, so that the hot region in-
so much heat released that the cold inflow can
sulates itself, and a multibed arrangement may
be heated. In the “extinguished” state the reac-
be used to avoid flushing losses when reversing
tor cools to the inflow temperature, so that no
the flow direction, one bed being backflushed
further detectable conversion takes place. The
each time (Fig. 28 B). The arrangements of Fig-
object of reaction control of autothermal reac-
ure 29 offer an elegant possibility of a valveless,
tors is to prevent extinction of the reaction, but
continuous operation with an integrated flushing
also to limit the rise in the maximum temper-
stage [11]. Analogous to the Ljungström heat ex-
ature in the reactor due to the positive thermal
changer, the rotation of the segmented fixed bed
feedback (see Section 6.3).
 Fixed-Bed Reactors 29

With regard to the combined handling of au- tically constant because the heat capacity of the
tothermal reaction control with indirect and di- packing is ca. 1000 times that of the gas, whereas
rect (regenerative) heat exchange, it is conve- the gas temperature is quasi-stationary com-
nient to consider the limiting case of a very rapid pared to the packing temperature and therefore,
reversal of the flow direction [11]. For the sake of depending on the flow direction, is somewhat
simplicity the discussion is restricted to a simple, below or above the packing temperature. To il-
irreversible exothermic reaction. A typical ex- lustrate this, the principal temperature profiles
ample is the catalytic oxidation of a combustible are shown disproportionately far apart in Fig-
component in a waste air stream. ure 30 B. These profiles are completely equiva-
lent to those of a countercurrent heat exchange
reactor in which the heat- exchanging partition
is coated with catalyst (Fig. 30 C).
Since the stationary behavior of the coun-
tercurrent reactor can be calculated much more
simply than the steady state of the reactor with
periodic flow reversal, the equivalence model is
suitable for rapid parameter studies. In addition,
it permits straightforward assessment and inter-
pretation of the somewhat unusual operating be-
havior of autothermal reactors. Considering the
concentration profile corresponding to the tem-
perature behavior in Fig. 30 D it can be seen that
the reaction starts at an “ignition temperature”
T i and goes to rapid completion over a short sec-
tion.
Thus it can be assumed to a first approxima-
tion that the temperature difference ∆T in Fig-
ure 30 D can be calculated from:
∆T =Ti +∆Tad −T0 (5.1)

A detailed analysis shows that for more accu-

rate estimates, heat exchange in the region of
the reaction zone must also be included. In the
following discussion the ignition temperature is
therefore designated somewhat pragmatically as
the temperature that lies ∆T ad below the maxi-
mum temperature.
The gradient of the temperature curves below
the ignition temperature can be derived from the
conditions of countercurrent heat exchange with
axial thermal conduction [11]:
Figure 30. Equivalence of operating with periodical flow dT Uw ·ap ·ε·G ·cpG ·v
reversal and integrated countercurrent heat exchange =   ·∆Tad (5.2)
A) Matros reactor; B) Temperature profiles in the Matros dz 2·Uw ·ap ·λeff +4 ε·G ·cpG ·v
reactor with rapid flow reversal; C) Countercurrent reactor
with catalyst at the wall; D) Schematic concentration and
This allows a simple graphical interpretation of
temperature profiles in natros and countercurrent reactors the influence of the operating parameters on the
[11] reactor behavior.
Figure 31 A shows the change in the temper-
The mean gas temperature and mean catalyst ature and concentration profiles in the case of
temperature in the packing are considered sepa- sufficiently quick reversal or countercurrent op-
rately. With a very frequent reversal of the flow eration for gases with different ignition temper-
direction, the catalyst temperature remains prac- atures. The feed concentrations in each case are
30 Fixed-Bed Reactors

chosen such that the same adiabatic temperature this case autothermal operation exhibits a for-
increase occurs. The plateau region of the maxi- tunate tendency to self-stabilization: the maxi-
mum temperature becomes increasingly narrow mum temperature adapts quasi-automatically to
with rising ignition temperature. If the ignition the rising ignition temperature, so that total con-
temperature lies above the point of intersection version is ensured over a large activity range. If
T s of the two lateral straight lines, then operation the catalyst activity is too low, then extinction
in the ignited state is not possible. Accordingly, from a state with highest maximum tempera-
the narrower the plateau region of the maximum ture occurs rather abruptly. In the case where
temperature, the closer the operating point is to the catalyst is deactivated by excess tempera-
the stability boundary; the wider the maximum ture, the self-stabilization of course leads to a
temperature plateau, the more stable is the oper- vicious circle: the higher the maximum temper-
ation. ature, the greater the deactivation, and the higher
the maximum temperature, etc.
The influence of inert front and end zones,
which are frequently used with this type of re-
actor, can also easily be explained by means of
Figure 31 A. If the ignition temperature is T I1
and the fixed bed of the reactor is inert up to
the point z2 , then the catalytic reaction can be
initiated at the earliest at z2 ; the maximum tem-
perature is thus raised from T I1 to T I2 , compared
to the case of a continuously active catalyst.
Figure 31 B shows the influence of the feed
concentration in the form of the adiabatic tem-
perature rise on the temperature profile in the
steady state. According to Equation (5.2), an in-
crease in ∆T ad broadens the temperature profile
and raises the maximum temperature, whereby
the increase in the maximum temperature above
the ignition temperature is roughly proportional
to ∆T ad .
The above discussion refers to countercurrent
operation and to the limiting case of a very rapid
reversal of the flow direction. Normally during
operation with periodic flow reversal, the reac-
tion zone first migrates a certain extent into the
reactor. As shown in Chapter 6, a relationship
for the front migration velocity w can be derived
from the total energy balance around the moving
reaction front, and in the case of a large temper-
ature rise ∆T and a small adiabatic temperature
increase ∆T ad , w can be approximated as fol-
lows:
Figure 31. The influence of operating parameters on reac-
ε·G ·cpG
tor behavior w= ·vG (5.3)
A) Temperature and concentration profiles for gases with ε·G ·cpG + (1−ε) ·s ·cs
different ignition temperatures T I1 , T I2 ; B) Influence of
the feed concentration c01 , c02 , in the form of an adiabatic w from the above equation also corresponds to
temperature rise ∆T ad [11] the migration velocity of a temperature front in
a packing without reaction traversed with a ve-
In this connection, the influence of catalyst locity v G . The influence of the period duration
deactivation can also be illustrated. Deactiva- on the reactor behavior with periodic alternation
tion means a rise in the ignition temperature. In of the flow direction can easily be estimated by
 Fixed-Bed Reactors 31

using Equation (5.3). For stable, ignited oper- Fixed-bed reactors for industrial syntheses
ation the maximum temperature and full con- are generally operated over a long production
version must be reached during the entire pe- period with almost constant operating parame-
riod. A semiperiod may only be so long that the ters. The task of process control engineering is
temperature profile after reversal changes to the simply to keep these parameters optimal. In con-
gradient specified in Equation (5.2), without the trast, for supply or disposal plants that have sev-
maximum temperature falling below the igni- eral users or suppliers in a production network,
tion temperature. Thus, a conservative estimate there are frequent changes of feed material and
of the maximum semiperiod duration τ max is throughput which require fast, automatic reac-
tion control. Examples are fixed-bed reactors for
∆lmax synthesis gas production or off-gas treatment.
τmax =
w
with
6.2. Parametric Sensitivity
dT
∆lmax =L−2 (Ti −T0 ) · (5.4)
dz Parametric sensitivity is the property typical of
with catalyst bed length L as well as w, ∆T , all highly exothermic reactions with high acti-
and dT /dz from Equations (5.3), (5.1), and (5.2), vation energy: small changes in the operating
respectively. The behavior of autothermal com- parameters can lead to large changes in the max-
bustion reactors with periodically alternating imum temperature and yield. The reason is the
flow direction or integrated countercurrent heat exponential dependence of the reaction rate on
exchange can be estimated by using the above temperature (Arrhenius law). Figure 32 shows
equations [11]. calculated temperature profiles for partial oxida-
tion in a wall-cooled, fixed-bed reactor tube of
typical dimensions. In Figure 32 A only the main
reaction is considered, while in Figure 32 B the
6. Stability, Dynamics, and Control total combustion to CO2 and water is addition-
of Industrial Fixed-Bed Reactors ally taken into account. Since considerably more
heat is liberated in the total combustion than in
6.1. Introduction the desired main reaction, the sensitivity is in-
creased considerably. As a measure of the para-
Stability, dynamics, and control of fixed-bed re- metric sensitivity, Figure 32 C shows the change
actors with strongly exothermic reactions has in the maximum temperature via the cooling
been studied in great detail since the early 1970s. temperature for case B. The sensitivity is only
The numerous publications could give the im- moderate at low cooling temperatures, whereas
pression that this is a particularly critical reac- above T c = 343 ◦ C small changes in T c – and also
tor type with a large potential risk. In fact, the in other parameters such as throughput, feed
opposite is true. Compared to a liquid-phase re- concentration, or pressure –lead to large changes
actor of the same size, a fixed-bed reactor with in reactor behavior. Due to the unavoidable dif-
a gas-phase reaction contains a mass of reac- ferences between individual tubes, multitubular
tants several orders of magnitude smaller. There reactors cannot be operated in the range of high
is therefore no danger of a runaway exothermic parametric sensitivity. In this case the cooling
reaction due to reactants accumulating in the re- temperature must be lowered to ca. 340 ◦ C, and
actor, especially as the heat capacity of the cat- the tubes made longer to give a good conversion.
alyst mass additionally damps the uncontrolled This example emphasizes the requirement, dis-
temperature rise. cussed in Chapter 4, for making the conditions
Nevertheless, instabilities can arise in fixed- in the tubes of the tube bundle and in the cooling
bed reactors, particularly with strongly exother- circuit as uniform as possible to avoid premature
mic reactions, and can lead to excess tempera- runaway reaction in individual tubes.
tures that can damage the catalyst and the reactor In the literature there are numerous runaway
construction materials. Some causes of this are criteria with which operating ranges of high
discussed below. parametric sensitivity can be precalculated for
32 Fixed-Bed Reactors

Figure 32. Parametric sensitivity of a partial oxidation reaction in a fixed-bed reactor of typical dimensions as a function of
the coolant temperature T C with T (z = 0) = T C
A) Temperature profile over reaction length (main reaction only); B) Temperature profile including total oxidation as side
reaction; C) Maximum temperature T max and yield as a function of coolant temperature T C in case B; D) T max as a function
of T C for both cases

known reaction kinetics [35–37]. In practice, the quantification of the heat-transfer parameters
however, these parameters are of only limited (see Section 2.3).
importance because they rarely take into ac- An operating fixed-bed reactor can enter the
count the peculiarities of individual cases. Sen- region of high parametric sensitivity through
sitive reactions such as partial oxidation and par- changes in the catalyst properties or operating
tial hydrogenation are therefore generally tested conditions. Initially a few particularly sensitive
in single-tube reactors of the same dimensions tubes of the bundle will runaway, i.e., the re-
as those in the subsequent multitubular reactor. action changes, for example, from a selective
This allows the range of parametric sensitivity partial oxidation to a total combustion, and the
to be determined directly. Recalculation of the temperature rises rapidly. In a multitubular re-
results for other tube diameters is only possi- actor with thousands of tubes every tube cannot
ble to a limited extent due to the uncertainties in be equipped with temperature-profile measure-
 Fixed-Bed Reactors 33

ments; it is therefore likely that this runaway will process of ignition and extinction is associated
remain undetected, especially if it involves only with a local displacement of the main reaction
a few tubes. Although temperatures > 1000 ◦ C zone. This can be most readily demonstrated by
can often be reached in the catalyst during such the example of an exothermic reaction in an adia-
runaways, they are generally safe provided the batic fixed-bed reactor.
tube is surrounded by heat-transfer medium. Be-
cause of the good heat transfer to the fluid the
tube temperature remains close to that of the
heat-transfer medium, and melting of the tube
does not occur. The most certain method of de-
tecting a runaway is on-line analysis of a product
formed in the runaway reaction. For example,
CO2 can be monitored in the off-gas during the
runaway-sensitive synthesis of ethylene oxide.
If its concentration increases above a specified
limit, the reactor must be shut down and for a
certain period cooled to a lower cooling temper-
ature before operation is recommenced. The rea-
son why lowering the cooling temperature dur-
ing operation does not extinguish the runaway
reaction is discussed below.

6.3. Multiple Stationary States Figure 33. Ignition – extinction hysteresis in the region of
multiple steady states
Ignition occurs at T c = T cI and extinction at T c = T cE .
The term parametric sensitivity applies when,
according to Figure 32 D, a state quantity (T max ) Figure 34 shows the temperature profile for
is a single-valued function of a control quantity the catalytic total oxidation of ethane as a func-
(T C ). However, in the runaway examples dis- tion of feed temperature. If this temperature is
cussed in Section 6.1 this dependence can also raised only slightly above the value for profile I,
be multiple valued. Then the runaway occurs not the reaction ignites in the rear portion of the re-
in a finite range of the control quantity, but on ex- actor. Due to the axial thermal conduction in the
ceeding a fixed limit T ci , often referred to as the developing steep temperature front, the main re-
ignition limit (Fig. 33). Between ignition and ex- action zone moves slowly towards the entrance
tinction of the runaway reaction (at T C = T c E ), and is stabilized in position II a. The feed tem-
there is a hysteris region in which two stable perature must be lowered considerably to the
stationary states are possible; at least one un- value of position II b before the reaction extin-
stable intermediate state must lie between them. guishes completely to profile III upon a further
Various causes of multiple stationary states in slight lowering of the feed temperature. A sim-
fixed-bed reactors are known [38], [39]. Here, ilar ignition – extinction behavior can also arise
only the so-called thermal instabilities are dis- on changing the throughput or the feed concen-
cussed. They occur in exothermic reactions and tration. The multiple stationary states I–II a and
arise because the evolution of heat increases ex- II b – III are partly a result of the axial backward
ponentially with increasing temperature, while conduction of heat in the reaction front. This re-
the heat removal at constant cooling tempera- presents a positive feedback which stabilizes ei-
ture in-creases only linearly. Thus on exceeding ther the ignited or the extinguished state. Mech-
a certain temperature limit, the heat release in- anisms that transport heat from the end of the
creases more rapidly than the heat removal, and bed to its beginning stabilize multiple stationary
the reaction ignites. On dropping below a sec- states in a similar manner. These include the ax-
ond, lower temperature limit, the heat release ial thermal conduction in the tube wall [41] and
becomes less than the heat removal, and the re- especially the influence of countercurrent cool-
action is extinguished. In fixed-bed reactors, this ing when the temperature of the coolant rises sig-
34 Fixed-Bed Reactors

nificantly [42]. In autothermal reaction control

(see Chap. 5), countercurrent cooling is used to
stabilize the ignited state, which is desired in this
case. However, in the case of strongly exother-
mic reactions with a risk of runaway, counter-
current cooling should generally not be used.
The destabilizing effect of countercurrent cool-
ing is demonstrated by the examples discussed
in Figure 23. Another effect that can result in
multiple stationary states is single-grain insta-
bility (see → Principles of Chemical Engineer-
ing, Chap. 7.2., → Principles of Chemical Engi-
neering, Chap. 7.3.), which in fixed-bed reactors
is always coupled with the effect of the reverse
axial backward thermal conduction of heat [43]
and intensifies the above-mentioned hysteresis
behavior.

Figure 34. Measured axial temperature profile in the region

of multiple steady states in an adiabatic fixed-bed reactor for
the oxidation of ethane [40]
Ignition from profile I to II a; extinction from II b to III.

Whether a fixed-bed reactor goes runaway

due to high parametric sensitivity or whether
the reaction ignites on passing from a lower to a
higher stationary state, the results in practice are
the same: the maximum temperature increases
rapidly to an unacceptably high value. However,
in the case of parametric sensitivity, decreasing
the cooling temperature or feed concentration
during operation results in the maximum tem-
perature returning to the safe range, whereas Figure 35. Measured (points) and calculated temperature
when multiple stationary states are present, this profiles showing the transient of an adiabatic fixed-bed re-
need not be the case. If a certain limit is ex- actor for the methanation of CO and CO2 [44]
A) Transition after increase in feed concentration; B) Tran-
ceeded on ignition, then the runaway reaction sition after decrease in feed concentration; C) Transition
proceeds towards the ignited stationary state, after decrease in feed temperature
SV = V̇ /V R (space velocity)
 Fixed-Bed Reactors 35

even if the feed concentration or cooling temper- perature to T 0 (Fig. 36), gas flows from the left
ature is lowered considerably. Extinction of the into the reaction zone with velocity v −w and
reaction occurs only on passing below the ex- temperature T 0 (v = gas velocity), while from
tinction limits, which particularly for strongly the right catalyst enters the reaction zone with
exothermic reactions lie far below the ignition velocity w and temperature T 0 + ∆T and reacted
conditions. In this case, the best strategy is to gas leaves with velocity v − w and the same tem-
switch off the feed followed by inert gas purg- perature. The energy balance for the migrating
ing, until all temperatures have fallen to uncrit- reaction zone is thus:
ical values.

6.4. Migrating Reaction Zones

The discussion in the previous sections refers ex-
clusively to the stationary state, i.e., the temper-
ature and concentration profiles established after
a sufficiently long operating time. However, in
practice it is often more important in which way
and with which velocity these profiles approach
the next stationary state. This dynamic behavior
of fixed-bed reactors with exothermic reactions
exhibits several special features which are con-
nected with the axial displacement of the main
reaction zone in the form of a so-called migrat-
ing or moving reaction zone. The behavior can
be most easily discussed by using the example
of an adiabatic fixed-bed reactor.
Figure 35 shows measured temperature pro-
files for the methanation of traces of CO and
CO2 . This reaction is carried out in an adia-
batic fixed-bed reactor during ammonia synthe- Figure 36. Derivation of the energy balance in a quasi-
sis gas production. If the feed concentration is stationary migrating reaction zone in a fixed-bed reactor
increased, a new main reaction zone forms in the It follows that for the temperature increase
front part of the reactor, and the temperature rises ∆T at the reaction front:
here to a new maximum value. At the same time,
the reactor outlet temperature initially drops be- ∆Tad
∆T = (1−ε)·w ·s ·cs
(6.2)
low the original value before increasing to the 1− ε·(v −w)·
G ·cpG
new final value. This temporary reaction in the
wrong direction is known as wrong-way behav- Thus for w > 0 (i.e., reaction zone moving
ior. More surprising is the wrong-way behav- downstream), the temperature increase of the
ior in the examples of Figure 35 B (decrease in reaction front is always larger than the adia-
feed concentration) and Figure 35 C (decrease in batic temperature rise because the entering gas
feed temperature). Particularly in the latter case, is heated by the hot catalyst (which is cooled)
the maximum temperature in the fixed bed ini- and because of the liberated heat of reaction.
tially increases rapidly while the main reaction The examples of autothermal reaction con-
zone moves slowly backwards out of the reac- trol with periodic reversal of the flow direction
tor. An explanation for this behavior in terms (Section 5.2) show that the temperature increase
of the heat balance around a migrating combus- of the combustion zone can be conserably higher
tion zone was first derived by Wicke and Vort- than the adiabatic temperature rise. According to
meyer [45]. In a migrating reaction zone that Equation (6.2), the temperature increase in the
moves through an adiabatic fixed-bed reactor combustion can even rise to arbitrarily high val-
with velocity w due to lowering of the feed tem- ues when the denominator approaches zero; i.e.,
36 Fixed-Bed Reactors

the migration velocity reaches the critical limit Particularly problematic is catalyst deactiva-
W crit : tion due to excess temperature deactivation of
ε·G ·cpG the catalyst because it results in a vicious circle:
Wcrit = ·v (6.3) the catalyst is deactivated in the region of the
ε·G ·cpG + (1−ε) ·s ·cs
main reaction zone due to an excessive max-
In this case, the reaction front moves with ex- imum temperature. This leads to a migrating
actly the velocity of a temperature front without combustion zone in which the maximum tem-
reaction. If dispersion effects such as thermal perature rises further, and so on. Impressive ex-
conduction are neglected, the liberated heat of amples of this behavior in wall-cooled reactor
reaction can no longer be transported out of the tubes have been described by Blaum [47] and
reaction zone and thus accumulates there. Emig [48].
The migration velocity w of a reaction front Figure 38 shows measured profiles in a bed
can generally not be preset from outside, but is of thermally unstable nickel catalyst in the case
instead a result of the complex interaction of of CO oxidation. Figure 39 shows the tempera-
material and heat transport with the reaction, as ture profile for vinyl acetate synthesis over zinc
is approximately described by fixed-bed reactor acetate. Since the zinc acetate catalyst decom-
models. However, there is one noteworthy ex- poses above 500 K, the result is a reaction front
ception, which occurs when the catalyst in the that moves downstream. The dip in the temper-
main reaction zone is deactivated with exactly ature profile (d) clearly indicates deactivation at
the critical velocity. the position of the original temperature maxi-
In the example of Figure 37, this deactiva- mum. In the past, this was sometimes cited as
tion was carried out deliberately by adding a a good example of parametric sensitivity. The
catalyst poison (thiophene) to the feed at time above discussion, however, shows that the cause
t = 0. This results in a deactivation of the nickel of the “runaway” reaction should rather be at-
catalyst by irreversible adsorption of thiophene, tributed to the dynamic influence of the migrat-
whereby the adsorption front moves through the ing combustion zone.
bed with velocity w, pushing the reaction front
before it. The accidental addition of a catalyst
poison can thus lead to migrating combustion
zones with very high maximum temperatures in
both adiabatic and nonadiabatic reactors, if a mi-
gration velocity in the critical range is initiated.

Figure 38. Migrating combustion zone in the case of CO

oxidation over nickel, caused by thermal deactivation of the
Figure 37. Migrating reaction front in an adiabatic fixed-
catalyst [47]
bed reactor due to intentional catalyst poisoning (hydrogen-
ation of benzene over nickel) [46]
At t = 0, a catalyst poison thiophene is added to the feed.
 Fixed-Bed Reactors 37

efforts for heating, cooling, and separation of the

inert gas, while the latter gives only low conver-
sions of the reactants in a single pass. New de-
velopments in partial oxidation therefore aim for
stoichiometric operation in the ignitable range
[51]. A prerequisite for this is pressure-resistant
construction with check valves and flame barri-
ers so a possible that ignition is confined to the
interior of the reactor.

Figure 39. Migrating reaction front during the synthesis of

vinyl acetate over zinc acetate, caused by thermal damage
to the catalyst [48]
a) 60 min; b) 75 min; c) 100 min; d) 165 min

6.5. Safety Aspects

Because of the small mass storage capacity com-
pared to liquid-phase reactors, the danger of sud-
den reaction of accumulated reactants in gas-
phase fixed-bed reactors is low. Leaving out the
peculiarities of individual cases, the following
safety risks can be assumed for fixed-bed reac-
tors:
1) Leaks which result in the release of large
amounts of gas or vapor and the formation
of explosive clouds
2) Leaks resulting in release of large amounts
of liquid heat-transfer media (oils, salt melts)
3) Occurrence of ignitable or decomposable gas
mixtures in the reactor
4) Melting of the reactor due to a runaway re-
action
The safety aspects of liquid heat-transfer me-
dia are discussed in Section 4.3.1. Ignitable gas
mixtures can arise particularly during partial ox-
idation reactions. They are especially critical
where large packing-free volumes are present.
This is the case in the inflow and outflow hoods
of the reactor, while in the reactor tubes the cata-
lyst packing dampens the propagation of a flame
front due to its heat capacity. Complete avoid- Figure 40. Effect of disturbances in the coolant circuit of
ance of ignitable mixture is generally not possi- a multitubular reactor (Fig. 41) with a partial oxidation re-
action [49]
ble in partial oxidations because at least during A) Profile of maximum temperature with time after change
mixing of the gas streams prior to the reactor the of the valve position (∆ṁc ), after pump failure (v c → O),
ignition limit is exceeded locally. Nevertheless, and after valve closure (ṁc → O); B) Temperature profile
in the past, operation of fixed-bed reactors with after failure of the coolant circulation pump
ignitable mixtures was avoided, either by dilu- Melting of reactor tubes during runaway reac-
tion with inert gas or by operating in the nonstoi- tion is only to be feared in multitubular reactors
chiometric range. The former requires additional
38 Fixed-Bed Reactors

if the respective tube is not surrounded by heat- ichiometry control, control of the total pressure
transfer medium. Thus, appropriate design must (generally in the reactor outlet), as well as feed
ensure that running dry of reactor tubes cannot temperature and heat-transfer medium temper-
occur. In the case of corrosive reaction gases, ature control are therefore the most important
apparatus for the detection of leaks caused by automatic control circuits in fixed-bed reactors.
corrosion must be provided, particularly when In the following, some special points con-
pressurized or boiling water is used as coolant. cerning the cooling temperature control of mul-
If the coolant circulation is interrupted dur- titubular fixed-bed reactors are considered. In
ing an exothermic reaction, the reactor must be a multitubular reactor with molten-salt cooling
shut down. Nevertheless, the heat storage capac- (Fig. 41) the cooling temperature is controlled
ity of the catalyst and the heat-transfer medium by a control unit in the connecting channel to the
surrounding the tubes allows sufficient reaction steam generator. In this way, varying amounts of
time for controlled shutdown of the reactor. This colder salt melt can be introduced into the circu-
is shown by simulation calculations for a mul- lation system, with effective mixing taking place
titubular reactor (Fig. 40) with a partial oxida- in the circulating pump. This cooling circuit can
tion reaction. It was assumed that at t = 0 either be unstable [37]. Since the reaction rate or lib-
the circulating pump fails or that the regulating erated heat Q̇E increases exponentially with in-
valve in the pipe to the steam generator closes. creasing cooling temperature, while the heat re-
As can be seen in Figure 40, there is a time span moved in the steam generator Q̇A increases only
of 200 or 350 s, respectively before the maxi- linearly, the conditions shown in Figure 42 may
mum temperature in the catalyst reaches unper- occur in the desired state. On a slight increase of
missably high values. the cooling temperature above T C, set , the cool-
In large-volume adiabatic fixed-bed reactors, ing circuit warms up since Q̇E > Q̇A , and on
local temperature maxima (hot spots) can form dropping slightly below T C, set cools down be-
due to nonuniform distribution of the flow or cause Q̇A > Q̇E . Because of the large thermal in-
inhomogeneities in the catalyst packing. They ertia, however, the unstable operating point can
can be intensified by front migration phenomena easily be stabilized via the control TC (Fig. 41).
(Section 6.4) and can lead to thermal damage of
the reactor. This is particularly true of runaway-
prone reactions such as partial hydrogenation
with a large excess of hydrogen, which can
change from selective hydrogenation to com-
plete methanation. This can be detected by on-
line analysis of methane in the product.

6.6. Control of Fixed-Bed Reactors

The control of fixed-bed reactors for chemical
synthesis generally only involves maintaining
the operating conditions at the optimum val-
ues. For runaway-prone reactions, this is sup-
plemented by an extensive measurement and
control system with built-in redundancy for giv-
ing alarm and shutting down the reactor. Slow
changes in catalyst activity during multistage
adiabatic reactors are corrected by “manual” ad-
justment of the set value for the feed temperature
of each stage in multitubular reactors or by the
Figure 41. Temperature control in a fixed-bed reactor with
adjustment of the heat-transfer medium temper- molten-salt cooling
ature. The target is usually to keep the desired
conversion constant. Mass flow control, feed sto-
 Fixed-Bed Reactors 39

result in liquid entering the vapor line. This is

discussed in detail in [49].

Figure 42. Heat generation Q̇E and heat removal Q̇A for
the cooled multitubular reactor of Figure 41 as a function
of coolant temperature [37]

To obtain optimum conversion, attempts are

usually made to operate with a cooling temper-
ature so high that a previously determined max-
imum temperature in the reactor is just reached
but not exceeded. The maximum temperature
can be measured by equipping several tubes of
the bundle with multiple thermoelements which
allow simultaneous measurement of, for exam-
ple, 10 – 20 temperatures along the tube length.
This allows regulation of the maximum tempera-
ture, which influences the set point of the cooling Figure 43. Multitubular reactor with evaporative cooling
temperature in a cascade circuit. However, deter- If the fixed bed to be regulated is part of a
mining the maximum temperature from various supply or off-gas treatment plant that is sub-
discrete measurement points is not trivial [50]. ject to large variations in feed concentration
Therefore, methods for the model-based mea- and throughput, then a fixed control is difficult,
surement techniques should be used here. mainly because of the complex wrong-way be-
In the case of cooling with a boiling medium, havior (see Section 6.4). Hence, in practice a
a multitubular reactor generally has the struc- catalyst with a wide operating range is used and
ture shown in Figure 43. The cooling tempera- the reactor is made larger.
ture here corresponds to the boiling temperature
in the vapor drum, which is controlled by a con-
trol unit in the saturated vapor line. The cooling
temperature control is thus performed by con-
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and Hazards: an Annotated Bibliography,” J.
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Hazard. Mater. 4 (1980) 145 – 175.
32. G. K. Boreskow, G. A. Bunimovich, Y. S.
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Matros, A. A. Ivanov: “Catalytic Processes
Modellbildung bei technischen
Carried Out Under Non-Steady-State
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Conditions: Switching the Direction of the
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Int. Chem. Eng. 22 (1982) 335 – 342.
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170 – 175.
19. M. S. G. Cristina et al.: “Modelling Eng. Sci. 45 (1990) 2097 – 2102.
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 Fixed-Bed Reactors 41

34. Y. S. Matros: “Catalytic Processes under 44. H. von Doesburg, W. A. de Jong: “Transient
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 Flame Retardants 1

Flame Retardants
Burton J. Sutker, Ethyl Corporation, Sayreville, New Jersey 08872, United States

1. Introduction . . . . . . . . . . . . . . . . . 1 4.3. Formulation with Additive Flame Re-

2. Mechanism . . . . . . . . . . . . . . . . . 1 tardants . . . . . . . . . . . . . . . . . . . . 11
2.1. Dilution . . . . . . . . . . . . . . . . . . . . 1 4.4. Interactions between Flame Retar-
2.2. Generation of Noncombustible Gas . 2 dants and Other Formulation Ingredi-
2.3. Gas-Phase, Free-Radical Inhibition . 2 ents . . . . . . . . . . . . . . . . . . . . . . . 14
2.4. Solid-Phase Char Formation . . . . . . 3 4.5. Formulation to Reduce Smoke . . . . . 15
3. Test Methods . . . . . . . . . . . . . . . . 5 5. Flame Retardant Markets . . . . . . . . 15
4. System Development . . . . . . . . . . . 7 6. Toxicology . . . . . . . . . . . . . . . . . . 17
4.1. Selection Criteria of Flame Retardants 7 7. Future Directions
4.2. Formulation with Reactive Flame Re- in Flame Retardants . . . . . . . . . . . . 18
tardants . . . . . . . . . . . . . . . . . . . . 8 8. References . . . . . . . . . . . . . . . . . . 19

1. Introduction 2) heat, supplied either externally or from the

combustion process itself
Flame retardationis a process by which the nor- 3) an oxidizing gas, primarily oxygen.
mal degradation or combustion processes of
polymers have been altered by the addition of
certain chemicals. The polymers exhibit resis-
tance to decomposition by thermal stress when 2.1. Dilution
measured by standard tests. The degree of resis-
tance to flammability is usually defined by a nu- Reducing the total quantity of combustible mat-
merical value of the test as being more resistant ter improves overall flame retardation. For ex-
to flame or fire than the unmodified polymer. Re- ample, adding fillers, such as clays, to polymer
sults of these tests should not be used exclusively systems (often 50 – 200 parts by weight per 100
to predict performance in an actual fire, although parts of polymer) reduces flammability. How-
they are a guide in selecting materials. Flame- ever, in some cases, such as glass fiber reinforced
retarded materials, can be formulated to be more composites, the glass fiber stiffens the polymer.
resistant to ignition than non-flame-retarded ma- On exposure to heat or a flame, the glass may
terials, or to have slower rates of flame spread prevent the polymer from melting away from
in a major fire that is initiated by some other the flame; thus, the material burns. In addition,
source; however, the flame-retarded article will the glass can act as a heat sink so that less en-
ultimately burn. ergy input is required to ignite the polymer on a
second exposure to heat.

2. Mechanism
A basic understanding of the different theories 2.2. Generation of Noncombustible Gas
by which flame retardants function is essential [1]
for identifying and selecting the optimum ma-
terial for any given situation. Many alternative Some materials decompose when heated, gener-
materials can be used, and the cost performance ating noncombustible gases. These gases lower
often dictates the choice. Flame retardants func- the oxygen concentration at the front of the flame
tion by their interaction or interference with one and often result in flame snuffing because of lack
of the three required components of a fire: of oxygen. This result is transitory because once
the material decomposes the residual matter acts
1) a combustible substance or fuel

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11 123
2 Flame Retardants

as an incombustible diluent of the polymer ma- HO · + CO −→→ CO2 + H · Highly exothermic

trix. An example of this type of flame retardant H · + O2 −→→ HO · + O · Chain branching
is calcium carbonate [471-34-1] which decom- O · + HBr −→→ HO · + Br · Chain transfer
HO · + HBr −→→ H2 O + Br · Chain termination
poses at 825 ◦ C to generate the solid, calcium ox-
ide, and the gas, carbon dioxide; these products
do not support combustion. The use of calcium The HBr from decomposing brominated
carbonate with brominated flame retardants is compounds is very effective in deactivating free
not recommended, however. Calcium carbonate radicals in the vapor phase. The formation of
and its more alkaline decomposition product, new radicals is also reduced as less heat is gen-
calcium oxide, absorb hydrogen bromide that is erated, and the entire combustion process is
liberated from the brominated flame retardants slowed.
to form inactive species, such as calcium bro- Chlorinated compounds function in the same
mide. manner. In practice, often twice as much
Some materials decompose to produce wa- chlorine-containing compound is required as
ter vapor as the noncombustible gas. Heat is bromine-containing compound. The difference
absorbed because of decomposition as well as approaches the atomic mass ratio for the two
vaporization of liquid water. Aluminum oxide halogens, i.e., 79.90 : 35.45 = 2.25.
trihydrate [21645-51-2], (Al2 O3 · 3H2 O) be- Compounds containing iodine are known, but
gins to decompose at 230 ◦ C with the release are of limited use as flame retardants because of
of 34.5 wt % of its original mass as water va- their poor thermal stability. The dark color of
por. Magnesium hydroxide [1309-42-8], or hy- many organoiodine compounds is also a nega-
drated magnesium oxide, begins to decompose tive factor.
at 340 ◦ C with the release of 31 wt % of the orig- Compounds containing fluorine generally ex-
inal mass as water. For processing polymers at ist as functional polymers instead of as mate-
elevated temperature, the higher decomposition rials added to other polymeric systems to pro-
temperature of magnesium hydroxide makes it vide flame retardation. These polymers are very
preferable to hydrated alumina [1]. Typically, stable and decompose only at high temperature.
50 – 100 parts by weight of these compounds Hydrofluoric acid, when finally liberated, is an
are required per 100 parts of polymer to achieve effective free-radical deactivator.
flame retardation. Antimony oxide acts as a synergist with halo-
Azo compounds are used in forming foam gens, particularly chlorine and bromine [3]. It is
polymer systems. These materials liberate ni- almost totally ineffective if used without halo-
trogen. Although effective in producing foams, gen. The trioxide [1309-64-4] is the common
their cost effectiveness compared to that of other material used, although the pentoxide is also
compositions has eliminated their use as flame available. The pentoxide [1314-60-9], as manu-
retardants. factured, generally has a much finer particle
size and is more efficient per unit mass added
than the trioxide. Semitranslucent thermosetting
polyester laminates containing the pentoxide are
2.3. Gas-Phase, Free-Radical Inhibition
also possible. Because some thermoplastic poly-
[2], [3] esters are sensitive to residual activity in all
forms of antimony oxide, alkaline salts of an-
Combustion of hydrocarbons creates highly ac- timony oxide are used in these critical cases.
tive fragments in the solid or condensed phase. Synergism may occur through a series of re-
These fragments vaporize, react with oxygen, actions; the basic reaction in the case of bromi-
and form free radicals. Free-radical formation is nated flame retardants is:
highly exothermic, resulting in volatilization of
additional active fragments from the condensed −→
Sb2 O3 + 6 HBr ←− 2 SbBr3 + 3 H2 O
phase. The process continues unless free-radical
Antimony tribromide forms a dense white
formation is interrupted and stable species are
smoke that snuffs the flame by excluding oxy-
produced. Some of the reactions that may occur
gen from the front of the flame. Water from nor-
are as follows [2]:
mal combustion causes the equilibrium to shift
 Flame Retardants 3

to the left, forming antimony oxide, which is Phosphorus and Boron Compounds.
then available to react with fresh HBr from de- Phosphorus is available in the elemental state,
composing brominated compounds. as organic phosphates, or as inorganic acid phos-
Some applications cannot take advantage of phates. All forms are used as flame retardants in
the synergy between halogen and antimony ox- different polymer systems, e.g., elemental red
ide. For example, epoxy – glass fiber printed cir- phosphorus in polyamides, organophosphates
cuit boards contain high levels of bromine in- in polyphenylene oxides or polyurethanes, and
stead of combinations of bromine and antimony inorganic acid phosphates in cellulosics. In the
oxide. Trace quantities of antimony oxide poison presence of heat and oxygen, phosphorus com-
chemical treatments used to etch the copper-foil pounds decompose to form water vapor and
printed circuits. phosphorus oxides. The phosphorus oxides sub-
The effectiveness of halogen in inhibiting sequently react with the polymer matrix and
radical formation is often a function of the dehydrate it, reforming phosphoric acids. These
organic structure to which it is attached. In acids again decompose to reform water vapor
polypropylene, a cycloaliphatic bromine com- and phosphorus oxides.
pound is more efficient at low levels than a Ultimately as the water available from nor-
more stable aromatic bromine compound. This mal combustion of hydrocarbons diminishes,
is because of the relative decomposition char- the phosphorus oxides react with hydrocarbon
acteristics of the bromine compound and the fragments to produce a very high melting point
polymer. However, with rubber-modified, high- char at the interface between the polymer and
impact polystyrene, the more thermally stable the heat source. The chars, which contain phos-
aromatic compound is more efficient. phorus, rapidly dissipate heat energy and lose
Typically, halogenated compounds used in their “glow”. This antiglow property of phos-
applications of flame retardants contain either phorus contributes to its effectiveness as a flame
40 – 70 wt % chlorine or 45 – 80 wt % bromine. retardant.
From 20 to 40 parts of chlorinated compound or Boron compounds can function in a manner
5 – 30 parts of brominated compound would be similar to phosphorus compounds. However, el-
used per 100 parts of polymer, depending on the emental boron is not used commercially as a
flame retardant requirements. Antimony oxide flame retardant. Organoboron compounds are
use is typically 25 – 50 % that of the halogenated less stable and typically much more expensive
material. than organophosphorus compounds. Inorganic
Poly(vinyl chloride) has inherently good boron compounds are used as extenders for an-
flame-retardant characteristics because of the timony oxide or in low-cost treatments for cel-
high chlorine content. Antimony oxide (3 – lulosics.
5 wt %) is often helpful in passing the more strin- Typically, 1 – 10 parts of contained phos-
gent flammability tests. phorus or boron is used per 100 parts of polymer.
Care should be taken, however, in developing
formulations that use both gas-phase and solid-
2.4. Solid-Phase Char Formation phase flame retardant mechanisms because com-
binations of halogen, antimony oxide, and phos-
Several different types of flame retardants form phorus can be synergistic or antagonistic.
insulating or minimally combustible chars on
polymer surfaces exposed to external heat Sulfur Compounds. Some inorganic sulfur
sources. This char reduces volatilization of ac- compounds, such as ammonium sulfate and am-
tive fragments and absorbs and dissipates heat. monium sulfamate, form anhydrous sulfur ox-
The effectiveness of the flame retardant is spe- ides on decomposition. Sulfur compounds are
cific for each polymer. For example, phos- used almost exclusively as low-cost flame re-
phorus-based flame retardants are effective in tardants for cellulosics. Sulfur compounds are
producing a minimally combustible char in not used commercially as flame retardants in
phenylene oxide – ether polymers, but are essen- thermoplastics or other polymer systems, al-
tially ineffective in styrenic polymers. though research is being conducted in this
4 Flame Retardants

area. On the basis of improved flame retar- herently flame retardant (→ High-Performance
dancy of poly(phenylene sulfide) nonmigrvs. Fibers).
poly(phenylene ether) as a neat polymer, an im- The concept of polynuclear aromatic ef-
provement in flame-retardant properties from fectiveness is also used in additive bromine
those of sulfur-containing materials vs. oxy- compounds, such as decabromodiphenyl ox-
genated materials could be predicted. ide [1163-19-5] (Saytex 102 flame retar-
dant) and ethylene bis(tetrabromophthalimide)
Silicon Compounds [4], [5]. Organosilicon [32588-76-4] (Saytex BT-93 flame retardant). In
compounds can decompose to form incom- many systems BT-93 is more effective than 102
bustible silicon oxide structures. For example, even though BT-93 has a lower bromine content.
organosilicon-containing polymers can be for- Thermal gravimetric analysis shows significant
mulated to produce low-density silicone foams char formation on decomposition for BT-93 and
with excellent flame-retardant characteristics. almost none for decabromodiphenyl oxide.
Proprietary metallic catalysts, such as platinum,
are quite efficient in these systems. Intumescence [6]. Systems containing a
Halogenated phenol organosilicon com- polyhydric alcohol (e.g., pentaerythritol), a ni-
pounds have been developed and are more ef- trogen source (e.g., melamine), and a phos-
ficient than analogous compounds without sili- phorus donor (e.g., ammonium polyphosphate)
con [4], [5]. This efficiency is probably a result can form thermally stable foams when heated.
of formation of a char containing silicon oxide, The major historical use of this intumescent
and of the vapor-phase activity of the halogen. chemistry has been in water-based paints and
Care must be exercised in the choice and use coatings. Untreated polypropylene has also been
of silicon-containing materials. Finely divided flame retarded effectively with intumescent sys-
calcium silicates used as thickening agents in tems, but at high loadings of 30 – 50 parts per
polymer systems can adversely affect flame re- 100 parts of polymer. These polymer formula-
tardation. tions generate little smoke when burned.
Even under polypropylene processing condi-
Polynuclear Aromatics. Some materials, tions, care is required to avoid premature foam-
which form highly condensed aromatic struc- ing of the ingredients. More thermally stable sys-
tures when heated, ultimately burn because they tems have been proposed for styrenic polymers
are hydrocarbons, but do so with difficulty. Un- [6]. These systems are reported to produce little
treated phenolic polymers have good flame- smoke and good resistance to ultraviolet light.
retardant properties. However, they can glow
and radiate heat for prolonged periods of time
after the original heat source is removed and, 3. Test Methods
therefore, can ignite combustible matter in con-
tact with them. Test methods have been developed that vary in
Complex aromatic polyesters resulting from complexity from simple (e.g., ASTM D 2863
the alkaline hydrolysis of poly(ethylene tereph- and UL 94, which require specimens that are
thalate) residues are effective in polyurethane, 10 cm long) to very complex (e.g., ASTM E 84,
polyisocyanurate, and hybrid foam systems as which require specimens 750 cm long) [7].
char formers. Isocyanurate foams show better Test methods may evolve on the basis of par-
flame retardation than conventional urethanes ticular requirements of a country or industrial
because of the more condensed polynuclear aro- group. In the United States, materials must meet
matic structure. Polyamides based on aliphatic Underwriters Laboratory standards of perfor-
diamines and aliphatic diacids have a limited mance: polymer compositions used in general
degree of inherent flame-retardant properties. electrical components must satisfy the UL 94
However, polyamides that have aromatic rather test; wire and cable compositions, UL 44 or
than aliphatic reactant groups have been made 62; television components, UL 1410. Products
into fibers with excellent flame retardation. In going into coal mines in the People’s Repub-
fact, Nomex fibers can be made into firefight- lic of China must meet standards based on
ers’ uniforms. Aromatic polyimides are also in- ASTM D 2863. Insulating foams for sale in the
 Flame Retardants 5
Polyolefins 17.4
Federal Republic of Germany must be rated by Flame-retarded polyolefins 24 – 28
a DIN test. Polystyrene 18.1
These tests are conducted on small specimens Flame-retarded polystyrene 27 – 30
Epoxy resin 24.0
instead of finished articles, even though config- Polyurethane foam 18.0
uration does affect flammability results. Many Rigid poly(vinyl chloride) 40.0
Polytetrafluoroethylene 95.0
industrial and regulatory authorities have real-
ized the shortcoming of such simplistic test pro-
cedures and have developed larger-scale tests
on finished articles. Full-scale burns of finished The oxygen index test is simple and repro-
electrical wires and cables, foam-upholstered ducible and is used to guide development work.
chairs, and total roofing assemblies are now Conclusions about fire performance in an actual
more common. Because of cost, only the largest fire should not be made based on results from
companies have facilities to conduct these tests. the oxygen index test or any other test.
Specialized consulting testing laboratories have
emerged to do this work for smaller companies UL 94 of Underwriters Laboratory. The
and to provide unbiased data for product accep- UL 94 test rates materials on the basis of their
tance or regulatory purposes for companies of ability to resist combustion on repeated applica-
all sizes. tion of a flame. The test also rates materials for
their resistance to dripping with subsequent ig-
nition of a combustible substance (cotton) from
the resulting drips.
Test specimens (12.7×1.27 cm×various
thicknesses) are mounted vertically in a cham-
ber (Fig. 2). Ignition takes place at the lower end
of the test specimen. After a 10-s ignition, the
flame is removed. If the specimen extinguishes,
the afterflame time is recorded and the specimen
is reignited for 10 s.
Materials are classified on the basis of af-
terflame time and ignition of the cotton caused
by flaming drips. The most widely accepted
classes are 94 V-0, 94 V-1, and 94 V-2. Class
94 V-1 allows a longer afterflame time than 94 V-
Figure 1. Oxygen index tester, ASTM D 2863 [7, p. 183]
0, whereas class 94 V-2 has the same afterflame
a) Pilot flame; b) Burning specimen time as 94 V-1 but allows for cotton ignition.
Variations of the test utilize different shape spec-
imens and orientations, e.g., horizontal.
Many applications require UL 94 V-0 ratings
ASTM D 2873-77. The oxygen index or at very thin sections. Historically, a V-0 rating at
limit oxygen index test determines the oxy- 0.32 cm was acceptable; however, more recent
gen concentration at which sustained combus- products are formulated to achieve a V-0 clas-
tion occurs using a vertically mounted speci- sification at 0.08 cm. Achieving the V-0 classi-
men ignited at the upper end (Fig. 1). The test fication at thinner sections is difficult because
is performed at room temperature, but equip- of the tendency of thermoplastics to melt and
ment is available to test for oxygen index drip. Although polymers that drip are permitted
at elevated temperature. Results are expressed by UL 94 V-0, a delicate formulating balance is
as [V O2 /(V O2 + V N2 )] · 100 %. Typical oxygen required to ensure consistent passage of the test.
index values (in vol %) for polymers are as fol- Because of the worldwide importance of the
lows: United States market, companies that export
electronic assemblies to the United States manu-
facture products to the UL 94 standard. This
6 Flame Retardants

standard often becomes the accepted norm for their flame spread, fuel contribution, and smoke
products for the individual domestic market- evolution.
place as well. Multinational corporations seek- Test specimens (51.43 ± 1.9 cm wide by
ing uniformity in many countries also utilize the 629.9 ± 1.27 cm long) are placed in a tunnel and
UL 94 standard to simplify testing. ignited at one end. Ratings are based on the per-
formance of a standard redwood board (flame
spread 100) and asbestos board (flame spread
0).
Typically only the flame spread and smoke
values are used to rank materials. Local United
States building codes often include E-84 values
in their material acceptance criteria. Code val-
ues for flame spread are 25 for class I and 75 for
class II; smoke density values are 450 for both
classes, relative to cement – asbestos (0) and red
oak (100).

DIN 4102 Part 1. The Federal Republic of

Germany rates building and construction mate-
Figure 2. Underwriters Laboratory, UL 94 ∗ [7, p. 350]
rials by this test as noncombustible (A) or com-
a) Specimen; b) Burner; c) Surgical cotton (ca. 50×50 bustible with low (B-1), moderate (B-2), or high
×6.5 mm) (B-3) flammability characteristics.
∗ Dimensions are in mm. Four specimens (19×100 cm) are mounted
around a chimney and ignited from the bottom
for 10 min. At the end of the test, specimens are
measured and other observations made. To be
rated B-1, the mean length of the specimens must
still be 15 cm.
In some variations of the DIN test, surface
charring is an important test criteria. Thus, the
total specimen could still be B-1 by DIN 4102,
but surface charring would render it a B-2 or B-
3 classification. Some aliphatic bromine com-
pounds are more effective in reducing this sur-
face flash charring than others.

4. System Development
Flaming can be retarded by incorporation of the
flame-retardant molecule into the polymer itself
or by admixture of the flame retardant with the
polymer. The former is the reactive approach,
Figure 3. Steiner tunnel, ASTM E 84 [7, p. 229] and the latter is the additive approach.
A) Longitudinal view: a) Test chamber (7.62 m); b) Fire end;
c) Vent end; e) Viewing windows The major advantage of the reactive approach
B) Cross-sectional view of section x – y: d) Removable cover is the non-migratory nature of the flame retar-
plate; e) Viewing windows; f) Gas burner; g) Specimen dant. This eliminates mold plate-out or bloom-
ing, which often occurs with flame retardants in
plastics systems. A secondary advantage is the
ASTM E 84. The ASTM E 84, or Steiner ability to produce optimum polymer properties
tunnel test (Fig. 3), is used to rate building and by using the proper balance of reactive material
construction materials in the United States for and other monomers. Additive-type flame retar-
 Flame Retardants 7

dants generally reduce some property, such as bis(tetrabromophthalimide) has superior resis-
impact resistance or heat resistance. tance to UV light in styrenic polymers com-
Costs associated with reactive systems are pared with halogenated diphenyl oxides. How-
usually higher than with additive systems be- ever, television cabinets and computer compo-
cause of the required development of new poly- nents are often painted to mask color changes
merization technology. Reactive systems may resulting from fluorescent or UV light exposure
not be as effective as additive systems because in preference to using flame retardants with good
of the more controlled availability of the flame light resistance. Other special environmental ex-
retardant. The ability of flame retardants to melt posure criteria are optical clarity and corrosion
and migrate to the flame front in the heat of a fire resistance.
is often desirable; such movement is restricted if Aromatic bromine-based flame retardants
the flame retardant is part of the polymer back- have resulted in the development of new prod-
bone. ucts that overcame previous performance defi-
Typical examples of systems in which ciencies [8]; these compounds are listed in Ta-
reactive flame retardants can be used are ble 1.
polyurethanes, unsaturated polyesters, epoxy Compounding (or reacting) of the flame re-
resins, and polycarbonates. However, some ad- tardant must take into account the stability of
ditive systems exist for each of these polymer the flame retardant, the matrix in which it is sus-
classes, and the choice between additive, reac- pended, and the effect of the flame retardant or
tive, or hybrid systems is based on other formu- its degradation products on processing or com-
lation parameters, such as properties and costs. pounding equipment. Typically, thermal gravi-
For example, glass fiber reinforced bathroom metric analysis is used to evaluate the decompo-
showers and tubs are typically produced with sition or volatilization of flame retardants and to
high loadings of aluminum oxide trihydrate as an aid in selection of the most cost-effective mate-
additive flame retardant. Alternatively, a bromi- rial.
nated or chlorinated acid or alcohol can be used
in forming the polyester resin itself.
4.2. Formulation with Reactive Flame
Retardants [9], [10]
4.1. Selection Criteria of Flame
Retardants [8] Reactive flame retardants must be combined
with the polymer during manufacture or be ca-
Identification of the flammability test require-
pable of being grafted during subsequent pro-
ments is the initial criterion for selection of
cessing. Each flame retardant has a unique tech-
the appropriate flame retardant. In some cases,
nology that provides the desired level of flame
changing part design or construction material
retardation and polymer properties.
obviates the need for flame retardants.
Establishing the desired cost – performance
Polyurethane Foams. Flame-retardant rigid
parameters is the second key criterion. For ex-
foams can be produced from polyhydroxy-
ample, a UL 94 V-0 polypropylene may be pro-
terminated chlorine- and bromine-containing
duced with 10 – 100 parts of various flame retar-
compounds with a nonreactive organophosphate
dants per 100 parts of polypropylene. The prop-
as diluent to reduce viscosity (Solvay IXOL B-
erties and costs of systems containing high load-
251), or from ester ethers of tetrabromoph-
ings of flame retardant are vastly different from
thalic anhydride (Ethyl Saytex RB-79 flame re-
those at low loadings.
tardant) [75790-69-1]. Derivatives of dibromo-
Environmental exposure requirements of the
neopentyl glycol or organophosphates that have
finished article is a third criterion. For ex-
a hydroxyl functionality, such as diethyl-N,N-
ample, unsaturated polyesters based on di-
bis(2-hydroxyethyl)aminomethyl phosphonate
bromoneopentyl glycol [3296-90-0] have su-
(Stauffer’s Fyrol 6) [2781-11-5], can also be
perior resistance to discoloration by UV
used. A formulation for a rigid urethane foam
light compared to products based on tetra-
that meets ASTM E 84 Class I is as follows:
bromophthalic anhydride [632-79-1]. Ethylene
8 Flame Retardants
Table 1. Aromatic bromine-based flame retardants

Bromine compound CAS registry no. Bromine, % mp, ◦ C 10 wt %,

loss by
TgA, ∗ ◦ C

Pentabromotoluene [87-83-2] 82 280 220

Pentabromophenylallyl ether [3555-11-1] 76 163 190
Pentabromoethylbenzene [85-22-3] 80 136 231
Decabromodiphenyl [13654-09-6] 84 375 330
Pentabromodiphenyl oxide [32534-81-9] 71 260
Octabromodiphenyl oxide [32536-52-0] 79 70 – 150 322
Decabromodiphenyl oxide [1163-19-5] 83 300 – 310 365
Ethylene bis(tetrabromophthalimide) [32588-76-4] 67 445 450
Tetradecabromodiphenoxybenzene [58965-66-5] 82 370 420

∗ TgA = thermogravimetric analysis.

Mobay Multranol 4034 18.6 wt %

Saytex RB-79 flame retardant 28.0 wt %
phases. The reaction between bisphenol A
Dow Corning 193 surfactant 0.7 wt % [80-05-7] and phosgene [75-44-5] is as follows:
Abbott Labs Polycat 8 0.7 wt %
DuPont Freon 11 13.0 wt %
Upjohn PAPI 135 39.0 wt %
Isocyanate index 110.0
Bromine 14.0 wt %
ASTM E 84 test
Thickness 5.1 cm 10.2 cm
Flame spread index 25.0 25.0
Smoke density 135.0 65.0

Manufacturers of foam may make their own A reactive flame-retarded polycarbonate is

formulation or may purchase preformulated produced by substituting tetrabromobisphe-
packaged systems, which come in two or three nol A [79-94-7] or another halogenated biphe-
parts. One part is usually polymeric isocyanate. nol for some of the bisphenol A.
A second part contains polyol or a polyol mix-
ture, water, flame retardant, silicone surfactant, Unsaturated Polyesters [11]. Polyesters are
catalyst, and a blowing agent. Special catalysts produced by reacting glycols with organic acids.
may be supplied as a third part. Typical ingredients are ethylene and propylene
High-speed, high-intensity mixers are used glycols and phthalic or maleic anhydride. Acid
to ensure adequate mixing. Reaction takes anhydrides are preferred because they generate
place between hydroxyl groups and isocyanate only half as much water of reaction as the cor-
groups: responding diacid. Esterification catalysts, such
as p-toluenesulfonic acid or titanium complexes,
are often used.
Unsaturated polyesters contain maleic anhy-
dride or tetrahydrophthalic anhydride, which re-
sults in aliphatic unsaturation of the backbone.
These polyesters are capable of further cross-
As the complex structure begins to form, heat linking with styrene, divinylbenzene, or another
is generated, the fluorocarbon blowing agent vinyl monomer to produce highly rigid, complex
volatilizes, and the foam rises. Cross-linking oc- networks. The styrene – unsaturated polyester
curs between the active hydrogens of the carba- systems are usually further reinforced with fiber-
mate groups with additional isocyanate. glass to produce a wide range of products from
bathtubs to boats.
Polycarbonates are produced in complex When flame retardation is required, halogens,
systems containing both aqueous and organic most often chlorine or bromine, are selected. The
halogen is introduced in several ways:
 Flame Retardants 9
Table 2. Formulation of two typical flame-retardant unsaturated Table 3. Formulation of a flame-retardant unsaturated polyester
polyesters containing tetrabromophthalic anhydride containing dibromoneopentyl glycol

Component mol mol Component mol

Tetrabromophthalic anhydride 0.40 0.73 Part A ∗

Phthalic anhydride 0.60 0.27 Maleic anhydride 1.9
Maleic anhydride 1.00 1.00 Phthalic anhydride 1.9
Ethylene glycol 2.06 Dibromoneopentyl glycol 4.0
Propylene glycol 2.06 Part B ∗
% Bromine 18.0 25.0 Maleic anhydride 4.5
Oxygen index 34.3 34.0 Phthalic anhydride 4.5
Propylene glycol 10.0

∗ Part A contains 30 wt % bromine and part B contains no

bromine; the two parts are mixed to achieve 21 wt % bromine.

1) Direct bromination of the unsaturated organic halides can adversely affect electrical
aliphatic polyesters (Koppers Dion resins) properties in finished epoxy resin–glass fiber
2) Dibromoneopentyl glycol [3296-90-0] as a printed circuit boards. Organic halides that are
replacement for ethylene or propylene gly- readily hydrolyzed by mild alkali can interfere
cols (Dow Chemical FR-1138 or Dead Sea with the rate and extent of cure. Most epoxy
Bromine FR-522) resin manufacturers stress consistency of both
3) Hydroxyethylated tetrabromobisphenol A hydrolyzable and ionic halides so that users need
[4162-45-2] as a replacement for a portion not make changes in their formulation or opera-
of the glycols tion.
4) Tetrabromophthalic anhydride as a replace- Table 4. Formulation of a low-bromine flame-retardant epoxy resin
ment for a portion of the phthalic anhydride
(Ethyl Saytex RB-49 flame retardant or Great Component parts by wt
Lakes Chemical PHT-4) Solution A
5) Chlorendic anhydride [115-27-5] (Velsicol Shell Epon 828 resin 64.57
Chemical Co.) as a replacement for a portion Saytex RB-100 35.43
Triphenyl phosphine 0.20
of the phthalic anhydride Acetone 25.00
6) Tetrachlorophthalic anhydride [117-08-8] Solution B ∗
Resin solution A 125.20
(Monsanto Tetraphthal) as a replacement for Dicyandiamide 2.90
a portion of the phthalic anhydride Benzyldimethylamine 0.20
Acetone or methyl cellosolve 75.00
7) Diallyl tetrabromophthalate [49693-09-6] to
replace some or all of the cross-linking ∗ Solution B is used to make the glass laminates.
styrene
8) Halogenated styrene of divinylbenzene to re- Flame-retarded epoxy resins are made by us-
place some or all of the cross-linking styrene ing tetrabromobisphenol A to partially or almost
Cost and product performance are the con- totally replace the bisphenol A. These resins
trolling variables in selecting the flame retar- contain either 20 or 40 wt % bromine and are
dant. Typical formulations containing tetrabro- referred to as low bromine and high bromine,
mophthalic anhydride or dibromoneopentyl gly- respectively. The choice of which resin to use
col [11] are shown in Tables 2 and 3. is based on the flame-retardant requirements of
the printed circuit board or other application.
Epoxy Resins. Epoxy resins are produced Typical FR-4 board manufacture. Printed cir-
from the reaction of bisphenol A and epichloro- cuit board stock is manufactured from catalyzed
hydrin (→ Epoxy Resins). Reaction conditions epoxy resins and glass cloth. The resin is applied
are chosen carefully to ensure consistency of ep- in an impregnating bath. Partial curing or B stag-
oxide concentration in the resin. Of particular ing occurs so that the glass cloth can be handled
concern are trace impurities, such as inorganic but is not too tacky or sticky. Multilayers of the
halides, that remain in the finished product. In- B-staged cloth and copper foil are placed in a
10 Flame Retardants

curing press, and the lamination is then formed and the end-use requirements [12–17]. Com-
and cured (→ Epoxy Resins, Chap. 4.2.1.). binations of chain-stiffening and plasticizing
A typical low-bromine epoxy resin formula- flame retardants to achieve an optimum balance
tion is given in Table 4. of properties in thermoplastics have been de-
Printed circuit boards are also made with scribed [16], [17].
polyester or phenolic resins. The polyester The major emphasis in this section is on ad-
boards are based on brominated resins with ditives used in conjunction with thermoplastics.
antimony oxide synergist. Phenolic boards of- Instead of the reactive flame retardants discussed
ten contain brominated diphenyl oxides and in Section 4.2, additives may be used in the same
occasionally a phosphate plasticizer or diami- polymer systems as follows:
nodiphenylsulfone.
1) polyurethane foams – organophosphates,
Halogenated monomers , if available, can brominated organics, alumina trihydrate
be used to make inherently flame-retarded 2) polycarbonates – brominated organic
polymers, such as vinyl chloride [75-01-4] in oligomers, sulfonate salts
poly(vinyl chloride) or ethylene – vinyl chlo- 3) unsaturated polyesters – brominated organ-
ride copolymers. Vinylidene chloride [75-35-4] ics, alumina trihydrate
resins are also inherently flame-retardant. Vinyl 4) epoxy resins – brominated organics
bromide [593-60-2] is copolymerized with
acrylic monomers in flame-retardant carpet fiber Laboratory Compounding [1], [18], [19].
applications. The equipment used for laboratory compound-
Halogenated styrene monomers have been in- ing of thermoplastics, such as polyolefins,
vestigated to find compounds having high halo- styrenics, and polyesters, depends on the char-
gen content, adequate storage stability, and a sat- acteristics of the polymer, flame retardant, and
isfactory reaction rate. Although development other additives.
quantities of both chloro- and bromostyrenes are Typically the polymer is fluxed, masticated,
available, none have achieved commercial suc- or otherwise prepared for acceptance of the
cess. flame retardant mixture. When both halogenated
Acrylic or allylic monomers with pendant flame retardant and antimony oxide are used,
tribromophenol [118-79-6] or pentabromophe- they are preblended and added to the fluxed poly-
nol [608-71-9] groups are also available. These mer. In general, the procedures and equipment
can be either co- or homopolymerized. The for thermoplastics are also used for thermoplas-
homopolymer itself can be used as a flame tic or thermosetting elastomeric polymers.
retardant. Two examples of polymeric or Three types of laboratory equipment are em-
oligomeric flame retardants from halogenated ployed:
monomers are poly(dibromophenylene oxide) The laboratory Brabender Plasticorder
[26023-27-8] (Great Lakes PO-64P), made has two counter-rotating, intermeshing, shear
from 2,4,6-tribromophenol [118-79-6]; and kneading rollers that masticate the polymer.
poly(pentabromobenzyl)acrylate [59447-57-3] Heat is provided electrically.
(Dead Sea FR-1025), made from pentabromo- A typical compounding mill has two counter-
benzyl bromide [38521-51-6]. rotating chrome-plated steel rolls, which run at
Glycidyl derivatives of brominated phenols different speeds to increase shearing and mixing,
have also been manufactured and have many and can be individually heated or cooled.
uses. The Haake compounding twin-screw ex-
truder has two intermeshing screws and a single
drive. More complex equipment has indepen-
dent drives with either concurrent or counter-
4.3. Formulation with Additive Flame
current rotation. Heat is varied along the barrel
Retardants to increase or reduce melt viscosity and shear.
Some equipment has an individual port along
Compounds and formulations with additive the barrel for addition of various ingredients or
flame retardants depend on the polymer matrix for venting off-gas.
 Flame Retardants 11
Table 5. Thermoplastics processing temperatures

Polymer Operating temperature, ◦ C

Brabender Mill Extruder

Acrylonitrile – butadiene – styrene 175 170 170

Polystyrene (high-impact) 190 175 175 – 200
Polypropylene 175 210 175 – 200
Polyethylene (low-density) 120 140
Polyethylene (high-density) 175 165 175 – 200
Polyamide 260 260 – 270
Poly(butylene terephthalate) 270 240 – 260
Poly(ethylene terephthalate) 270 240 – 260

Operating temperatures for the three types of tance, whereas low-melting flame retardants re-
plastics compounding equipment are shown for duce thermal deformation resistance. Flexural
a variety of polymers in Table 5. strength and tensile strength are increased with
Once the plastic mass has been well com- high-melting flame retardants, but percent elon-
pounded, finished plaques for further testing gation is reduced. Table 7 shows the wide di-
are formed by compression molding in standard vergence in some physical properties attainable
heated presses or by injection molding. Molding in an acrylonitrile – butadiene – styrene polymer
conditions for some thermoplastics are shown in with five flame retardants [8].
Table 6. Chlorine and bromine flame-retardant com-
Table 6. Thermoplastics injection molding
pounds have been compared in wire and cable
compositions [18]; retardants for thermoplastic
Temperature, Pressure,
◦
polyurethanes have been described [19]. Differ-
C MPa
ences in flame retardation were observed bet-
Polyethylene 190 – 260 3.6 – 3.8 ween ester and ether polyurethanes.
Polypropylene 230 – 275 3.6 – 3.8
Poly(vinyl chloride) 175 – 200 3.4 – 3.8
Polystyrene (crystalline) 220 – 260 4.0 – 4.1
Commercial Compounding. Commercial
Polystyrene (high-impact) 205 – 230 4.0 – 4.1 equipment varies only slightly from the labo-
Acrylonitrile – butadiene – styrene 220 – 260 3.6 – 4.1 ratory counterparts. Mills are larger or contain
Poly(ethylene terephthalate) (glass filled) 235 – 275 3.6 – 4.1
Poly(butylene terephthalate) (glass filled) 230 – 275 3.8 – 4.1 three rolls rather than two. Extruders are also
Polyamide 6 and Polyamide 66 (natural 275 – 295 3.4 – 3.6 larger.
resin only)
Polycarbonate (natural resin only) 260 – 295 3.4 – 3.6
In place of the Brabender, commercial facili-
ties use Banburys with various designs of knead-
ing devices. The Farrel continuous mixer (FCM,
Test specimens are evaluated for flame retar- Farrel Manufacturing Co.) combines some of the
dation and for other physical properties. These features of both a Banbury and an extruder. The
tests are also used in thermoplastic or thermo- FCM has two counter-rotating mixing motors
setting systems based on reactive flame retar- similar to a Banbury. The ends of the rotors are
dants. Typical property tests are extended with screw flights evolving into a me-
tering twin-screw extruder. The plastic is con-
Heat distortion temperature ASTM D 648 tinuously extruded through a pelletizer die.
Vicat softening point ASTM D 1525
Izod impact strength ASTM D 256 The producer of a television set, for exam-
Dart drop resistance ASTM D 1709 ple, purchases a molded cabinet from a custom
Tensile – elongation ASTM D 638
Flexural strength ASTM D 790 molder. The molder purchases plastic pellets
from a manufacturer who warrants that the plas-
tic meets a UL 94 V-0 rating. The pellet manu-
In almost all cases, flame-retardant addi-
facturer has the following two options:
tives reduce the impact strength of virgin poly-
mers. Very high-melting or reinforcing flame 1) Mix base resin with flame retardant and anti-
retardants increase thermal deformation resis- mony oxide and make a finished compound
in pellet form.
12 Flame Retardants
Table 7. Properties of flame-retardant acrylonitrile – butadiene – styrene polymers

Neat resin DBDPOa OBDPOb TDBDPBc TBBPAd HBDPEe

Oxygen index 18.4 27.1 28.3 31.2 33.7 25.8

UL 94 (0.32 cmf ) burn V-0 V-0 V-0 V-0 V-0
(0.16 cmf ) burn V-0 burn V-0 V-0 burn
Tensile strength, MPa 36 40 44 39 33 40
Flexural modulus, GPa 2.2 1.7 2.0 2.3 2.7 2.0
Vicat softening point (0.32 cmf ), ◦ C 100 102 97 102 85 96
Izod impact strength (0.32 cmf ), J/m 34.3 6.9 13.7 5.9 4.9 12.8
a
Decabromodiphenyl oxide.
b
Octabromodiphenyl oxide.
c
Tetradecabromodiphenoxybenzene.
d
Tetrabromobisphenol A.
e
Bis(tribromophenoxy)ethane.
f
Sample thickness.

2) Mix base resin with a premixed concen- melamines produce a V-0 rating at 24 – 40 parts
trate of flame retardant and antimony oxide per 100 of polymer; V-0 is also achievable with
purchased from a concentrate manufacturer. 40 – 80 parts of aluminum oxide trihydrate or
These concentrates, which can contain up magnesium hydroxide (hydrated magnesia).
to 90 wt % of active material with 10 wt % Glass-reinforced (30 wt %) poly(buylene
binder, are “let down” with base resin to the terephthalate) (PBT) or poly(ethylene tereph-
desired level of active ingredient in the fin- thalate) (PET) :
ished compound. several products are used commercially
Although individual manufacturers are the such as tribrominated polystyrene (Ferro Py-
best source of specific formulation information, rochek 68PB) [57137-10-7], polycarbonate
following are some typical flame-retardant sys- oligomers of tetrabromobisphenol A (Great
tems for various thermoplastics. All are based on Lakes Chemical BC-52 [28906-13-0] or BC-
100 parts of original base polymer. Unless other- 58 [71342-77-3] ), poly(dibromophenylene
wise indicated, the formulations give UL 94 V-0 oxide) (Great Lakes Chemical PO64P),
compositions of 0.32 cm thickness. decabromodiphenyl oxide or ethylene
High-impact polystyrene: 14 parts decabro- bis(tetrabromophthalimide) (EthylSaytex BT-
modiphenyl oxide with 4.75 parts of antimony 93 flame retardant). From 6 to 8 wt % aromatic
oxide. bromine with 3 – 5 parts of antimony oxide are
Acrylonitrile – butadiene – styrene (ABS): used. Actual levels of the flame-retardant com-
A total of 23 parts of octabromodiphenyl ox- pound itself are adjusted on the basis of its
ide [32536-52-0] with 5 parts of antimony ox- individual bromine content. The ratio of bromi-
ide, or 34 parts of tetrabromobisphenol A and nated compound to antimony oxide is generally
8.6 parts of antimony oxide. 2 – 3 : 1. However, in countries such as the Peo-
Polypropylene: ple’s Republic of China, where antimony oxide
A total of 4 parts of ethylene bis(5,6- is plentiful, economics often dictate the ratio of
dibromonorbornane-2,3-dicarboximide) (Ethyl materials, with the result that more antimony
Saytex BN-451 flame retardant) [41291-34-3], oxide is used.
or bis(2,3-dibromopropyl ether)tetrabromo- Systems not containing glassrequire a higher
bisphenol S (Great Lakes Chemical PE68) amount of flame retardant. Levels are increased
[21850-44-2], or bis(2,3-dibromopropyl ether) to 10 – 14 % of contained bromine and 4 – 8 parts
tetrabromobisphenol S (Marubishi Non-Nen 52) of antimony oxide.
[42756-55-1] with 2 parts of antimony oxide Low-density polystyrene foam:
produces UL 94 V-2 formulations. Ten parts of A total of 1 – 2 parts of hexabromocy-
Non-Nen 52 with four parts of antimony ox- clododecane [3194-55-6], pentabromomono-
ide produces a V-0. Intumescent formulations chlorocyclohexane (Dow Chemical 651P)
based on pentaerythritol, phosphorus donor, and [87-84-3], and dibromoethyldibromocyclo-
 Flame Retardants 13

hexane (Ethyl Saytex BCL-462 flame retardant) dants are most often applied to the paper in a
[3322-93-8] are adequate to produce foam that saturation or coating operation.
meets building code requirements in the United
States; UL 94 values on these foams are not
significant. 4.4. Interactions between Flame
Poly(phenylene oxide) high-impact polystyrene Retardants and Other Formulation
blends:
Ingredients
A total of 15 – 20 parts of an aromatic phos-
phate, such as triphenylphosphate [115-86-6], in
Fillers. Calcium carbonate can interfere with
nominal 50 : 50 blends of the two polymers.
the flame-retardant action of halogenated flame
In addition to their use in plastics, flame re-
retardants because it absorbs and neutralizes
tardants are also necessary in other polymer sys-
HCl or HBr. Carbon blacks, with high levels
tems, such as elastomers, textiles, paints, paper,
of residual oils on their surface, make flame re-
and coatings. Where processing temperatures or
tarding difficult in any system. Fine-particle col-
environmental exposure requirements are not se-
loidal silica used to minimize dripping in flame-
vere, chlorinated alkanes can economically re-
retarded thermoplastics also contributes to in-
place brominated organics. Where mass per unit
creased flammability because of its high surface
volume or physical properties are not critical,
area.
aluminum oxide trihydrate or other fillers can
When high loadings or fillers are used, disper-
replace more expensive flame retardants.
sion is difficult and the effect on polymer phys-
ical properties is significant. Fillers with sur-
Commercial applications of the flame re- face treatments of organotitanate or organosil-
tardant are a function of end-use requirements. icon coupling agents are useful to overcome the
For example, flame retardants can be made an dispersion and physical property loss problems.
integral part of a polypropylene upholstery or In some instances flame retardance has been im-
carpet fiber through melt processing or can be proved because of the addition of a coupling
applied to the finished fabric as a back coating. agent.
In the former case, the retardant must be fluid Some evidence even suggests that aluminum
at the spinning temperature or be a fine, uni- oxide trihydrate or magnesium hydroxide at low
form particle size powder. Either a liquid or solid loadings can act synergistically with halogen an-
flame retardant can be used for back coating; timony oxide systems.
decabromodiphenyl oxide dispersed in a latex
binder system is used widely for polypropylene
Colorants. Some inorganic cadmium and
drapery or upholstery fabric.
zinc pigments are deleterious to flame retarda-
Clothing has also been treated for flame re-
tion. The mechanism for this phenomenon is un-
tardation with a variety of halogen- and phos-
known.
phorus-containing materials. Of particular con-
cern are the effects of the chemicals on di-
Thermal Stabilizers and Processing Aids.
rect skin contact. Durability to washing and dry
Zinc-based processing aids can cause discol-
cleaning are also critical factors. Finally, the
oration of a polymer matrix when used in com-
flame retardant must not affect the fabric color
bination with halogenated materials. Calcium
or feel. In most cases, proprietary formulations,
stearates are generally used when this prob-
which are specific for fiber content, have been
lem occurs. Depolymerization of styrenic poly-
developed. Testing of flame-retarded fabrics is
mers caused by some halogenated flame retar-
by both horizontal and vertical procedures.
dants during polymer processing can be mini-
Paper is also flame-retarded. Typical non-
mized by organotin systems. These systems also
durable systems are based on inorganic salts,
usually contain complex phenolic antioxidants,
such as ammonium phosphates and sodium bo-
such as Irganox 1010 (Ciba-Geigy) [6683-19-8],
rates. More durable flame retardants are based
Ethanox 330 (Ethyl) [1709-70-2], and occasion-
on chlorine-containing emulsion polymers syn-
ally thiols.
ergized with antimony oxide. The flame retar-
14 Flame Retardants

Synergists [20]. Tin compounds are effec- aliphatic halogen compound was improved with
tive synergistic agents as partial or total replace- benzotriazoles. Hindered amines were effective
ments for antimony oxide [21]. A total flame when combined with benzotriazoles.
retardant for polypropylene is reported to con- Flame retardants that are stable to UV light
tain 32 % bromine, 1 % phosphorus, and 1.5 % have been developed. However, the most de-
tin. manding applications require additional UV sta-
Phosphites can act synergistically with cer- bilizers. The UV stability of brominated flame
tain brominated flame retardants in the absence retardants has been rated as follows [8]:
of antimony oxide. In other systems containing
antimony oxide, loss of flame retardation has 1) brominated diphenyl oxides: poor
been observed with phosphites. 2) bis(tribromophenoxy)ethane (Great Lakes
Peroxide-producing chemicals, such as 2,3- Chemical FF680) [37853-59-1]: good
dimethyl-2,3-diphenylbutane [1889-67-4], can 3) ethylene bis(tetrabromophthalimide) (Ethyl
be used in combination with aliphatic or cy- Saytex BT-93 flame retardant): excellent
cloaliphatic bromine compounds in styrenic
polymers. Additive levels of the bromine can
sometimes be significantly reduced by as much
as 50 % in polystyrene foam manufacture. 4.5. Formulation to Reduce Smoke
Combinations of zinc borate [12536-65-1]
and antimony oxide mixed with de- All burning materials generate smoke as a result
cabromodiphenyl oxide or ethylene of incomplete combustion. Styrenic polymers
bis(tetrabromophthalimide) are used in wire and polyurethanes, for example, produce thick
and cable formulations based on thermoplastic black, carbonaceous, sooty smoke. Flame retar-
styrene – butadiene copolymers. Higher oxygen dants that interfere with the normal combustion
indices are obtained with these mixtures than process change the rate of smoke evolution and
with antimony oxide alone. the amount and composition of the smoke. Less
smoke allows individuals more time to safely
Ultraviolet Light Stabilizers and Antiox- exit from confined areas.
idants (→ Antioxidants, Chap. 5.4.), [22–24]. Much of the development work on smoke
Each polymer system with its flame retardant suppression has been done with poly(vinyl chlo-
is unique and requires a specific stabilization ride). Zinc borate reduces smoke and can be
package. What is acceptable in high impact used as a partial replacement for antimony oxide
polystyrene or ABS may be totally ineffective in in some formulations. Molybdenum compounds
alloys or blends of these substances with other are also used in PVC formulations.
polymers. Unfortunately, PVC smoke reduction tech-
Consistency of color under exposure to ultra- nology has had limited success in other poly-
violet or fluorescent light has become a critical mers. Molybdenum compounds do function in
issue in business machines and other plastic cab- unsaturated polyesters, however.
inetry. It is equally important in fabrics, paints, Iron compounds, such as ferrocene (Ara-
and coatings. pahoe DFR-121) [102-54-5], have been used
Impact polystyrene containing an aromatic in poly(vinyl chloride) and polyurethanes. Iron
bromine or an aliphatic bromine – chlorine com- compounds have also been reported to reduce
pound has been studied with a wide range of smoke in polyamide formulations that contain
light stabilizers in combination with antioxi- chlorinated organic flame retardants and anti-
dants [22], [23]. In all cases, the flame-retarded mony oxide.
impact polystyrene had poorer light stability Other metals, such as lead or bismuth,
than the polymer alone. have had limited applications as have quinoline
Benzotriazoles combined with hindered phe- [91-22-5] and phthalocyanine complexes. Typ-
nolic antioxidants were most effective with aro- ically from 0.5 to 6 parts of smoke suppressant
matic bromine-based flame retardants. Further per 100 parts of polymer are used.
color improvement was obtained by adding Smoke from halogen – antimony oxide for-
an epoxy novolac. The system containing an mulations can be eliminated by using other flame
 Flame Retardants 15

retardants. Aluminum oxide trihydrate and mag- in consumption of flame-retardant chemicals in

nesium hydroxide do not generate smoke. In- Western Europe from 1985 to 1992 is shown in
tumescing systems based on pentaerythritol, a Table 9 [32]. The Japanese market for flame re-
phosphorus donor, and melamine also do not tardant chemicals was estimated to be 80×103 t
materially contribute to smoke. in 1984. Japan is the predominant consumer in
the Far East, although Taiwan, Korea, and the
Measurement of Smoke Evolution [21], People’s Republic of China are growing users.
[25], [26]. Smoke is measured peripherally to There are smaller users in South America and
flammability in some tests, such as ASTM E 84, South Africa.
and independently in others. Smoke measure- Table 8. Consumption of flame retardants by type ∗ [27]
ment testing by small-scale laboratory tech-
niques and full-scale experiments has been re- Type of flame retardant U.S. consumption, 103 t
viewed [21]. 1984 1985
Little correlation between test methods was
observed, as each initiates combustion with dif- Additives
Aluminum oxide trihydrates 91.8 93.7
ferent energy input and either a fixed volume or Antimony oxides 15.0 15.9
moving air stream. Some protocols include ei- Boron compounds 5.0 5.0
Bromine compounds 15.0 16.9
ther a radiant energy source or a flaming source Chlorinated alkanes 15.0 13.0
as the combustion initiator. Most are based on and cycloaliphatics
some form of visual observation; however, the Phosphate esters
Nonhalogenated 16.9 17.0
Arapahoe smoke test (ASTM D 4100) rates ma- Halogenated 11.0 11.0
terials by mass transfer per unit time from the Others ∗∗ 8.0 8.1
Total 177.7 180.6
specimen to a collecting filter. Reactives
Smoke measuring devices and smoke reduc- Epoxy resin intermediates 11.0 10.0
tion techniques in olefin polymers have been Polycarbonate intermediates 3.0 3.0
Polyester intermediates 5.0 5.9
studied [25]. Urethane intermediates
The most widely used device in the United Flexible foam 1.0 1.0
Rigid foam 4.0 4.0
States is the National Bureau of Standards Others 4.0 4.0
Chamber (ASTM E 662). The chamber is shown Total 28.0 27.9
in Figure 4. Grand total 205.7 208.5
The Ohio State University release rate appa-
ratus is gaining acceptance. This device moni- ∗ Include secondary plasticizers with flame retardant
functionality.
tors smoke continuously as it exits the apparatus. ∗∗ Include molybdenum, zinc, and metal oxides.
Since air flow rates can be varied, actual fire sit-
uations can be simulated more closely than with
Electronic, electrical [29], and construction
the fixed-volume, static ASTM E 662 procedure.
[30] applications use the bulk of flame retar-
Flame retardants that reduced smoke levels sig-
dants. Wire and cable applications represent a
nificantly have been found using the device [24].
significant specialty subset of electronics and
electrical [31].
The Fire Retardant Chemicals Association,
5. Flame Retardant Markets [27–32] with headquarters in Lancaster, Pennsylvania,
Modern Plastics magazine publishes an annual was formed to allow a common forum for dis-
listing of the major classes of flame retardants cussion and interchange on matters of concern
in the United States [27]. Included in the article to manufacturers and users of flame retardants.
are new products that have appeared in the trade Listings of suppliers of flame retardants in the
press. Table 8 is the September, 1985 list of ma- United States are given in the SRI report [28],
jor flame-retardant types and their consumption. and lists of suppliers on a worldwide basis in-
Flame retardants in the United States were cluding the United States, Europe, and Japan are
the subject of studies by SRI International [28]. available [2].
Updates appear in SRI’s tabulations of plastics Markets for flame retardants were developed
additives and specialty chemicals. The growth after governmental regulatory action; loss of life
16 Flame Retardants

Figure 4. National Bureau of Standards (NBS) smoke chamber, ASTM E 662 [7, pp. 394, 395]
A) View of chamber: a) Door with glass window; b) Blow-out panel; c) Controls and measuring instruments; d) Photometer;
e) Window for optical system; f) Test chamber; g) Photodetector housing
B) Operational schematic: a) Light source; b) Light beam; c) Photodetector; d) Photometer; e) Infrared radiator; f) Specimen;
g) Trough for specimen melt; h) Six-tube burner

and property because of fire resulted in pub- tors) must meet flammability standards. Printed
lic pressure to provide “safer materials.” Insur- circuit boards and internal wires are also pro-
ance companies also exerted pressure by in- cessed with flame retardants.
creasing payment rates in unprotected environ- All commercial wires and cables along with
ments. Pressure still exists for improved prod- connectors, plugs, and spacers are treated with
ucts with lower levels of smoke and with reduced flame retardants.
toxicity of the combustion products.
Construction. Thermal insulating materials
Table 9. Estimated West European consumption of flame-retardant
chemicals are flame retardant. Molded fiberglass units to
be used as tubs and shower stalls must meet
Product group Consumption, 103 t
flammability standards. Institutional mattresses
1985 1992 represent a specific use of flame retardants. Fur-
Polystyrene 4.0 – 4.5 4.5 – 5.0
niture cushioning of all types is under active
ABS 1.0 – 1.5 1.2 – 1.8 flame retardant development.
Polyesters 7.5 – 8.0 8.5 – 9.0
Epoxy resins 3.5 – 4.0 4.0 – 4.5
Polyolefins 10.0 – 12.0 11.0 – 13.0 Transportation. Polymer components in-
Poly(vinyl chloride) 25.0 – 27.0 27.0 – 29.0 side mass transit vehicles (airplanes, buses, and
Polyurethanes 12.0 – 13.5 13.5 – 15.0
Engineering plastics 1.5 – 1.8 1.7 – 2.0
subways) must meet flammability standards.
Paper and textiles 9.0 – 10.0 10.0 – 11.0 Most polymeric materials in private automobiles
Rubber and elastomers 5.0 – 6.0 6.0 – 7.0 are flame-retardant, but comply with different
Other 11.5 – 11.7 12.6 – 12.7
Total 90.0 – 100.0 100.0 – 110.0 flammability standards than mass transit vehi-
cles. Smoke and toxic gas generation from burn-
ing vehicle interiors are a significant concern in
restricting free exit. Seating material is a major
Electrical and Electronic Applications. problem because of its total mass in the vehicle
Cabinets and housings for television sets and the and accessibility to accidental or deliberately set
polymeric components in the sets (e.g., connec- fires.
 Flame Retardants 17

Fabrics and Apparel. Children’s sleepwear other aspects of a material’s performance, not in-
is subjected to flammability standards, as is dependently. Resistance to ignition, reduction in
workers’ clothing in specific industries. Car- the rate or extent of flame spread, and minimiza-
pets and draperies are treated with flame re- tion of smoke evolution are all effects produced
tardants. Military fabrics, such as tenting, are by flame retardants, which result in the saving of
flame-retardant. life and property. Combustion toxicity should be
included in an overall hazard index with proper
emphasis on other protection benefits.
6. Toxicology Currently, an accepted standard method for
measuring combustion toxicology does not ex-
Regulatory Influences. The development ist. More work is needed in evaluating laboratory
and introduction of new materials are becoming tests before material-restricting regulations can
complex. Information is required by regulatory be formulated on the basis of the test results [33].
agencies on the health, safety, and disposal of the Material design with total fire safety in mind is
product and on its raw materials and byproducts. essential [34].
Often, expensive and lengthy toxicology test- Time and concentration factors in combus-
ing is required prior to commercialization. This tion toxicology have been evaluated [34]. Both
testing can include developmental toxicology, are important in determining short- and long-
as well as teratology. term toxicologic effects. Because fires are dy-
Workers are becoming more concerned with namic, both time and concentration of various
the long-term safety and health effects of toxicant gases change. Reducing this complex
the chemicals they handle and use. Tris(2,3- situation to laboratory testing of relatively pure
dibromopropylphosphate) [126-72-7] has been substances is a difficult, if not impossible, task.
banned for use in children’s sleepwear, but other Some chair-seat cushioning material pro-
uses have not been banned in the United States. duces more toxic gases under smoldering ig-
The Federal Republic of Germany is evaluating nition than others [35]. The toxicologic effects
legislation that would restrict the use of chemi- of thermoplastics have been compared at nor-
cals containing or generating chlorinated diben- mal processing temperatures and above [36]. At
zoparadioxins. The Japanese Ministries require some elevated temperatures, Douglas fir had a
detailed testing on the effects of chemicals on higher irritation potency than many of the plas-
various fish species. tics although the effect was more transitory.
The regulatory climate and its cost will hinder Large amounts of carbon monoxide were liber-
development of new materials and will empha- ated from commercial plastics formulations with
size compounding already existing products as and without a flame retardant at temperatures
much as possible. significantly above normal processing tempera-
tures.
Toxic Products of Combustion [32–36]. Several states in the United States are review-
When materials burn, they liberate both gaseous ing toxicity of products of combustion data to
and solid combustion productions. Inhalation of determine whether or not regulatory action is
these decomposition products can cause both required. Political activists in the Federal Re-
short-term and long-term effects. Flame retar- public of Germany are pressing for a ban on cer-
dants alter the combustion process so that the tain flame retardants because they produce toxic
decomposition products are different from non- combustion products.
flame-retarded materials. The entire process
is dynamic, with the composition of liberated
gases varying with time. 7. Future Directions in
The evaluation of the toxic effects of com- Flame Retardants
bustion products has only recently received sig-
nificant attention. Toxicity of combustion prod- New Market Requirements. Flame retar-
ucts is important with materials exposed to fire, dants are used only when this is required by
but the situation should be viewed together with the marketplace. Market changes can increase
18 Flame Retardants

or decrease the usage of flame retardants. Al- for Polypropylene, 2nd International Flame
though few regulations exist in South America, Retardants Symposium, London 1985, pp. 2/1.
multinational companies producing subassem- 2. Herbert Jenkner in R. Gachter, H. Muller
blies for the United States, Japanese, or Eu- (eds.): “Flame Retardants for Thermoplastics.”
ropean markets meet the importing country’s Plastics Additives Handbook, Hanser
flame retardant requirements. To ease inventory Publishers, München p. 535.
and production problems, the same companies 3. Irv Touval, Plast. Compd. 1982, (Sept. – Oct.)
make flame retardant assemblies for domestic 31.
4. Ethyl Corp., US 4 476 268, 1984 (H. J. Barda,
consumption.
S. Hussain)
Polyurethane and polystyrene foams are ef- 5. Ethyl Corp., US 4 476 267, 1983 (H. J. Barda,
ficient thermal insulators per unit thickness, but S. Hussain)
are more combustible than traditional materials, 6. Reference I, O. Cichetti, R. Fontanelli, A.
such as rock wool or fiberglass. Flame retardants Pagliavi: “Advances in the Field of
are required, therefore, as these materials replace Intumescent Halogen-Free FRs for Polymers,
conventional insulation. Other polymer foams pp. 13/1.
(isocyanurate and phenolic) have inherent flame 7. J. Troitzch: International Plastics
retardance but are deficient in physical proper- Flammability Handbook, Hanser Publishers,
ties. Munich 1983, Chapter 7.
Glass fiber reinforced epoxy printed circuit 8. Reference I, B. J. Sutker, C. J. Abbott:
boards and phenolic paper boards are flame re- “Evolution of Aromatic Flame Retardants,”
tarded. These low-cost mass-produced articles pp. 5/1.
have been used widely. Developments in flexi- 9. D. P. Miller, Plast. Eng. 1980, (Feb.) 29.
ble circuitry and molded circuits have overcome 10. R. C. Nametz, Plast. Compd. 1984,
the rigidity of previous materials. Many high- (Sept. – Oct.) 54.
performance polymers (e.g., polyimides) used 11. E. R. Larsen, W. C. Weaver: “FR-1138
Dibromoneopentyl Glycol-Based Unsaturated
in newer circuits are inherently flame retardant.
Polyesters: Preparation and Evaluation. Proc.
28th Annual Technical Conference, Reinforced
Specification Changes. Electronic cabi- Plastics/Composites Institute, Soc. of the
netry is almost exclusively rated UL 94 V-0, Plastics Industry, Washington, D.C., 1973,
with some rated UL 94 V-2. This evolved from sec. 2 – A, p. 1.
electron-tube-powered television sets, where 12. N. Albee, Plast. Compd. 1981, (Jul. – Aug.) 89.
heat evolution from the tubes could result in 13. N. Albee, Plast. Compd. 1981, (Sept. – Oct.)
fire. With the advent of transistorized circuitry 95.
with little heat output, no commensurate change 14. J. P. Hamilton, Plast. Compd. 1978,
was made in the flammability test requirement. (Sept. – Oct.) 54
An effort is under way to modify the internal 15. R. C. Nametz, Plast. Compd. 1979, (Jan./Feb.)
configuration of electronic components, shield 31.
them, and thus totally eliminate the possibility 16. E. P. Chang, J. Appl. Polym. Sci. 21 (1977)
of their causing plastics ignition. If the rating 937.
does change, the need for flame retardants would 17. E. P. Chang, J. Appl. Polym. Sci. 21 (1977)
be reduced or eliminated. 2167.
On the other hand, institutional bedding and 18. J. M. Lesniewski: “Comparison of the
Relative Cost Effectiveness of Brominated and
mass transit vehicles are developing more strin-
Chlorinated Flame Retardants in EPDM,”
gent requirements for flame retardants. The ef-
Proc. Symp. International Wire and Cable,
fort to thwart damage results from purposeful 1980, Cherry Hill, N.J., p. 90.
and accidental ignition. 19. J. Sutker, S. Walter, J. Fire Sci. 1 1983,
(Jan./Feb.) 66.
20. “Tin Chemicals Fight Fire, Tin and its Uses”
8. References International Tin Research Institute,
Middlesex, England, 1985 p. 146.
1. G. E. Bowen: Magnesium Hydroxide: A 21. J. G. Quintiere, Fire Mater. 6 (1982) no. 3, 4,
Halogen-Free Flame and Smoke Suppressant 145.
 Flame Retardants 19

22. R. Bradley, J. Farber, L. Tests: “Light Polymers, II,” a multiple client study by Skeist
Stabilization of Flame Retardant Impact Laboratories, Livingston, N.J., 1982.
Polystyrene,” National Technical Conf. of Soc. 30. “A Market, Technical, and Opportunity Study,
of Plastic Engineers, Louisville, Ky., Flame Retardant Plastics in the Construction
Nov. 17 – 19, 1975. Industry,” TPC Business Research Group,
23. R. Bradley, J. Farber, L. Tests, Polym. Eng. Sci. Westport, Conn., 1981.
7 (1977) no. 11, 782. 31. G. C. Tesoro, Polym.-Plast. Technol. Eng. 18
24. Polyplastics Co., EP 0 054 392, 1981 (M. (1982) no. 2, 123.
Matsuoka, Y. Ikenaga, O. Matsuno). 32. H. L. Kaplan, A. F. Grand, G. E. Hartzell: “A
25. B. J. Sutker: “Factors Affecting Smoke Critical Review of the State-of-the-Art of
Production During Combustion of Polyolefin Combustion Toxicology, final report, SwRI
Polymers,” Standard Technical Publication project no. 01-6862, The Society of the
816, ASTM, Philadelphia, 1983, p. 78. Plastics Industry, New York 1982.
26. A. L. Bridgman, G. L. Nelson, J. of Fire 33. J. O. Punderson, Fire Mater. 5 (1981) no. 1, 41.
Flammability 13 (1982) 114. 34. S. C. Packam, G. E. Hartzell, J. Test. Eval.
27. “Chemicals and Additives, Special Report,”
(ASTM) 9 (1981) 341.
Mod. Plast. 1985, (Sept.) 59.
35. Y. Alarie, M. F. Stock, M. Matijak-Schaper,
28. A. Brief, T. Chastain, C. Cipriani, S. Epstein et
M. M. Birky, Fundam. Appl. Toxicol. 3 (1983)
al.: “Fire Retardant Plastics,” a multiple client
619.
study by Skeist Laboratories, Livingston, N.J.,
36. G. K. Shanga, M. Matijak, Y. Alarie, J. Am.
1985.
29. T. Chastain, S. Epstein, M. Kusumgar, G. F. Ind. Hyg. Assoc. 42 (1981) 481.
Lillquist et al.: “Electronic Applications for
 Flavors and Fragrances 1

Flavors and Fragrances

Karl-Georg Fahlbusch, Corporate Research Division, DRAGOCO Gerberding & Co. Aktiengesellschaft,
Holzminden, Federal Republic of Germany
Franz-Josef Hammerschmidt, Corporate Research Division, DRAGOCO Gerberding & Co. Aktienge-
sellschaft, Holzminden, Federal Republic of Germany
Johannes Panten, Corporate Research Division, DRAGOCO Gerberding & Co. Aktiengesellschaft,
Holzminden, Federal Republic of Germany
Wilhelm Pickenhagen, Corporate Research Division, DRAGOCO Gerberding & Co. Aktiengesellschaft,
Holzminden, Federal Republic of Germany
Dietmar Schatkowski, Corporate Research Division, DRAGOCO Gerberding & Co. Aktiengesellschaft,
Holzminden, Federal Republic of Germany
based on the article of:
Kurt Bauer, Haarmann & Reimer GmbH, Holzminden, Federal Republic of Germany
Dorothea Garbe, Haarmann & Reimer GmbH, Holzminden, Federal Republic of Germany
Horst Surburg, Haarmann & Reimer GmbH, Holzminden, Federal Republic of Germany (Chap. 3)

1. Introduction . . . . . . . . . . . . . . 4 2.2.5.3. Citronellyl Esters . . . . . . . . . . . 27

1.1. The Chemical Senses . . . . . . . . 4 2.2.6. Miscellaneous Compounds . . . . . 27
1.2. Definition . . . . . . . . . . . . . . . . 4 2.3. Cyclic Terpenes . . . . . . . . . . . . 28
1.3. History . . . . . . . . . . . . . . . . . 4 2.3.1. Hydrocarbons . . . . . . . . . . . . . . 28
1.4. Odor Descriptors, Odor Thresh- 2.3.2. Alcohols and Ethers . . . . . . . . . . 30
olds, Odor Value . . . . . . . . . . . 5 2.3.3. Aldehydes and Ketones . . . . . . . . 34
1.4.1. Qualitative Measurements . . . . . . 5 2.3.4. Esters . . . . . . . . . . . . . . . . . . . 40
1.4.2. Quantitative Measurements . . . . . 5 2.3.5. Miscellaneous Compounds . . . . . 42
1.4.2.1. Odor Threshold . . . . . . . . . . . . 5 2.4. Other Cycloaliphatic Compounds 42
1.4.2.2. Odor Value . . . . . . . . . . . . . . . 5 2.4.1. Alcohols . . . . . . . . . . . . . . . . . 43
1.5. Regulations and Labeling Re- 2.4.2. Aldehydes . . . . . . . . . . . . . . . . 44
quirements . . . . . . . . . . . . . . . 6 2.4.3. Ketones . . . . . . . . . . . . . . . . . 45
1.5.1. Flavors . . . . . . . . . . . . . . . . . . 6 2.4.4. Esters . . . . . . . . . . . . . . . . . . . 48
1.5.2. Fragrances . . . . . . . . . . . . . . . . 6 2.5. Aromatic Compounds . . . . . . . . 50
2. Single Fragrance and Flavor Com- 2.5.1. Hydrocarbons . . . . . . . . . . . . . . 50
pounds . . . . . . . . . . . . . . . . . . 6 2.5.2. Alcohols and Ethers . . . . . . . . . . 50
2.1. Aliphatic Compounds . . . . . . . . 7 2.5.3. Aldehydes and Acetals . . . . . . . . 53
2.1.1. Hydrocarbons . . . . . . . . . . . . . . 7 2.5.4. Ketones . . . . . . . . . . . . . . . . . 56
2.1.2. Alcohols . . . . . . . . . . . . . . . . . 7 2.5.5. Esters of Araliphatic Alcohols and
2.1.3. Aldehydes and Acetals . . . . . . . . 8 Aliphatic Acids . . . . . . . . . . . . . 59
2.1.4. Ketones . . . . . . . . . . . . . . . . . 11 2.5.6. Aromatic Acids . . . . . . . . . . . . 60
2.1.5. Acids and Esters . . . . . . . . . . . . 11 2.5.7. Esters Derived from Aromatic and
2.1.6. Miscellaneous Compounds . . . . . 14 Araliphatic Acids . . . . . . . . . . . 60
2.2. Acyclic Terpenes . . . . . . . . . . . 14 2.5.7.1. Benzoates . . . . . . . . . . . . . . . . 60
2.2.1. Hydrocarbons . . . . . . . . . . . . . . 14 2.5.7.2. Phenyl acetates . . . . . . . . . . . . . 61
2.2.2. Alcohols . . . . . . . . . . . . . . . . . 14 2.5.7.3. Cinnamates . . . . . . . . . . . . . . . 61
2.2.3. Aldehydes and Acetals . . . . . . . . 21 2.5.8. Miscellaneous Compounds . . . . . 62
2.2.4. Ketones . . . . . . . . . . . . . . . . . 24 2.6. Phenols and Phenol Derivatives . 63
2.2.5. Acids and Esters . . . . . . . . . . . . 25 2.6.1. Phenols, Phenyl Esters, and Phenyl
2.2.5.1. Geranyl and Neryl Esters . . . . . . 25 Ethers . . . . . . . . . . . . . . . . . . . 63
2.2.5.2. Linalyl and Lavandulyl Esters . . . 26 2.6.2. Phenol Alcohols and their Esters . . 67

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11 141
2 Flavors and Fragrances

2.6.3. Phenol Aldehydes . . . . . . . . . . . 67 3.1. Introduction . . . . . . . . . . . . . . 83

2.6.4. Phenol Ketones . . . . . . . . . . . . . 70 3.2. Isolation of Natural Fragrance
2.6.5. Phenol Carboxylates . . . . . . . . . 70 and Flavor Concentrates . . . . . . 83
2.7. O- and O, S-Heterocycles . . . . . 72 3.2.1. Essential Oils . . . . . . . . . . . . . . 84
2.7.1. Cyclic Ethers . . . . . . . . . . . . . . 72 3.2.2. Extracts . . . . . . . . . . . . . . . . . 84
2.7.2. Lactones . . . . . . . . . . . . . . . . . 76 3.3. Survey of Natural Raw Materials 85
2.7.3. Glycidates . . . . . . . . . . . . . . . . 81 4. Quality Control . . . . . . . . . . . . 121
2.7.4. Miscellaneous Compounds . . . . . 81 5. Economic Aspects . . . . . . . . . . 122
2.8. N- and N, S-Heterocycles . . . . . . 81 6. Toxicology and Environmental
3. Natural Raw Materials in the Fla- Aspects . . . . . . . . . . . . . . . . . 122
vor and Fragrance Industry . . . . 83 7. References . . . . . . . . . . . . . . . 123

1. Introduction sense of sight has become predominant, odor in-

fluences considerably the behavior, consciously
1.1. The Chemical Senses and subconsciously, it controls for example in-
take of food and emotions and according to
The sensations “taste” and “odor” are part of Proust helps in the “search for the past”.
our five senses. Whereas seeing, hearing, and
feeling react to a physical input (visible light
waves, sound waves, and temperature and pres- 1.2. Definition
sure, respectively) the two so-called chemical
senses are stimulated by direct interactions with Flavor and fragrance compounds are molecules
defined chemicals. The chemical senses are re- that stimulate the human chemical senses. The
garded phylogenetically as the oldest senses, physiological importance of compounds that
i.e., the earliest living species communicated by elicit a sensory reaction in other living beings
emitting and receiving chemical signals in their apart from humans will not be treated in the con-
aqueous environment. This communication sys- text of this paper.
tem was refined when the first species left wa- In the following only compounds that stimu-
ter to live on land and had to rely on molecules late the sense of smell for flavors and fragrances
that were transported in the surrounding atmo- are discussed. These compounds, that are de-
sphere. These molecules had to be volatile and tected in the upper end of the nose have to have
were detected by the odor receptors which con- a certain volatility to be transported with the
sequently developed to a much higher sophis- aspired air stream to the receptors. It is gen-
tication than the taste receptors. The currently erally assumed that compounds with a molec-
accepted doctrine is that only four basic taste ular mass > 300 are not volatile enough to ful-
impressions (salty, sweet, sour, and bitter [1]) fill these conditions. Even if many compounds
exist, whereas the types of odor impressions are are used both as flavor and fragrance ingredi-
unlimited. Newer results, however, indicate that ents, some distinctions exist: in general, flavor
the limitation to only four taste impressions is compounds consist of molecules that occur natu-
too narrow and that more complex stimulations rally in edible materials whereas many fragrance
to the sense of taste do exist [2]. compounds are not produced in nature (see Sec-
According to E. L. Wick, the term flavor as tion 1.5).
sensory impression results from the simultane-
ous stimulation of the two chemical senses, odor
and taste [3], so the description of volatile ma- 1.3. History
terials will cover both flavor and fragrance ma-
terials. As mentioned above, the sense of odor The history of odor is as old as the history of
developed to a much higher degree than the sense mankind. Incense was already offered to the
of taste and in some highly developed mammals God of the Sea in Ninive, in 5000 b.c. The
(e.g., all canine species) became the most im- Gilgamesch Epos, which is considered to be
portant sense of all. Even in humans, where the the oldest written document about the genesis
 Flavors and Fragrances 3

of mankind, mentions the use of cedarwood as compounds) for the synthesis of other not natu-
source of odorants already in 3200 b.c. Sandal- rally occurring odorants.
wood is described as part of the gifts that the
Queen of Sheba gave to Salomon. Greeks and
Romans used oil extracts of herbs and flowers 1.4. Odor Descriptors, Odor
as therapeutic agents and for their sensory plea- Thresholds, Odor Value
sures. During the middle ages, no real progress
in preparing and using odorant materials was re- Odors can be measured and described qualita-
ported, apart from the discovery of making con- tively and quantitatively, but contrary to the stim-
centrated alcohol by the Arabs [4]. Real progress uli that elicit our other senses (i.e., sight, hear-
in preparation of odorant compounds and mix- ing, touch, temperature) no physical analytical
tures started nearly simultaneously with the be- method exist for odor measurement.
ginning of organic chemistry which is marked
by Wöhler’s synthesis of urea [5].
Already in 1830, Wöhler and Liebig syn- 1.4.1. Qualitative Measurements
thesized benzaldehyde, which was subsequently
identified as the main aroma compound in Qualitative measurements are restricted to ver-
bitter almonds by Robiquet and Boutron- bal descriptions of the odor impression. First
Charlard in 1932. Worthy of mention is the approaches to classify odors by their descrip-
synthesis of vanillin by Reimer and Thiemann tors were initiated by Harper, Bate Smith, and
in 1876, which led to the foundation of the Ger- Land [9]. Their general conclusion is that the
man flavor and fragrance industry. more complex the odor perception the more im-
Analysis of food flavors proved to be cum- possible becomes an exact odor description. A
bersome due to the very low natural abundance more detailed analysis into description of odors
of these molecules and the analytical meth- and thus their qualitative measurement has been
ods available at that time. By 1960, about 450 initiated by Kastner [10], who distinguishes
molecules had been identified to occur in the three main descriptor categories, i.e., general de-
volatile part of edible materials. scriptive terms, special descriptive terms, and
The real breakthrough in knowledge about precise descriptive terms, in which the first one
the chemical nature of odorants started with the refers to adjectives like attractive, good, bad,
invention and application of gas chromatogra- stinky, rough, etc.; the second category com-
phy by James and Martin [6]. This analytical prises explications like green, herbaceous, flow-
and also preparative separation method is the ery, earthy; and the third one uses terms like sul-
technique of choice for volatile materials such as fury, ambery, sweaty, etc.
odorants. The value of gas chromatography was
quickly recognized and this technique has under-
gone enormous progress, e.g., through the intro- 1.4.2. Quantitative Measurements
duction of capillary columns [7] and coupling
of this separation tool to identification systems 1.4.2.1. Odor Threshold
such as mass spectrometry and infrared spec-
troscopy. Extensive use of these and other ana- Odor strength can be described by its odor
lytical procedures have since allowed the iden- threshold. Generally, two different thresholds
tification of about 8000 volatile compounds in are used: (1) the detection threshold, which is
food materials [8]. Parallel to investigations into defined as the lowest detectable concentration
foods this method was also used to analyze many of a compound versus the pure solvent and (2)
odorant extracts from materials such as flowers, the recognition threshold, which is the lowest
leaves, and other natural sources used histor- concentration that allows an identification of the
ically as fragrance materials. Development in odor impression of a compound. Both values are
synthetic procedures allowed economical syn- strongly dependent on the solvent system [11].
theses of these identified compounds which can Thresholds measured in air are generally
be used as such or as molecular models (lead much lower than those measured in water. A
compilation of about 2000 thresholds in water
4 Flavors and Fragrances

and in air document the enormous differences juice, edible yeast, herb, bark, bud, root, leaf
that can occur [12]. or similar plant material, meat, seafood, poul-
Thresholds in air can be measured with try, eggs, dairy products, or fermentation prod-
commercial olfactometers or by standardized ucts thereof, whose significant function in food
smelling from a gas chromatograph as described is flavoring rather than nutritional [17]. In Eu-
in [13], whereas thresholds in water and other rope, these regulations are defined in the “EU
liquid solvents are determined by the so-called Flavouring Directive 88/388 EEC”. The term fla-
multiple pair test [14], in which the panel mem- voring is restricted to flavoring substances, fla-
bers have to decide which of the bottles contain voring preparations, process flavorings, smoke
the compound in question. The concentrations flavorings, or mixtures thereof. A flavoring sub-
are generally presented in a geometrical line. stance is a defined chemical substance with fla-
The threshold is defined as the concentration that voring properties which is obtained: (i) by ap-
is correctly identified by 50 % of a panel consist- propriate physical processes (including distilla-
ing of a statistically relevant number of testers tion and solvent extraction) or enzymatic or mi-
[15]. crobiological processes from material of veg-
etable or animal origin either in the raw state
or after processing for human consumption by
1.4.2.2. Odor Value traditional food-preparation processes (includ-
ing drying, torrefaction, and fermentation), (ii)
The quantitative contribution of a compound to by chemical synthesis or isolated by chemical
the total odor impression can be described by processes and which is chemically identical to
its odor value. This term has been introduced a substance naturally present in material of veg-
by Rothe et al. [16] and is defined as the con- etable or animal origin as described in (i), (iii)
centration of a compound in a given mixture di- by chemical synthesis but which is not chemi-
vided by the odor threshold of this compound, cally identical to a substance naturally present in
i.e., the higher the concentration and the lower material of vegetable or animal origin. “Process
the threshold the more the compound contributes flavoring” means a product which is obtained
to the overall odor impression. according to good manufacturing practices by
heating to a temperature not exceeding 180 ◦ C
for a period not exceeding 15 min from a mixture
1.5. Regulations and Labeling of ingredients not necessarily themselves having
Requirements flavoring properties in which at least one con-
tains nitrogen (amino) and another is a reducing
1.5.1. Flavors sugar. “Smoke flavoring” means a smoke extract
used in traditional foodstuffs smoking processes
Different legislative situations for definition and [18].
labeling of flavor active materials exist: The
Americas base their systems on the United States
Code of Federal Regulations, specifically CFR 1.5.2. Fragrances
101.22, which describes as artificial flavor or
artificial flavoring any substance that imparts For fragrances no differentiation is made bet-
flavor, which is not derived from a spice, fruit ween natural, nature-identical, and artificial sub-
or fruit juice, vegetable or vegetable juice, ed- stances. Many compounds used in fragrances are
ible yeast, herb, bark, bud, root, leaf or similar components of natural origin, e.g., constituents
plant material, meat, fish, poultry, eggs, dairy of essential oils, resins, and, to a much lesser
products, or fermentation products thereof [16]. extent, of animal secretions. In addition many
Natural flavor or natural flavoring means the chemicals are used in fragrances, whose molec-
essential oil, oleoresin, essence or extractive, ular structures are not found to occur in nature
protein hydrolysate, distillate, or any product but their fragrance characteristics mimic those
of roasting, heating or enzymolysis, which con- of natural products. For use in fragrance com-
tains the flavoring constituents derived from a ponents, these chemicals have to comply with
spice, fruit or fruit juice, vegetable or vegetable the national legal requirements. In addition they
 Flavors and Fragrances 5

have to pass the so-called IFRA tests for (see 2.1. Aliphatic Compounds
Chap. 6):
The acyclic terpenes are discussed separately
Acute toxicity
in Section 2.2. Some of the cycloaliphatic fra-
Skin irritation
grance and flavor compounds are structurally re-
Skin sensitization
lated to the cyclic terpenes and are, therefore,
Phototoxicity and photosensitization
discussed in Section 2.4 after the cyclic terpenes.
For those products (e.g., fragrance chemicals,
essential oils, resinoids) for which IFRA has
edited use recommendations this is mentioned 2.1.1. Hydrocarbons
by ’IFRA recommendation’. If IFRA suggests
a maximum use level then one will find the re- Saturated and unsaturated aliphatic hydrocar-
mark ’limiting IFRA recommendation’. In those bons with straight as well as branched chains
cases one may refer to the IFRA publications for occur abundantly in natural foodstuffs, but they
further information. contribute to the odor and taste only to a limited
extent. The highly unsaturated hydrocarbons
1,3-trans-5-cis-undecatriene [51447-08-6] and
2. Single Fragrance and Flavor 1,3-trans-5-trans-undecatriene [19883-29-5],
however, contribute to the odor of galbanum oil
Compounds [19].
Fragrance and flavor compounds of commercial
interest are arranged according to the Beilstein
2.1.2. Alcohols (→ Alcohols, Aliphatic;
system of functional groups, not according to
→ Fatty Alcohols)
their organoleptic properties, since relationships
between odor and structure are difficult to es-
Free and esterified saturated primary alcohols
tablish. However, the Beilstein system has been
occur widely in nature, e.g., in fruit. Since their
abandoned in a few cases for practical reasons.
odor is relatively weak, their use as components
In each class of parent compounds, hydro-
in fragrance compositions is limited. Their use
carbons and oxygen-containing compounds are
in aroma compositions, especially for fruit fla-
described first. Nitrogen- and sulfur-containing
vors, is by far more important (e.g., straight-
compounds are treated at the end of each of these
chain C4 – C10 alcohols, isoamyl alcohol). Un-
sections under the heading Miscellaneous Com-
saturated alcohols are most important (e.g., leaf
pounds. Aliphatic compounds are discussed in
alcohol with its intensely green odor) and may
Section 2.1, followed by the terpenes. The ter-
impart characteristic notes to compositions.
penes constitute a very important group of com-
Naturally occurring fatty alcohols used in
pounds and are subdivided into acyclic ter-
the fragrance industry are produced princi-
penes (Section 2.2) and cyclic terpenes (Sec-
pally by reduction of the methyl esters of
tion 2.3). Nonterpenoid cycloaliphatics are de-
the corresponding carboxylic acids, which are
scribed in Section 2.4. Aromatic compounds are
obtained by transesterification of natural fats
discussed in Section 2.5. Phenols and phenol
and oils with methanol. Industrial reduction
derivatives are described under a separate head-
processes include catalytic hydrogenation in
ing (Section 2.6) on account of their biogenetic
the presence of copper–chromium oxide cat-
and odor relationships. Methylenedioxyphenyl
alysts (Adkins catalysts) and reduction with
derivatives are also described under this head-
sodium (Bouveault–Blanc reduction); for de-
ing for the same reason even though, system-
tails, see → Alcohols, Aliphatic, Chap. 2.3.3.,
atically, they belong to the oxygen-containing
→ Fatty Alcohols, Chap. 2.3., → Fatty Alco-
heterocycles (Section 2.7). Compounds that are
hols, Chap. 2.4. Unsaturated alcohols can also
only produced in small quantities, but which are
be prepared by the latter method. Alcohols are
important due to their high odor intensity, are
starting materials for aldehydes and esters.
mentioned but not described in detail.
6 Flavors and Fragrances

3-Octanol [589-98-0], the triple bond in the presence of palladium cat-

CH3 (CH2 )4 CH(OH)CH2 CH3 , C8 H18 O, M r alysts yields cis-3-hexen-1-ol. Leaf alcohol is
130.23, bp (97.6 kPa) 176 – 176.5 ◦ C, d 20 4 used to obtain natural green top notes in per-
0.8264, n20
D 1.4252, may occur in its optically fumes and flavors. In addition, it is the start-
active form. It is a colorless liquid that has a ing material for the synthesis of 2-trans-6-cis-
mushroomy-earthy odor and occurs in mush- nonadien-1-ol and 2-trans-6-cis-nonadien-1-al.
rooms. 3-Octanol can be obtained by hydro-
genation of 3-octanone; it is used in lavender 1-Octen-3-ol [3391-86-4],
compositions and for imparting mushroom-like CH3 (CH2 )4 CH(OH)CH=CH2 , C8 H16 O, M r
odors. 128.21, bp (94.6 kPa) 175 – 175.2 ◦ C, d 20 4
0.8383, n20
D 1.4378, may occur in the optically
2,6-Dimethyl-2-heptanol [13254-34-7], active form. It is found, for example, in lavender
C9 H20 O, M r 144.26, bp (101.3 kPa) 170 – oil and is a steam-volatile component of mush-
172 ◦ C, d 20 20
4 0.8085, nD 1.4248, which has not
rooms. 1-Octen-3-ol is a liquid with an intense
yet been found in nature, is a colorless liquid mushroom, forest-earthy odor that can be pre-
with a delicate, flowery odor reminiscent of fre- pared by a Grignard reaction from vinylmagne-
sias. It is synthesized from 2-methyl-2-hepten- sium bromide and hexanal. It is used in lavender
6-one and methylmagnesium chloride by a Grig- compositions and in mushroom aromas.
nard reaction, followed by hydrogenation, and Trade Name. Matsutake alcohol (Takasago).
is used in flowery perfume compositions.
9-Decen-1-ol [13019-22-2],
CH2 =CH(CH2 )6 CH2 OH, C9 H18 O, M r 142.24,
bp (270 Pa) 85 – 86 ◦ C, n20
D 1.4480, has been
identified as a trace constituent of cognac. It is
a colorless liquid with a fresh, dewy, rose note
that can be prepared by partial dehydration of
1,10-decanediol. It is used in rosy-floral soap
perfumes.
Trade Names. Dimetol (Givaudan Roure), Trade Name. Rosalva (IFF).
Freesiol (Haarmann & Reimer).
10-Undecen-1-ol [112-43-6],
trans-2-Hexen-1-ol [928-95-0], CH2 =CH(CH2 )8 CH2 OH, C11 H22 O, Mr
CH3 CH2 CH2 CH=CHCH2 OH, C6 H12 O, M r 170.29, bp (2.1 kPa) 133 ◦ C, d 20 0.8460, n 20
4 D
100.16, bp (101.3 kPa) 155 ◦ C, d 20
4 0.8459, nD
20
1.4500, has not yet been found in nature and
1.4382, occurs in many fruits and has a fruity, is a colorless liquid with a fatty-green, slightly
green odor, which is sweeter than that of the citrus-like odor. It can be synthesized from 10-
isomeric cis-3-hexen-1-ol and is, therefore, pre- undecylenic acid and is used to give flower
ferred in aroma compositions. perfumes a fresh note.
cis-3-Hexen-1-ol [928-96-1], leaf alcohol, 2-trans-6-cis-Nonadien-1-ol [28069-72-9],
CH3 CH2 CH=CHCH2 CH2 OH, C6 H12 O, M r CH3 CH2 CH=CHCH2 CH2 CH=CHCH2 OH,
100.16, bp (101.3 kPa)156 – 157 ◦ C, d 204 0.8495, C9 H16 O, violet leaf alcohol, M r 140.22, bp
n20
D 1.4384, is a colorless liquid with the charac- (1.5 kPa) 96 – 100 ◦ C, d 10 20
4 0.8622, nD 1.4740,
teristic odor of freshly cut grass. Robinia pseu- occurs, for example, in cucumber oil, violet leaf
dacacia and mulberry leaf oil contain up to 50 % oil, and violet blossom oil. It is a colorless liquid
leaf alcohol, and green tea up to 30 %. Small with an intense, heavy-fatty, green odor, rem-
quantities occur in the green parts of nearly all iniscent of violet leaves. The starting material
plants. for the synthesis of 2-trans-6-cis-nonadien-1-ol
A stereospecific synthesis for cis-3-hexen-1- is cis-3-hexen-1-ol, which is converted via its
ol starts with the ethylation of sodium acetylide halide into the corresponding Grignard reagent.
to 1-butyne, which is reacted with ethylene oxide The Grignard reagent is reacted with acrolein
to give 3-hexyn-1-ol. Selective hydrogenation of to give 1,6-nonadien-3-ol, which is converted
 Flavors and Fragrances 7

into 2-trans-6-cis-nonadien-1-ol by allylic rear- able since the resultant products are often not
rangement. pure enough for flavor and perfume purposes.
Nonadienol is a powerful fragrance sub- Specific syntheses for the branched-chain and
stance. It is used in fine fragrances to create unsaturated aldehydes that are important in per-
refined violet odors and to impart interesting fumery and flavoring techniques are described
notes to other blossom compositions. In aroma under the individual compounds.
compositions it is used for fresh-green cucumber
notes. Hexanal [66-25-1], caproaldehyde,
CH3 (CH2 )4 CHO, C6 H12 O, M r 100.16, bp
(101.3 kPa) 128 ◦ C, d 20 20
4 0.8139, nD 1.4039, oc-
2.1.3. Aldehydes and Acetals curs, for example, in apple and strawberry aro-
mas as well as in orange and lemon oil. It is a
(→ Aldehydes, Aliphatic and Araliphatic) colorless liquid with a fatty-green odor and in
Aliphatic aldehydes are among the most low concentration is reminiscent of unripe fruit.
important components used in perfumery. Al- Hexanal is used in fruit flavors and, when
though the lower fatty aldehydes C2 – C7 occur highly diluted, in perfumery for obtaining fruity
widely in nature, they are – with the exception notes.
of hexanal – seldom used in fragrance com-
positions. The lower aldehydes (e.g., acetalde- Octanal [124-13-0], caprylaldehyde,
hyde, isobutyraldehyde, isovaleraldehyde, and CH3 (CH2 )6 CHO, C8 H16 O, M r 128.21, bp
2-methylbutyraldehyde) impart fruity and roast (101.3 kPa) 171 ◦ C, d 20 20
4 0.8211, nD 1.4217, oc-
characters to flavor compositions. Fatty alde- curs in several citrus oils, e.g., orange oil. It is
hydes C8 –C13 , however, are used, singly or in a colorless liquid with a pungent odor, which
combination, in nearly all perfume types and becomes citrus-like on dilution. Octanal is used
also in aromas. Their odor becomes weaker with in perfumery in low concentrations, in eaux de
increasing molecular mass, so that aldehydes cologne, and in artificial citrus oils.
> C13 are not important as perfume ingredients.
In addition to the straight-chain saturated al- Nonanal [124-19-6], pelargonaldehyde,
dehydes, a number of branched-chain and unsat- CH3 (CH2 )7 CHO, C9 H18 O, M r 142.24, bp
urated aliphatic aldehydes are important as fra- (101.3 kPa) 190 – 192 ◦ C, d 20 0.8264, n20
4 D
grance and flavoring materials. The double un- 1.4273, occurs in citrus and rose oils. It is a
saturated 2-trans-6-cis-nonadienal [557-48-2], “ colorless liquid with a fatty-roselike odor and
violet leaf aldehyde” (the dominant component is used in floral compositions, particularly those
of cucumber aroma), is one of the most potent with rose characteristics.
fragrance and flavoring substances; it is, there-
fore, only used in very small amounts. Decanal [112-31-2], capraldehyde, caprin-
Acetals derived from aliphatic aldehydes aldehyde, CH3 (CH2 )8 CHO, C10 H20 O, M r
have odor characteristics that resemble those of 156.27, bp (101.3 kPa) 208 – 209 ◦ C, d 20 4
the aldehydes but are less pronounced. These ac- 0.8259, n20D 1.4287, is a component of many es-
etals contribute to the aroma of alcoholic bever- sential oils (e.g., neroli oil) and various citrus
ages, but can rarely be used in flavoring compo- peel oils. It is a colorless liquid with a strong
sitions because they are not sufficiently stable. odor, reminiscent of orange peel, that changes to
Since they are resistant to alkali, a number of a fresh citrus odor when diluted. Decanal is used
them (e.g., heptanal dimethyl acetal and octanal in low concentrations in blossom fragrances (es-
dimethyl acetal) are occasionally incorporated pecially to create citrus nuances) and in the pro-
into soap perfumes. duction of artificial citrus oils.
Fatty aldehydes are generally produced by
dehydrogenation of alcohols in the presence of
Undecanal [112-44-7], CH3 (CH2 )9 CHO,
suitable catalysts (see → Aldehydes, Aliphatic
C11 H22 O, M r 170.29, bp (2.4 kPa) 117 ◦ C, d 20
4
and Araliphatic, Chap. 2.3.). The alcohols are
0.8250, n20
D 1.4325, occurs in citrus oils. It is a
often cheap and available in good purity. Alde-
colorless liquid with a flowery-waxy odor that
hyde synthesis via the oxo process is less suit-
8 Flavors and Fragrances

has aspects of freshness. Undecanal is the pro-

totype of the perfumery aldehydes and is widely
used in perfume compositions for imparting an
“aldehydic note”.

Dodecanal [112-54-9], lauraldehyde, lau-

ric aldehyde, CH3 (CH2 )10 CHO, C12 H24 O, M r
184.32, bp (13.3 kPa) 185 ◦ C, d 204 0.8350, nD
20

1.4350, is a colorless liquid with a waxy odor; 2-Methylundecanal is produced by two

in high dilution it is reminiscent of violets. Do- routes:
decanal occurs in several citrus oils and has been 1) Methyl nonyl ketone is converted into its
found in small amounts in essential oils obtained glycidate by reaction with an alkyl chloro-
from several Pinus species. It is used in per- acetate. Saponification of the glycidate, fol-
fumery in conifer fragrances with fatty-waxy lowed by decarboxylation, yields 2-methyl-
notes, but also in many other odor types. It is undecanal.
added to aroma compositions to obtain citrus 2) The second synthesis is based on the
notes. conversion of undecanal into 2-methy-
leneundecanal by reaction with formalde-
Tridecanal [10486-19-8], CH3 (CH2 )11 CHO, hyde in the presence of catalytic amounts
C13 H26 O, M r 198.34, bp (1.3 kPa) 128 ◦ C, d 20
4 of amines [20]. Hydrogenation of 2-methy-
0.8358, n18
D 1.4384, occurs in lemon oil and leneundecanal yields methylnonylacetalde-
has been identified as a volatile constituent hyde. A convenient process starts from
of cucumber. It is a colorless liquid having a 1-decene: hydroformylation gives a mix-
fatty-waxy, slightly citrus-like odor. Addition ture consisting mainly of undecanal and 2-
of tridecanal to fragrance compositions imparts methyldecanal. Reaction of the crude prod-
fresh nuances in the top note as well as in the uct with formaldehyde in the presence of
dry out. dibutylamine yields a mixture containing
over 50 % 2-methyleneundecanal. After hy-
2-Methyldecanal [19009-56-4], methyl- drogenation of the double bond, pure 2-
octylacetaldehyde, CH3 (CH2 )7 CH(CH3 )CHO, methylundecanal is separated from byprod-
C11 H22 O, M r 170.29, bp (98.8 kPa) 119 – ucts by fractional distillation [21].
120 ◦ C, d 20 20
4 0.8946, nD 1.4205, is not reported
to have been found in nature. It is a colorless
liquid with an aldehydic, citrus-peel-like, waxy-
green odor. 2-Methyldecanal is obtained as a
byproduct in the manufacture of 2-methylun-
decanal by hydroformylation of 1-decene. It is
used in perfumery to refresh green and citrus
nuances.

2-Methylundecanal [110-41-8], methyl-

nonylacetaldehyde, CH3 (CH2 )8 CH(CH3 )CHO, In comparison with other fatty aldehydes, 2-
C12 H24 O, M r 184.32, bp (1.3 kPa) 114 ◦ C, d 20
4
methylundecanal is used in perfumery in rather
0.8303, n20
D 1.4321, has not yet been found in
large amounts to impart conifer notes, particu-
nature. It is a colorless liquid, with an odor larly fir impressions, but frequently also in phan-
markedly different from that of the isomeric do- tasy compositions.
decanal. It has a fatty odor with incense and am-
bergris notes. trans-2-Hexenal [6728-26-3], leaf alde-
hyde, CH3 CH2 CH2 CH =CHCHO, C6 H10 O, M r
98.14, bp (101.3 kPa) 146 – 147 ◦ C, d 20
4 0.8491,
n20
D 1.4480, is the simplest straight-chain un-
saturated aldehyde of interest for perfumes and
 Flavors and Fragrances 9

flavors. It occurs in essential oils obtained from 2.1.4. Ketones (→ Ketones)

green leaves of many plants. trans-2-Hexenal is
a colorless, sharp, herbal-green smelling liquid Aliphatic monoketones are of minor importance
with a slight acrolein-like pungency. Upon di- as fragrance and aroma substances. 2-Alkanones
lution, however, it smells pleasantly green and (C3 – C15 ) have been found in the volatile frac-
apple-like. The aldehyde can be synthesized tions of many fruits and foods, but they do not
by reacting butanal with vinyl ethyl ether in contribute significantly to their aroma. An ex-
the presence of boron trifluoride, followed by ception are the odd-numbered methyl ketones
hydrolysis of the reaction product with dilute C7 , C9 , C11 , which possess a characteristic nutty
sulfuric acid [22]. note; they are used, e.g., in cheese flavor compo-
sitions. In perfumery, aliphatic ketones are used
for accentuation, e.g., 3-octanone [106-68-3] for
lavender notes. The hydroxyketone acetoin and
the diketone 2,3-butanedione are commercially
important aroma substances.

Acetoin [52217-02-4], 3-hydroxy-2-buta-

none, CH3 COCH(OH)CH3 , C4 H8 O2 , M r
trans-2-Hexenal has an intense odor and is 88.11, bp (101.3 kPa) 148 ◦ C, d 20
4 1.0058, nD
20

used in perfumes to obtain a green-leaf note, and 1.4171, has a pleasant buttery odor and both
in fruit flavors for green nuances (limiting IFRA of its optical isomers occur widely in nature.
recommendation). (See Sec. 1.5.2 Fragrances). It is synthesized by partial oxidation of 2,3-
butanediol and is obtained as a byproduct in the
cis-4-Heptenal [6728-31-0], fermentation of molasses. It is used for flavoring
CH3 CH2 CH=CHCH2 CH2 CHO, C7 H12 O, M r margarine.
112.17, bp (1.33 kPa) 41 ◦ C, n20 D 1.4343, is a
widespread volatile trace constituent of food fla- 2,3-Butanedione [431-03-8], diacetyl,
vors. It is a colorless, oily liquid with a power- CH3 COCOCH3 , C4 H6 O2 , M r 86.09, bp 88 ◦ C
ful, fatty, somewhat fishy and, in high dilution, (101.3 kPa), d 20 20
4 0.9831, nD 1.3950, is a con-
creamy odor. It can be prepared from 1-butyne stituent of many fruit and food aromas and well-
(via lithium 1-butynide) and acrolein (which known as a constituent of butter. Many methods
is converted into 2-bromopropionaldehyde di- are known for its manufacture, e.g., dehydrogen-
methyl acetal). The resulting 4-heptynal di- ation of 2,3-butanediol with a copper chromite
methyl acetal is cleaved and the triple bond is hy- catalyst [24]. It is used mainly in aromas for
drogenated catalytically to give cis-4-heptenal butter and roast notes. Large quantities are used
[23]. for flavoring margarine; small amounts are used
cis-4-Heptenal is used in cream, butter, and in perfumes.
fat flavors.

10-Undecenal [112-45-8], 2.1.5. Acids and Esters (→ Carboxylic Acids,

CH2 =CH(CH2 )8 CHO, C11 H20 O, M r 168.28, Aliphatic; → Esters Organic)
bp (400 Pa) 103 ◦ C, d 20 20
4 0.8495, nD 1.4459, has
not yet been found in nature. It is a colorless liq- Straight-chain, saturated aliphatic acids are
uid with a fatty-green, slightly metallic, heavy- found in many essential oils and foods. These
flowery odor. The aldehyde can be synthesized acids contribute to aromas, but are not important
from undecylenic acid, for example, by hydro- as fragrance substances. In flavor compositions,
genation of the acid chloride ( Rosenmund re- aliphatic acids up to C10 are used to accentuate
duction) or by reaction with formic acid in the certain aroma characteristics (C3 – C8 for fruity
vapor phase in the presence of titanium diox- notes; C4 , C6 – C12 for cheese flavors). How-
ide. In perfumery, 10-undecenal is one of the ever, straight-chain and some branched-chain
aldehydes essential for creating the “aldehydic
note”.
10 Flavors and Fragrances

aliphatic acids are of considerable importance as (101.3 kPa) 77.1 ◦ C, d 20 20

4 0.9003, nD 1.3723, is
starting materials in the manufacture of esters, a fruity smelling liquid with a brandy note and
many of which are valuable fragrance and fla- is the most common ester in fruits. It is used in
vor materials. Aliphatic esters contribute to the fruit and brandy flavors.
aroma of nearly all fruits and many foods. Some
are responsible for a particular fruit aroma, or for Butyl acetate [123-86-4],
the smell of a particular flower; however, many CH3 COO(CH2 )3 CH3 , C6 H12 O2 , M r 116.16, bp
of these esters possess a nonspecific fruity odor. (101.3 kPa) 126.5 ◦ C, d 20 20
4 0.9003, nD 1.3942, is
Most of the esters used are acetates and etha- a liquid with a strong fruity odor. It occurs in
nol is the most common alcohol component. In many fruits and is a constituent of apple aromas.
nature, most esters are derived from alcohols and
acids with an even number of carbon atoms. In Isoamyl acetate [123-92-2],
addition to straight-chain saturated compounds, CH3 COO(CH2 )2 CH(CH3 )2 , C7 H14 O2 , M r
branched-chain compounds such as isoamyl es- 130.19, bp (101.3 kPa) 142.5 ◦ C, d 204 0.8730,
ters and unsaturated compounds such as hexenyl n20
D 1.4006, is a strongly fruity smelling liquid
esters are important. and has been identified in many fruit aromas. It
Although the odor of aliphatic esters with a is the main component of banana aroma and is,
small number of carbon atoms is strictly fruity, it therefore, also used in banana flavors.
changes to fatty-soapy and even metallic as the
number of carbon atoms increases. Hexyl acetate [142-92-7],
Esters are usually prepared by esterification CH3 COO(CH2 )5 CH3 , C8 H16 O2 , M r 144.21, bp
of carboxylic acids with alcohols. Industrial pro- (101.3 kPa) 171.5 ◦ C, d 20 20
4 0.8730, nD 1.4092, is
cedures depend on the physical properties of the a liquid with a sweet-fruity, pearlike odor. It is
esters concerned (see → Esters, Organic). present in a number of fruits and alcoholic bev-
In perfumery, acetates are the most important erages, and is used in fruit aroma compositions.
aliphatic esters; formates do not keep well. An-
imal and fatty notes become more pronounced 3,5,5-Trimethylhexyl acetate [58430-94-7],
in esters of higher fatty acids. Acetates of al- CH3 COO(CH2 )2 CH(CH3 )CH2 C(CH3 )3 , iso-
cohols up to C6 are used principally for fruity nonyl acetate, C11 H22 O2 , M r 186.29, does not
notes, whereas the acetates of C8 , C10 , and C12 occur in nature. Commercial isononyl acetate
alcohols are employed for blossom fragrances contains small amounts of byproducts. It is a
and for flower notes in general. Lauryl acetate colorless liquid with a woody-fruity odor and is
in particular is also used for conifer notes. prepared from diisobutene by the oxo synthesis,
In flavor compositions, aliphatic esters are followed by hydrogenation to the alcohol and
preferred for artificial fruit aromas; as in nature, acetylation. It is used in household perfumery.
acetates and ethyl esters prevail.
trans-2-Hexenyl acetate [2497-18-9],
Ethyl formate [109-94-4], HCOOCH2 CH3 , CH3 COOCH2 CH=CH(CH2 )2 CH3 , C8 H14 O2 ,
C3 H6 O2 , M r 74.08, bp (101.3 kPa) 54.5 ◦ C, d 20
4 M r 142.20, bp (2.1 kPa) 67 – 68 ◦ C, d 204 0.8975,
0.9168, n20
D 1.3598, occurs widely in fruits. It is n20 1.4277, occurs in many fruits and in some es-
D
a liquid with a slightly pungent, fruity, ethereal sential oils, e.g., peppermint. It is a fresh-fruity,
odor and is used in fruit flavors. slightly green smelling liquid and is used in fruit
flavors.
cis-3-Hexenyl formate [33467-73-1],
HCOO(CH2 )2 CH=CHCH2 CH3 , C7 H12 O2 , M r
cis-3-Hexenyl acetate [3681-71-8],
128.17, bp (101.3 kPa) 155 ◦ C, d 20
4 0.9121, nD
20
CH3 COO(CH2 )2 CH=CHCH2 CH3 , C8 H14 O2 ,
1.4270, has been identified in tea. It possesses a
M r 142.20, bp (1.6 kPa) 66 ◦ C, has been iden-
green-fruity odor and is used in perfumery and
tified in many fruit aromas and green tea. It is
flavor compositions to impart fruity green notes.
a prototype for green odors and is often used in
Ethyl acetate [141-78-6], combination with cis-3-hexenol.
CH3 COOCH2 CH3 , C4 H8 O2 , M r 88.11, bp
 Flavors and Fragrances 11

Ethyl propionate [105-37-3], Ethyl 2-methylbutyrate [7452-79-1],

CH3 CH2 COOCH2 CH3 , C5 H10 O2 , M r 102.13, CH3 CH2 CH(CH3 )COOCH2 CH3 , C7 H14 O2 ,
bp (101.3 kPa) 99 ◦ C, d 20 20
4 0.8896, nD 1.3839, is M r 130.19, bp (101.3 kPa) 131 – 132 ◦ C, d 25 4
found in many fruits and alcoholic beverages. It 0.8689, n20
D 1.3964, is a liquid with a green-
has a fruity odor reminiscent of rum and is used fruity odor reminiscent of apples. It is found, for
in flavor compositions for creating both fruity example, in citrus fruits and wild berries and is
and rum notes. used in fruit flavor compositions.

Ethyl butyrate [105-54-4], Ethyl hexanoate [123-66-0], ethyl caproate,

CH3 (CH2 )2 COOCH2 CH3 , C6 H12 O2 , M r CH3 (CH2 )4 COOCH2 CH3 , C8 H16 O2 , M r
116.16, bp (101.3 kPa) 121 – 122 ◦ C, d 20 4 144.21, bp (101.3 kPa) 168 ◦ C, d 204 0.8710, nD
20
0.8785, n20
D 1.4000, occurs in fruits and al- 1.4073, is a colorless liquid with a strong fruity
coholic beverages, but also in other foods such odor, reminiscent of pineapples. It occurs in
as cheese. It has a fruity odor, reminiscent of many fruits and is used in small amounts for
pineapples. Large amounts are used in perfume flowery-fruity notes in perfume compositions
and in flavor compositions. and in larger quantities in fruit flavors.

Butyl butyrate [109-21-7], 2-Propenyl hexanoate [123-68-2], allyl cap-

CH3 (CH2 )2 COOCH2 (CH2 )2 CH3 , C8 H16 O2 , roate, CH3 (CH2 )4 COOCH2 CH=CH2 ,C9 H16 O2 ,
M r 144.21, bp (101.3 kPa) 166 ◦ C, d 20
4 0.8709, M r 156.22, bp (2 kPa) 75 – 76 ◦ C, d 204 0.8869,
n20
D 1.4075, is a liquid with a sweet-fruity odor. n20
D 1.4243, and also to occurs in nature. It has a
It is a volatile constituent of many fruits and typical pineapple odor and is used in, for exam-
honey and is used in fruit flavor compositions. ple, artificial pineapple flavors. (Limiting IFRA
recommendation) (see Sec. 1.5.2 Fragrances).
Isoamyl butyrate [106-27-4],
CH3 (CH2 )2 COO(CH2 )2 CH(CH3 )2 , C9 H18 O2 , Ethyl heptanoate [106-30-9], ethyl enan-
M r 158.23, bp (101.3 kPa) 178.5 ◦ C, d 20
4 0.8651, thate, CH3 (CH2 )5 COOCH2 CH3 , C9 H18 O2 , M r
n20
D 1.4106, is a liquid with strongly fruity odor 158.24, bp (101.3 kPa) 187 – 188 ◦ C, d 20 4
that occurs, e.g., in banana. It is used mainly in 0.8680, n20D 1.4120, is a colorless liquid with
fruit flavors. a fruity odor reminiscent of cognac. It is found
in fruits and alcoholic beverages and is used in
Hexyl butyrate [2639-63-6], appropriate aroma compositions.
CH3 (CH2 )2 COO(CH2 )5 CH3 , C10 H20 O2 , M r
172.27, bp (101.3 kPa) 208 ◦ C, d 20 20
4 0.8652, nD 2-Propenyl heptanoate [142-19-8], al-
1.3920, is a liquid with a powerful fruity odor. lyl enanthate,CH3 (CH2 )5 COOCH2 CH=CH2 ,
It has been identified in a number of fruits and C10 H18 O2 , M r 170.25, bp (101.3 kPa) 210 ◦ C,
berries and is an important constituent of fruit d 20 20
4 0.8927, nD 1.4290, has not yet been found
flavor compositions. in nature. It is used in perfume compositions for
apple-like (pineapple) notes. (Llimiting IFRA
cis-3-Hexenyl isobutyrate [41519-23-7], recommendation) (see Sec. 1.5.2 Fragrances).
(CH3 )2 CHCOO(CH2 )2 CH=CHCH2 CH3 ,
C10 H18 O2 , M r 170.25 is found in spearmint oil.
Ethyl octanoate [106-32-1], ethyl capry-
It smells fruity-green and is used in perfumery
late, CH3 (CH2 )6 COOCH2 CH3 , C10 H20 O2 , M r
to create freshness in blossom compositions.
172.27, bp (101.3 kPa) 208 ◦ C, d 20 20
4 0.8693, nD
1.4178, is a liquid with a fruity-flowery odor. It
Ethyl isovalerate [108-64-5],
occurs in many fruits and alcoholic beverages
(CH3 )2 CHCH2 COOCH2 CH3 , C7 H14 O2 , M r
and is used in fruit flavors.
130.19, bp (101.3 kPa) 134.7 ◦ C, d 20 20
4 0.8656, nD
1.3962, is a colorless liquid with a fruity odor
reminiscent of blueberries. It occurs in fruits,
vegetables, and alcoholic beverages. It is used
in fruity aroma compositions.
12 Flavors and Fragrances

Ethyl 2-trans-4-cis-decadienoate [3025-30- can be prepared by reacting allyl chloride with

7], CH3 (CH2 )4 CH=CHCH=CHCOOCH2 CH3 , alkaline-earth or alkali isothiocyanates [26].
C12 H20 O2 , M r 196.29, bp (6 kPa) 70 – 72 ◦ C,
has been identified in pears and has the typ-
ical aroma of Williams pears. Synthesis of 2.2. Acyclic Terpenes
ethyl 2-trans-4-cis-decadienoate starts from cis-
1-heptenyl bromide, which is converted into a 1- For a general description of terpenes, see
heptenyllithium cuprate complex with lithium → Terpenes.
and copper iodide. Reaction with ethyl propi-
olate yields a mixture of 95 % ethyl 2-trans-4-
cis- and 5 % ethyl 2-trans-4-trans-decadienoate. 2.2.1. Hydrocarbons
Pure ethyl 2-trans-4-cis-decadienoate is ob-
tained by fractional distillation [25]. Acyclic terpene (C10 ) and sesquiterpene (C15 )
hydrocarbons find little use in flavor and fra-
Methyl 2-octynoate [111-12-6], grance compositions. They are relatively unsta-
CH3 (CH2 )4 C≡CCOOCH3 , C9 H14 O2 , M r ble and some have a slightly aggressive odor due
154.21, bp (1.3 kPa) 94 ◦ C, d 20 20
4 0.9320, nD to their highly unsaturated structure. Myrcene,
1.4464. Limiting IFRA recommendation. ocimene, and farnesene, are present in many
fruits and essential oils, but find only limited
Methyl 2-nonynoate [111-80-8], use in perfumery.
CH3 (CH2 )5 C≡CCOOCH3 , C10 H16 O2 , M r
168.24, bp (2.7 kPa) 121 ◦ C, d 20 4 0.9162, nD
25

1.4395. Both methyl 2-nonynoate and methyl

2-octynoate have a triple bond and are liquids
with a fatty, violet-leaf-like odor. They are used
in perfume compositions. Limiting IFRA rec-
ommendation. Myrcene Ocimene

2.1.6. Miscellaneous Compounds

A number of volatile aliphatic compounds

that contain nitrogen or sulfur atoms are im-
β-Farnesene
portant aroma constituents. Alkyl thiols, di-
alkyl sulfides and disulfides, and alkyl thio-
cyanates belong to this group. They occur
widely in foods and spices and determine 2.2.2. Alcohols
the odor of, for example, onions, garlic, and
mustard. Because of their potent smell, they Acyclic terpene and sesquiterpene alcohols oc-
are used in high dilution and are often pro- cur in many essential oils. These alcohols were
duced only in small quantities. The same formerly isolated from oils in which they are ma-
is true for 3-methylthiohexanol [51755-66-9], jor components. Currently, large-scale synthesis
CH3 (CH2 )2 CH(SCH3 )CH2 CH2 OH, a volatile of terpenoids permits production without the un-
constituent of passion fruits. Allyl isothio- certainties associated with isolation from natural
cyanate, however, is an exception in that it is sources. However, the odor qualities of synthetic
produced in large quantities. products often differ from those of compounds
isolated from natural sources, since the desired
Allyl isothiocyanate [57-06-7], allyl mus- natural product often cannot be separated from
tard oil, CH2 =CHCH2 N=C=S, C4 H5 NS, M r small amounts of compounds with similar phys-
99.14, bp (101.3 kPa) 152 ◦ C, d 20
4 1.0126, is the ical properties but different odor quality.
main component of mustard oil (> 95 %). It is The acyclic terpene alcohols geraniol,
a colorless oil with a typical mustard odor and linalool, and citronellol are the most important
 Flavors and Fragrances 13

terpene alcohols used as fragrance and flavor ble bond, they also have an additional possibil-
substances. Geraniol and linalool are, in addition ity for cis–trans-isomerism. Thus, there are four
to nerol and lavandulol, primary products in ter- stereoisomers of farnesol and two of nerolidol.
pene biosynthesis. The fully saturated alcohols
tetrahydrogeraniol and tetrahydrolinalool are Geraniol [106-24-1], 3,7-dimethyl-trans-
also used in large quantities in fragrance compo- 2,6-octadien-1-ol, C10 H18 O, M r 154.25, bp
sitions. The fragrance materials myrcenol, iden- (101.3 kPa) 230 ◦ C, d 20 20
4 0.8890, nD 1.4777,
tified in lavender oil, and its dihydro and tet- occurs in nearly all terpene-containing essential
rahydro derivatives, which have not yet been oils, frequently as an ester. Palmarosa oil con-
found in nature, belong structurally to the ter- tains 70 – 85 % geraniol; geranium oils and rose
penes. The sesquiterpene alcohols farnesol and oils also contain large quantities. Geraniol is a
nerolidol are popular materials for perfume com- colorless liquid, with a flowery-roselike odor.
positions. Since geraniol is an acyclic, doubly unsatu-
rated alcohol, it can undergo a number of re-
actions, such as rearrangement and cyclization.
Rearrangement in the presence of copper cata-
lysts yields citronellal. In the presence of min-
eral acids, it cyclizes to form monocyclic terpene
hydrocarbons, cyclogeraniol being obtained if
Geraniol Nerol the hydroxyl function is protected. Partial hy-
drogenation leads to citronellol, and complete
hydrogenation of the double bonds yields 3,7-di-
methyloctan-1-ol (tetrahydrogeraniol). Citral is
obtained from geraniol by oxidation (e.g., with
chromic acid), or by catalytic dehydrogenation.
Geranyl esters are prepared by esterification.
Linalool Myrcenol Production. Dehydrogenation of geraniol
and nerol is a convenient route for synthesiz-
ing citral, which is used in large quantities as
an intermediate in the synthesis of vitamin A.
Large-scale processes have, therefore, been de-
veloped for producing geraniol. Currently, these
are far more important than isolation from es-
Lavandulol Citronellol
sential oils. Nevertheless, some geraniol is still
isolated from essential oils for perfumery pur-
poses.
1) Isolation from Essential Oils. Geraniol is iso-
lated from citronella oils and from palmarosa
trans,trans-Farnesol trans-Nerolidol oil. Fractional distillation of, for example,
Java citronella oil (if necessary after saponi-
Geraniol and nerol are cis–trans-isomers. In fication of the esters present) yields a fraction
the rarely occurring lavandulol, the isoprene containing ca. 60 % geraniol, as well as cit-
units are not coupled in the normal head-to-tail ronellol and sesquiterpenes.
manner. A product with a higher geraniol content and
The farnesols and nerolidols are sesquiter- slightly different odor quality for use in fine
pene analogs of geraniol–nerol and linalool. fragrances is obtained by fractionating pal-
These compounds are formed by extending one marosa oil after saponification of the geranyl
of the methyl groups in the 7-position of the cor- esters.
responding monoterpene with an isoprene unit. 2) Synthesis from β-Pinene. Pyrolysis of β-
Because these compounds have an extra dou- pinene yields myrcene, which is converted
into a mixture of predominantly geranyl,
14 Flavors and Fragrances

neryl, and linalyl chloride by addition of of vanadates as catalysts to give geranyl and
hydrogen chloride in the presence of small neryl borates. The alcohols are obtained by
amounts of catalyst, e.g., copper(I) chlo- hydrolysis of the esters [30].
ride and an organic quaternary ammonium
Uses. Geraniol is one of the most frequently
salt [27]. After removal of the catalyst, the
used terpenoid fragrance materials. It can be
mixture is reacted with sodium acetate in
used in all flowery-roselike compositions and
the presence of a nitrogen base (e.g., tri-
does not discolor soaps. In flavor compositions,
ethylamine) and converted to geranyl acetate,
geraniol is used in small quantities to accentu-
neryl acetate, and a small amount of linalyl
ate citrus notes. It is an important intermediate
acetate [28]. After saponification and frac-
in the manufacture of geranyl esters, citronellol,
tional distillation of the resulting alcohols,
and citral.
a fraction is obtained that contains ca. 98 %
geraniol. Nerol [106-25-2], 3,7-dimethyl-cis-2,6-
octadien-1-ol, C10 H18 O, M r 154.25, bp
(99.3 kPa) 224 – 225 ◦ C, d 20 20
4 0.8796, nD 1.4744,
occurs in small quantities in many essential oils
where it is always accompanied by geraniol; its
name originates from its occurrence in neroli
oil. Nerol is a colorless liquid with a pleasant
roselike odor which, unlike that of geraniol, has
a fresh green note.
Nerol undergoes the same reactions as geran-
iol, but cyclizes more readily in the presence of
acids.
Nerol is produced along with geraniol from
myrcene in the process described for geraniol
(see Geraniol). It can be separated from geran-
iol by fractional distillation.

Uses. Nerol is used in perfumery not only for

the same purposes as geraniol, e.g., in rose com-
positions, to which it lends a particular fresh-
ness, but also in other blossom compositions. In
3) Synthesis from Linalool. Recently, a 96 % flavor work it is used for bouquetting citrus fla-
pure synthetic geraniol prepared by isomer- vors. Technical-grade nerol, often in a mixture
ization of linalool has become commercially with geraniol, is used as an intermediate in the
available. Orthovanadates are used as cata- production of citronellol and citral.
lysts, to give a > 90 % yield of a geraniol–
nerol mixture [29]. Geraniol of high purity is Linalool [78-70-6], 3,7-dimethyl-1,6-octa-
finally obtained by fractional distillation. dien-3-ol, C10 H18 O, M r 154.25, bp (101.3 kPa)
A considerable portion of commercially 198 ◦ C, d 20 20
4 0.8700, nD 1.4616, occurs as one
available geraniol is produced by a modified of its enantiomers in many essential oils, where
process: linalool obtained in a purity of ca. it is often the main component. (−)-Linalool
65 % from α-pinene is converted into lina- [126-90-9], for example, occurs at a concentra-
lyl borates, which rearrange in the presence tion of 80 – 85 % in Shiu oils from Cinnamo-
mum camphora; Cayenne linaloe oil contains
 Flavors and Fragrances 15

ca. 80 %. (+)-Linalool [126-91-0] makes up 60 – 25 % trans-pinane hydroperoxide. The mix-

70 % of coriander oil. ture is reduced to the corresponding pinanols
either with sodium bisulfite (NaHSO3 ) or
a catalyst. The pinanols can be separated
by fractional distillation and are pyrolized
to linalool: (−)-α-pinene yields cis-pinanol
and (+)-linalool, whereas (−)-linalool is ob-
tained from trans-pinanol [34].
(+)-Linalool (−)-Linalool

Properties. (±)-Linalool [22564-99-4] is,

like the individual enantiomers, a colorless liq-
uid with a flowery-fresh odor, reminiscent of lily
of the valley. However, the enantiomers differ
slightly in odor [31]. Together with its esters,
linalool is one of the most frequently used fra-
grance substances and is produced in large quan-
tities.
In the presence of acids, linalool isomerizes
readily to geraniol, nerol, and α-terpineol. It
is oxidized to citral by chromic acid. Oxida-
tion with peracetic acid yields linalool oxides,
which occur in small amounts in essential oils
and are also used in perfumery. Hydrogenation
of linalool gives tetrahydrolinalool, a stable fra-
grance compound. Its odor is not as strong as,
but fresher than, that of linalool. Linalool can be
converted into linalyl acetate by reaction with
ketene or an excess of boiling acetic anhydride
[32].
Production. In the 1950s nearly all linalool
used in perfumery was isolated from essential
oils, particularly from rosewood oil. Currently,
this method is used only in countries where oils
with a high linalool content are available and
where the importation of linalool is restricted.
Since linalool is an important intermediate in
the manufacture of vitamin E, several large-scale
processes have been developed for its produc-
3) Synthesis from β-Pinene. For a description
tion. Preferred starting materials and/or interme-
of this route, see under Geraniol. Addition
diates are the pinenes and 2-methyl-2-hepten-6-
of hydrogen chloride to myrcene (obtained
one. Most perfumery-grade linalool is synthetic.
from β-pinene) results in a mixture of ger-
1) Isolation from Essential Oils. Linalool can be anyl, neryl, and linalyl chlorides. Reaction
isolated by fractional distillation of essential of this mixture with acetic acid–sodium ac-
oils, for example, rosewood oil, Shiu oil, and etate in the presence of copper(I) chloride
coriander oil, of which Brazilian rosewood gives linalyl acetate in 75 – 80 % yield [35].
oil is probably the most important. Linalool is obtained after saponification.
2) Synthesis from α-Pinene. α-Pinene from tur- 4) Synthesis from 2-Methyl-2-hepten-6-one.
pentine oil is selectively hydrogenated to cis- The total synthesis of linalool starts with 2-
pinane [33], which is oxidized with oxy- methyl-2-hepten-6-one; several large-scale
gen in the presence of a radical initiator processes have been developed for synthe-
to give a mixture of ca. 75 % cis- and sizing this compound:
16 Flavors and Fragrances

a) Addition of acetylene to acetone results in the d) In another process, 2-methyl-2-hepten-6-one

formation of 3-methyl-1-butyn-3-ol, which is obtained by isomerization of 2-methyl-1-
is hydrogenated to 3-methyl-1-buten-3-ol in hepten-6-one [40]. The latter can be prepared
the presence of a palladium catalyst. This in two steps from isobutylene and formal-
product is converted into its acetoacetate dehyde. 3-Methyl-3-buten-1-ol is formed in
derivative with diketene [36] or with ethyl the first step [41] and is converted into 2-
acetoacetate [37]. The acetoacetate under- methyl-1-hepten-6-one by reaction with ace-
goes rearrangement when heated (Carroll re- tone [42].
action) to give 2-methyl-2-hepten-6-one: 2-Methyl-2-hepten-6-one is converted into
linalool in excellent yield by base-catalyzed
ethynylation with acetylene to dehydrolinalool
[43]. This is followed by selective hydrogen-
ation of the triple bond to a double bond in the
presence of a palladium–carbon catalyst.

Uses. Linalool is used frequently in per-

b) In another process, 2-methyl-2-hepten-6-one fumery for fruity notes and for many flowery
is obtained by reaction of 3-methyl-1-buten- fragrance compositions (lily of the valley, laven-
3-ol with isopropenyl methyl ether followed der, and neroli). Because of its relatively high
by a Claisen rearrangement [38]: volatility, it imparts naturalness to top notes.
Since linalool is stable in alkali, it can be used in
soaps and detergents. Linalyl esters can be pre-
pared from linalool. Most of the manufactured
linalool is used in the production of vitamin E.

Myrcenol [543-39-5], 2-methyl-6-methy-

lene-7-octen-2-ol, C10 H18 O, M r 154.25, bp
(6.7 kPa) 78 ◦ C, d 20 20
4 0.8764, nD 1.4731, is an
isomer of geraniol and linalool. It has been
identified in Chinese lavender oil [44] and some
c) A third synthesis starts from isoprene, which medicinal plants. It is a colorless liquid with a
is converted into 3-methyl-2-butenyl chlo- fresh-flowery, slightly limelike odor. Due to its
ride by addition of hydrogen chloride. Reac- conjugated double bonds, it tends to polymer-
tion of the chloride with acetone in the pres- ize; polymerization can be suppressed by adding
ence of a catalytic amount of an organic base inhibitors (e.g., antioxidants such as ionol).
[39] leads to 2-methyl-2-hepten-6-one: Myrcenol can be prepared by treating
myrcene with diethylamine to give a mixture
of geranyl- and neryldiethylamine. These com-
pounds are hydrated with a dilute acid to the
corresponding hydroxydiethylamines. Deami-
nation to myrcenol is effected by using a
palladium–phosphine-cation complex as a cat-
alyst [45].
 Flavors and Fragrances 17

Production. (−)-Citronellol is still obtained

mainly from geranium oil by saponification fol-
lowed by fractional distillation. Although of
high odor quality, it does not possess the true
(−)-citronellol odor due to impurities. Much
larger quantities of (+)- and (±)-citronellol are
used and are prepared by partial or total synthe-
sis.
1) Synthesis of (+)- and (±)-Citronellol from
the Citronellal Fraction of Essential Oils.
(+)-Citronellal is obtained by distillation of
Java citronella oil and is hydrogenated to (+)-
citronellol in the presence of a catalyst (e.g.,
Raney nickel). Similarly, (±)-citronellol is
prepared from the (±)-citronellal fraction of
Myrcenol is used in perfumery to obtain a Eucalyptus citriodora oil.
lifting top note in citrus and lavender composi- 2) Synthesis of (±)- or Slightly Dextrorotatory
tions. Citronellol from Geraniol Fractions of Es-
sential Oils. This citronellol is produced by
Citronellol [26489-01-0], 3,7-dimethyl-6- catalytic hydrogenation of saponified geran-
octen-1-ol, C10 H20 O, M r 156.27, bp (101.3 kPa) iol fractions (also containing (+)-citronellol)
244.4 ◦ C, d 20
4 0.8560, n20
D 1.4558, [α]D +
20 obtained from Java citronella oil, followed
◦
resp. − 5 to 6 , occurs as both (+)-citronellol by fractional distillation. Selective hydro-
[1117-61-9] and (−)-citronellol [7540-51-4] in genation of the double bond in the 2-position
many essential oils. of geraniol in geraniol–citronellol mixtures
(−)-Citronellol isolated from natural sources isolated from essential oils can be achieved
is often named rhodinol. At present, the name by using Raney cobalt as a catalyst; overhy-
rhodinol is also used for the isopropenyl isomer, drogenation to 3,7-dimethyloctan-1-ol can
α-citronellol; therefore, exclusive use of the sys- be largely avoided by this method [46].
tematic name is better.
In many natural products citronellol occurs
as a mixture of its two enantiomers; the pure
(+) or (−) form is seldom found. (+)-Citronellol
dominates in oils from Boronia citriodora (to-
tal citronellol content ca. 80 %) and Eucalyptus
citriodora (citronellol content 15 – 20 %). (−)-
Citronellol is the predominant enantiomer in
geranium and rose oils, both of which may con- 3) Synthesis of (±)-Citronellol from Synthetic
tain up to 50 % citronellols. Geraniol– Nerol or Citral. A consider-
Citronellol is a colorless liquid with a sweet able amount of commercial synthetic (±)-
roselike odor. The odor of (−)-citronellol is citronellol is produced by partial hydrogen-
more delicate than that of (+)-citronellol. ation of synthetic geraniol and/or nerol. An-
Citronellol undergoes the typical reactions other starting material is citral, which can be
of primary alcohols (→ Alcohols, Aliphatic, hydrogenated, e.g., in the presence of a cat-
Chap. 2.2.). Compared with geraniol, which alyst system consisting of palladium, ruthe-
contains one more double bond, citronellol is nium, and trimethylamine [47].
relatively stable. Citronellol is converted into 4) Preparation of (−)-Citronellol from Opti-
citronellal by dehydrogenation or oxidation; hy- cally Active Pinenes. (+)- cis-Pinane is read-
drogenation yields 3,7-dimethyloctan-1-ol. Cit- ily synthesized by hydrogenation of (+)-α-
ronellyl esters are easily prepared by esterifica- pinene or (+)-β-pinene, and is then pyrolyzed
tion with acid anhydrides. to give (+)-3,7-dimethyl-1,6-octadiene. This
18 Flavors and Fragrances

compound is converted into (−)-citronellol from geraniol or nerol. Because of its stability,
(97 % purity) by reaction with triisobutylalu- it is often used to perfume household products.
minum or diisobutylaluminum hydride, fol-
lowed by air oxidation and hydrolysis of the
resulting aluminum alcoholate [48].
Uses. Citronellol is one of the most widely
used fragrance materials, particularly for rose
notes and for floral compositions in general.
As flavor material, citronellol is added for bou-
quetting purposes to citrus compositions. It is Tetrahydrolinalool [78-69-3], 3,7-di-
the starting material for numerous citronellyl methyloctan-3-ol, C10 H22 O, M r 158.28, bp
esters and for hydroxydihydrocitronellol, an (1.3 kPa) 78 – 79 ◦ C, d 20 20
4 0.8294, nD 1.4335,
intermediate in the production of hydroxydi- is a constituent of honey aroma. It is a col-
hydrocitronellal. orless liquid with a linalool-like odor that is
slightly fresher but distinctly weaker than that
Dihydromyrcenol [18479-58-8], 2,6-di- of linalool. Tetrahydrolinalool is prepared by
methyl-7-octen-2-ol, C10 H20 O, M r 156.27, bp catalytic hydrogenation of linalool and is used
(1.3 kPa) 77 – 79 ◦ C, d 20 as a substitute for the less stable linalool in
4 0.841, is a colorless liq-
uid with a fresh citrus-like odor and a lavender perfuming aggressive media.
note. It is prepared from 2,6-dimethyl-2,7-octa-
diene, the pyrolysis product of cis-pinane [49],
by addition of hydrogen chloride and hydrolysis
of the resulting 2,6-dimethyl-2-chloro-7-octene
[50].

Farnesol [4602-84-0], 3,7,11-trimethyl-

2,6,10-dodecatrien-1-ol, C15 H26 O, M r 222.37,
bp (1.6 kPa) 156 ◦ C, d 20 20
4 0.8846, nD 1.4890,
is a component of many blossom oils. It is a
colorless liquid with a linden blossom odor,
which becomes more intense when evaporated,
possibly due to oxidation.
Of the four possible isomers (due to the dou-
ble bonds in the 2- and 6-positions), the trans–
trans-isomer is the most common in nature and
occurs, for example, in ambrette seed oil. 2-cis-
6-trans-Farnesol has been identified in petitgrain
oil Bigarade.

Dihydromyrcenol is used in soap perfumes

for lime and blossom notes.

Tetrahydrogeraniol [106-21-8], 3,7-di-

methyloctan-1-ol, C10 H22 O, M r 158.28, bp
(101.3 kPa) 212 – 213 ◦ C, d 20 4 0.8285, n20 D
trans-trans-Farnesol
1.4355, has been identified in citrus oils and Since the odors of the isomers differ very lit-
is a colorless liquid with a waxy, rose-petal-like tle, natural farnesol in compositions can be re-
odor. It is prepared by hydrogenation of geraniol placed by synthetic farnesol, which is a mixture
or citronellol in the presence of a nickel catalyst of isomers obtained by isomerization of neroli-
and is a byproduct in the synthesis of citronellol dol.
 Flavors and Fragrances 19

Farnesol is particularly suited for use in 2.2.3. Aldehydes and Acetals

flower compositions and is valued for its fixa-
tive properties. IFRA recommends to use only Among the acyclic terpene aldehydes, citral
qualities containing at least 96 % of the farnesol and citronellal hold key positions as fragrance
isomers. and flavor chemicals, as well as starting ma-
terials for the synthesis of other terpenoids.
Nerolidol [7212-44-4], 3,7,11-trimethyl- Hydroxydihydrocitronellal is one of the most
1,6,10-dodecatrien-3-ol, C15 H26 O, M r 222.37, important fragrance compounds. Derivatives of
bp (1.6 kPa) 145 ◦ C, d 20 20
4 0.8778, nD 1.4898, these aldehydes, particularly the lower acetals,
is the sesquiterpene analogue of linalool. Be- are also used as fragrance compounds. Acyclic
cause of the double bond at the 6-position, it sesquiterpene aldehydes are not very important
exists as cis- and trans-isomers. Each of these as such, but they contribute to the characteristic
isomers can exist as an enantiomeric pair, since fragrance and aroma of essential oils, for exam-
the carbon atom in the 3-position is chiral. ple, in the case of α- and β-sinensal and sweet
orange oil (seepage 94).

Citral [5392-40-5], 3,7-dimethyl-2,6-octa-

dien-1-al, C10 H16 O, M r 152.24, occurs as cis-
and trans-isomers (citral a and b, respectively)
analogous to the corresponding alcohols, geran-
iol and nerol: citral a [141-27-5] ( geranial), bp
(2.7 kPa) 118 – 119 ◦ C, d 20 20
4 0.8888, nD 1.4898;
citral b [106-26-3] ( neral), bp (2.7 kPa) 120 ◦ C,
d 20 20
4 0.8869, nD 1.4869.

Geranial (citral a) Neral (citral b)

Nerolidol is a component of many essential
oils. (+)-trans-Nerolidol occurs in cabreuva oil; Natural citral is nearly always a mixture of
(−)-nerolidol has been isolated from Dalbergia the two isomers. It occurs in lemongrass oil (up
parviflora wood oils. to 85 %), in Litsea cubeba oil (up to 75 %), and in
Synthetic nerolidol consists of a mixture of small amounts in many other essential oils. The
(±)-cis- and (±)-trans-nerolidol and is a col- citrals are colorless to slightly yellowish liquids,
orless liquid with a long-lasting, mild flowery with an odor reminiscent of lemon.
odor. Since citral is an α,β-unsaturated aldehyde
Industrial synthesis of nerolidol starts with with an additional double bond, it is highly re-
linalool, which is converted into geranylacetone active and may undergo reactions such as cy-
by using diketene, ethyl acetoacetate, or iso- clization and polymerization. Geraniol, citronel-
propenyl methyl ether, analogous to the synthe- lol, and 3,7-dimethyloctan-1-ol can be obtained
sis of 2-methyl-2-hepten-6-one from 3-methyl- from citral by stepwise hydrogenation. Citral
1-buten-3-ol (see page 16). Addition of acety- can be converted into a number of addition com-
lene and partial hydrogenation of the resultant pounds; the cis- and trans-isomers can be sep-
dehydronerolidol produces a mixture of cis- and arated via the hydrogen sulfite addition com-
trans-nerolidol racemates. pounds. The condensation of citral with active
Nerolidol is used as a base note in many del- methylene groups is used on an industrial scale
icate flowery odor complexes. It is also an in- in the synthesis of pseudoionones, which are
termediate in the production of vitamins E and starting materials for ionones and vitamins.
K1 .
20 Flavors and Fragrances

Production. Since citral is used in bulk as a

starting material for the synthesis of vitamin A, it
is produced industrially on a large scale. Smaller
quantities are also isolated from essential oils.
1) Isolation from Essential Oils. Citral is iso-
lated by distillation from lemongrass oil (see
p. page 98) and from Litsea cubeba oil (see p.
page 106). It is the main component of these
oils.
2) Synthesis from Geraniol. Currently, the most
important synthetic procedures are vapor-
phase dehydrogenation and oxidation of
geraniol or geraniol–nerol mixtures. Cat-
alytic dehydrogenation under reduced pres-
sure using copper catalysts is preferred [51].
3) Synthesis from Dehydrolinalool. Dehydroli-
nalool is produced on a large scale
from 2-methyl-2-hepten-6-one and acetylene
(see page 16) and can be isomerized to citral
in high yield by a number of catalysts. Pre- Uses. Because of its strong lemon odor, cit-
ferred catalysts include organic orthovana- ral is very important for aroma compositions
dates [52], organic trisilyl oxyvanadates [53], such as citrus flavors. In perfumery it can be
and vanadium catalysts with silanols added used only in neutral media due to its tendency
to the reaction system [54]. to undergo discoloration, oxidation, and poly-
merization. Limiting IFRA recommendation. It
is used as a starting material in the synthesis
of ionones and methylionones, particularly β-
ionone, which is an intermediate in vitamin A
synthesis.

Citral diethyl acetal [7492-66-2], 3,7-

dimethyl-2,6-octadien-1-al diethyl acetal,
C14 H26 O2 , M r 226.36, bp (2 kPa) 140 – 142 ◦ C,
d 20 20
4 0.8730, nD 1.4503, is a colorless liquid
4) Synthesis from Isobutene and Formalde- with a flowery, warm-woody citrus odor. It is
hyde. 3-Methyl-3-buten-1-ol, obtained from relatively stable in alkali and can, therefore, be
isobutene and formaldehyde [41], isomerizes used in soap.
to form 3-methyl-2-buten-1-ol [55]. How-
ever, it is also converted into 3-methyl-2-
butenal by dehydrogenation and subsequent
isomerization [56, 57]. Under azeotropic
conditions in the presence of nitric acid, 3-
methyl-2-buten-1-ol and 3-methyl-2-butenal
form an acetal (shown below) [58], which
eliminates one molecule of 3-methyl-2-
Citronellal [106-23-0], 3,7-dimethyl-6-
buten-1-ol at higher temperatures. The inter-
octen-1-al, C10 H18 O, M r 154.25, bp (101.3 kPa)
mediate enol ether undergoes Claisen rear-
207 – 208 ◦ C, d 20 20
4 0.851, nD 1.4477, [α]D +
20
rangement followed by Cope rearrangement
resp. − 15 ◦ , [α]20 D − 13.1 ◦
, occurs in essen-
to give citral in excellent yield [59]:
tial oils in its (+) and (−) forms, often together
with the racemate. (+)-Citronellal [2385-77-5]
occurs in citronella oil at a concentration of up
 Flavors and Fragrances 21

to 45 %; Backhousia citriodora oil contains up Uses. Citronellal is used to a limited extent

to 80 % (−)-citronellal [5949-05-3]. Racemic for perfuming soaps and detergents. Its main
citronellal [26489-02-1] occurs in a number of use is as a starting material for the produc-
Eucalyptus citriodora oils at a concentration of tion of isopulegol, citronellol, and hydroxydi-
up to 85 %. hydrocitronellal.
Pure citronellal is a colorless liquid with
a refreshing odor, reminiscent of balm mint. 7-Hydroxydihydrocitronellal [107-75-5],
Upon catalytic hydrogenation, citronellal hydroxycitronellal, 3,7-dimethyl-7-hydroxy-
yields dihydrocitronellal, citronellol, or di- octan-1-al, C10 H20 O2 , M r 172.27, bp (130 Pa)
hydrocitronellol, depending on the reaction con- 85 – 87 ◦ C, d 20 20
4 0.9220, nD 1.4488, has been
ditions. Protection of the aldehyde group, fol- reported to occur in essential oils [63]. It is a
lowed by addition of water to the double bond in colorless, slightly viscous liquid with a flow-
the presence of mineral acids or ion-exchange ery odor reminiscent of linden blossom and lily
resins results in formation of 3,7-dimethyl-7- of the valley. Commercially available hydroxy-
hydroxyoctan-1-al (hydroxydihydrocitronellal, citronellal is either optically active or racemic,
see page 24). Acid-catalyzed cyclization to isop- depending on the starting material used. Hy-
ulegol is an important step in the synthesis of droxycitronellal prepared from (+)-citronellal,
(−)-menthol (seepage 30). for example, has a specific rotation [α] 20D + 9 to
Production. Citronellal is still isolated from + 10 ◦ .
essential oils in considerable quantities; it is also Hydroxycitronellal is relatively unstable to-
produced synthetically. ward acid and alkali and is, therefore, sometimes
converted into more alkali-resistant acetals, par-
1) Isolation from Essential Oils. (+)-Citronellal ticularly its dimethyl acetal.
is obtained from citronella oils by fractional Production. The most important synthetic
distillation. (±)-Citronellal is isolated from routes to hydroxydihydrocitronellal are listed
Eucalyptus citriodora oil (see page 100); below.
when necessary, it is purified by using an ad-
dition compound, e.g., the bisulfite deriva- 1) Synthesis from Citronellal. One of the oldest
tive. routes to hydroxycitronellal is the hydration
2) Synthesis from Geraniol or Nerol. (±)- of the citronellal bisulfite adduct (obtained
Citronellal can be obtained by vapor-phase at low temperature) with sulfuric acid, fol-
rearrangement of geraniol or nerol (see page lowed by decomposition with sodium car-
16) in the presence of, e.g., a barium- bonate. A more recent development is hy-
containing copper–chromium oxide catalyst dration of citronellal enamines or imines, fol-
[60]. lowed by hydrolysis [64].
2) Synthesis from Citronellol. Citronellol (see
page 19) is hydrated to 3,7-dimethyloctan-
1,7-diol, for example, by reaction with 60 %
sulfuric acid. The diol is dehydrogenated cat-
alytically in the vapor phase at low pressure
to highly pure hydroxydihydrocitronellal in
excellent yield. The process is carried out in
the presence of, for example, a copper–zinc
3) Synthesis from Citronellol. (±)-Citronellal catalyst [65]; at atmospheric pressure noble
can also be obtained by dehydrogenation of metal catalysts can also be used [66].
citronellol (see page 19) under reduced pres- 3) Synthesis from 7-Hydroxygeranyl–Neryl Di-
sure with a copper chromite catalyst [61]. alkylamine. The starting material can be ob-
4) Synthesis from Citral. Selective hydrogen- tained by treatment of myrcene with a dialky-
ation of citral to citronellal can be accom- lamine in the presence of an alkali dialky-
plished in the presence of a palladium cata- lamide, followed by hydration with sulfu-
lyst in an alkaline alcoholic reaction medium ric acid. The 7-hydroxygeranyl–neryl dialky-
[62]. lamine isomerizes to the corresponding 7-hy-
22 Flavors and Fragrances

droxyaldehyde enamine in the presence of

a palladium(II)–phosphine complex as cat-
alyst. Hydrolysis of the enamine gives 7-
hydroxydihydrocitronellal [67].

Citronellyloxyacetaldehyde [7492-67-3],
C12 H22 O2 , M r 198.30, bp (1.6 kPa) 128 –
130 ◦ C, is a colorless, slightly viscous liquid
with a delicate-flowery odor reminiscent of rose
and lily of the valley. The aldehyde is obtained
by hydrolysis (with dilute acetic acid) of its ac-
etals, which are prepared from sodium citronel-
late and chloroacetaldehyde dialkyl acetals [68].
It is used in perfumery to obtain heavy-flowery
effects.

Uses. Because of its fine, flowery odor,

hydroxydihydrocitronellal is used in large quan- 2,6,10-Trimethyl-9-undecenal [141-13-9],
tities in many perfume compositions for creat- C14 H26 O, M r 210.36, bp (1.2 kPa) 133 –
ing linden blossom and lily of the valley notes. It 135 ◦ C, d 20 20
4 0.8483, nD 1.447 – 1.453, is a col-
is also used in other blossom fragrances such as orless to slightly yellow liquid with an intense
honeysuckle, lily, and cyclamen. Limiting IFRA aldehyde-waxy, slightly flowery odor. It is syn-
recommendation. thesized from hydrogenated pseudoionone (pri-
marily the tetrahydro compound) and an alkyl
Methoxydihydrocitronellal [3613-30-7], chloroacetate by means of a glycidic ester con-
3,7-dimethyl-7-methoxyoctan-1-al, C11 H22 O2 , densation; this is followed by hydrolysis and
M r 186.29, bp (60 Pa) 60 ◦ C, n20
D 1.4375, is a decarboxylation.
colorless liquid with a fresh, green, blossom
odor and is used in perfumery in floral compo-
sitions for fresh-green nuances.

2,6,10-Trimethyl-9-undecenal is a richly fra-

grant compound that is used in flower composi-
tions to obtain an aldehydic note.
Trade Names. Adoxal (Givaudan Roure), Fare-
Hydroxydihydrocitronellal dimethyl ac- nal (Haarmann & Reimer).
etal [141-92-4], 3,7-dimethyl-7-hydroxyoctan-
1-al dimethyl acetal, C12 H26 O3 , M r 218.34, bp
(1.6 kPa) 131 ◦ C, d 20 20
4 0.931, nD 1.4419, is a col- 2.2.4. Ketones
orless liquid with a weak, flowery odor. Since the
acetal is stable to alkali, it is used occasionally Unlike the terpene alcohols, aldehydes, and es-
in soap perfumes. ters, acyclic terpene ketones are not particularly
 Flavors and Fragrances 23

important as fragrance or flavor substances; thus,

they are not discussed here in detail. 2-Methyl-
2-hepten-6-one (see page 16) is an important
intermediate in the synthesis of terpenoids. Its
odor properties are not impressive. It occurs in
nature as a decomposition product of terpenes. cis-Geranic acid Citronellic acid
Tagetone [6752-80-3] is a major component
of tagetes oil. Solanone [1937-54-8] and pseu- Methyl geranate is an intermediate in α-
doionone [141-10-6] are acyclic C13 ketones damascone synthesis and is sometimes needed
with a terpenoid skeleton. Solanone is one of in the reconstitution of essential oils. However,
the flavor-determining constituents of tobacco, the lower fatty acid esters (particularly the ac-
pseudoionone is an intermediate in the synthe- etates) of the acyclic terpene alcohols geraniol,
sis of ionones (see page 36). linalool, and citronellol are extremely important
both as fragrance and as flavor substances. The
acetates occur in many essential oils, sometimes
in rather high amounts. Formates, propionates,
and butyrates occur less frequently. As a result of
the development of large-scale production pro-
cesses for terpenes, the esters of acyclic terpene
Tagetone Solanone alcohols are nearly always made synthetically.
All acyclic terpene esters that are used as fra-
grance and flavor materials can be prepared by
Geranylacetone [689-67-8], 6,10-dimethyl- direct esterification of the appropriate alcohols.
5,9-undecadien-2-one, C13 H22 O, M r 194.32, bp However, special precautions are required for
(1.3 kPa) 124 ◦ C, d 20 20
4 0.8729, nD 1.4674, occurs the esterification of linalool.
in cis as well as trans form and has been identi- Because the lower fatty acid esters of geran-
fied in fruits and in essential oils. It is a colorless iol, linalool, and citronellol are important con-
liquid with a fresh-green, slightly penetrating, tributors to the odor of many essential oils, these
roselike odor. esters are widely used in the reconstitution of
Geranylacetone is an intermediate in neroli- such oils, as well as in perfume and flavor com-
dol synthesis (see page 21). It is used in per- positions. The acetates, particularly linalyl ac-
fumery in rose compositions, for example, in etate, are most widely used. The use of formates
soap perfumes. is limited by their relative instability. Higher es-
ters are not important in terms of quantity, but
are indispensable for creating specific nuances.
In aroma compositions, fatty acid esters of
the acyclic terpene alcohols are used for obtain-
ing citrus notes and for rounding off other flavor
types.
trans-Geranylacetone The most important and most frequently used
acyclic terpene esters are described below.

2.2.5. Acids and Esters 2.2.5.1. Geranyl and Neryl Esters

Although a small amount of acyclic terpene Geraniol is described on page 15, nerol on page
acids such as geranic acid and citronellic acid 16.
occurs in many essential oils, often as esters,
they are rarely used in perfume and flavor com- Geranyl formate [105-86-2], C11 H18 O2 ,
positions. M r 182.26, bp (101.3 kPa) 229 ◦ C (decomp.),
d 20 20
4 0.9209, nD 1.4659, is a liquid with a fresh,
crisp-herbal-fruity rose odor. It is used as a mod-
24 Flavors and Fragrances

ifier of, among others, rose, geranium, and neroli Linalyl formate [115-99-1], C11 H18 O2 , M r
compositions. 182.26, bp (1.3 kPa) 100 – 103 ◦ C, d 20
4 0.9134,
n20
D 1.4530, is a liquid with a fruity odor, remi-
Geranyl acetate [105-87-3], C12 H20 O2 , M r niscent of bergamot. Linalyl formate is moder-
196.29, bp (1.5 kPa) 98 ◦ C, d 20 4 0.9136, nD
20
ately stable and is used in lavender fragrances
1.4624, occurs in varying amounts in many es- and eaux de cologne.
sential oils: up to 60 % in oils from Callitris and
Eucalyptus species, and up to 14 % in palmarosa Linalyl acetate [115-95-7], C12 H20 O2 , M r
oil. A smaller amount occurs in, for example, 196.29, bp (101.3 kPa) 220 ◦ C, d 20
4 0.8951, nD
20

geranium, citronella, petitgrain, and lavender 1.4500, occurs as its (−)-isomer [16509-46-9] as
oils. Geranyl acetate is a liquid with a fruity, rose the main component of lavender oil (30 – 60 %,
note reminiscent of pear and slightly of lavender. depending on the origin of the oil), of lavandin
It is used frequently in perfumery to create not oil (25 – 50 %, depending on the species), and of
only flowery-fruity nuances (e.g., rose), but also bergamot oil (30 – 45 %). It has also been found
for citrus and lavender notes. A small amount is in clary sage oil (up to 75 %) and in a small
added to fruit aromas for shading. amount in many other essential oils. (±)-Linalyl
acetate [40135-38-4] is a colorless liquid with a
Geranyl propionate [105-90-8], C13 H22 O2 , distinct bergamot-lavender odor.
M r 210.32, bp (101.3 kPa) 253 ◦ C, d 20
4 0.9207, Production. Linalyl acetate is synthesized by
n20
D 1.459, has a fruity rose odor and is used in two methods:
perfumery in heavy blossom fragrances with a
secondary fruity note. 1) Esterification of linalool requires special re-
action conditions since it tends to undergo
Geranyl isobutyrate [2345-26-8], dehydration and cyclization because it is an
C14 H24 O2 , M r 224.34, bp (101.3 kPa) 265 ◦ C, unsaturated tertiary alcohol. These reactions
d 20 20
4 0.9209, nD 1.4576, is a liquid with a fruity
can be avoided as follows: Esterification with
rose odor. It is used in floral perfume composi- ketene in the presence of an acidic esterifi-
tions and in fruit flavors. cation catalyst below 30 ◦ C results in forma-
tion of linalyl acetate without any byproducts
Geranyl isovalerate [109-20-6], [69]. Esterification can be achieved in good
C15 H26 O2 , M r 238.37, bp (101.3 kPa) 279 ◦ C, yield, with boiling acetic anhydride, whereby
d 20 20
4 0.8920, nD 1.4640, is a liquid with a strongly
the acetic acid is distilled off as it is formed;
fruity rose odor. It is used in perfume and flavor a large excess of acetic anhydride must be
compositions. maintained by continuous addition of anhy-
dride to the still vessel [32]. Highly pure lina-
Neryl acetate [141-12-8], C12 H20 O2 , M r lyl acetate can be obtained by transesterifica-
196.29, bp (3.4 kPa) 134 ◦ C, d 204 0.9110, nD
20 tion of tert-butyl acetate with linalool in the
1.4624, is the cis-isomer of geranyl acetate. It presence of sodium methylate and by con-
is present in helichrysum oil and has also been tinuous removal of the tert-butanol formed
identified in, among others, neroli oil and pe- in the process [70].
titgrain oil Bigarade. It is a colorless, flowery- 2) Dehydrolinalool, obtained by ethynylation of
sweet-smelling liquid and is used in perfumery 2-methyl-2-hepten-6-one, can be converted
for blossom compositions (e.g., orange blossom into dehydrolinalyl acetate with acetic anhy-
and jasmin). dride in the presence of an acidic esterifi-
cation catalyst. Partial hydrogenation of the
triple bond to linalyl acetate can be carried
2.2.5.2. Linalyl and Lavandulyl Esters out with, for example, palladium catalysts
deactivated with lead [71].
Among the linalyl esters (linalool, see page 16),
the acetate is by far the most important fragrance Uses. Linalyl acetate is used extensively in
and flavor substance. The formate, propionate, perfumery. It is an excellent fragrance mate-
and butyrates are used in small amounts. rial for, among others, bergamot, lilac, lavender,
 Flavors and Fragrances 25

linden, neroli, ylang-ylang, and phantasy notes Citronellyl acetate [67650-82-2],

(particularly chypre). Smaller amounts are used C12 H22 O2 , M r 198.30, bp (101.3 kPa) 240 ◦ C,
in other citrus products. Since linalyl acetate is d 20 20
4 0.8889, nD 1.4515, occurs in many essen-
fairly stable toward alkali, it can also be em- tial oils either as one of its optical isomers or
ployed in soaps and detergents. as the racemate. The odor of racemic citronel-
lyl acetate differs little from that of the optical
Linalyl propionate [144-39-8], C13 H22 O2 , isomers. (±)-Citronellyl acetate is a liquid with
M r 210.31, bp (101.3 kPa) 226 ◦ C, d 204 0.9009, a fresh-fruity rose odor. It is often used as a
n20
D 1.4505, is a liquid with a fresh bergamot fragrance, for example, for rose, lavender, and
note, reminiscent of lily of the valley. It is used geranium notes as well as for eaux de cologne
in perfumery in, for example, bergamot, laven- with citrus nuances. Since it is relatively stable
der, and lily of the valley compositions. to alkali, it can be used in soaps and detergents.
Citrus flavors acquire specific character through
Linalyl butyrate [78-36-4], C14 H24 O2 , M r the addition of citronellyl acetate; it is also used
224.34, bp (101.3 kPa) 232 ◦ C, d 20
4 0.8987, nD
20
to round off other fruit flavors.
1.4523, is a liquid with a fruity bergamot note
and a subdued animalic tone. It is used in laven- Citronellyl propionate [141-14-0],
der perfumes and in many blossom composi- C13 H24 O2 , M r 212.33, bp (2 kPa) 120 – 124 ◦ C,
tions. d 20 20
4 0.8851, nD 1.4452, is a fresh-fruity, roselike
smelling liquid. It is used in perfume and flavor
Linalyl isobutyrate [78-35-3], C14 H24 O2 , compositions in the same way as the acetate.
M r 224.34, bp (20 Pa) 63 – 65 ◦ C, d 20
4 0.8991,
n20
D 1.4513, has a fresh-fruity lavender odor, Citronellyl isobutyrate [97-89-2],
which is more refined than that of the butyrate. It C14 H26 O2 , M r 226.36, bp (1.6 kPa) 131 –
is used in lavender compositions and in several 132 ◦ C, d 20 20
4 0.8760, nD 1.4418, is a liquid with
flowery notes. a sweet-fruity note and is used in perfumery for
fruity-floral nuances.
Lavandulyl acetate [25905-14-0] (for
formula of lavandulol, see Section 2.2.2), Citronellyl isovalerate [68922-10-1],
C12 H20 O2 , M r 196.29, bp (1.7 kPa) 106 – C15 H28 O2 , M r 240.39, bp (4 kPa) 194 – 196 ◦ C,
107 ◦ C, d 20 20
4 0.9129, nD 1.4561, occurs in its d 20 20
4 0.8790, nD 1.4429, has a heavy, rosy-herbal
(−)-form at a concentration of ca. 1 % in French odor and is used in oriental perfume composi-
lavender oil and lavandin oil. It is a liquid with a tions among others.
fresh-herbal rose odor and is used in perfumery
for lavender- and lavandin-oil reconstitutions. Citronellyl tiglate [24717-85-9] (with
One synthetic route to lavandulyl acetate trans-CH3 CH=C(CH3 )COOH as the acid com-
starts with prenyl acetate, which dimerizes in ponent), C15 H26 O2 , M r 238.37, bp (900 Pa)
the presence of a Friedel–Crafts catalyst, such 144 –145 ◦ C, d 20
4 0.9043, is a liquid with a flow-
as boron trifluoride–diacetic acid [72]. ery rosy, fruity, mushroom-like odor. It is used
in geranium oil reconstitutions.

2.2.5.3. Citronellyl Esters

2.2.6. Miscellaneous Compounds
The following citronellyl esters (citronellol, see
page 19) are used in relatively large amounts as The number of nitrogen- and sulfur-containing
fragrance and flavor materials: derivatives of acyclic terpenoids that are known
to be important fragrance and flavor sub-
Citronellyl formate [105-85-1], C11 H20 O2 , stances is even smaller than in the non-terpenoid
M r 184.28, bp (2 kPa) 97 – 98 ◦ C, d 204 0.8972, aliphatic series discussed in Section 2.1.6. How-
n20
D 1.4556, is a liquid with a strongly fruity, ever, a few nitriles are used in rather large
roselike odor, which is suitable for fresh top amounts in soap perfumes because of their rela-
notes in rose and lily of the valley fragrances. tively high stability toward alkali.
26 Flavors and Fragrances

Geranyl nitrile [5146-66-7], geranonitrile,

C10 H15 N, M r 149.24, bp (1.3 kPa) 110 ◦ C, d 20 4
0.8642, n20D 1.4759, occurs as a mixture of its
cis- and trans-isomers. It is a liquid with a crisp-
fresh, lemon-like, green odor. The nitrile can be
prepared from citral by reaction with hydroxyl- Limonene α-Terpinene
amine and subsequent dehydration with acetic
anhydride.
Trade Name. Citralva (IFF).

γ-Terpinene Terpinolene

Citronellyl nitrile [51566-62-2], C10 H17 N,

M r 151.25, bp (2 kPa) 110 – 111 ◦ C, d 20
4 0.845 – α-Phellandrene β-Phellandrene
0.846, n20
D 1.4485 – 1.4500, is a colorless liquid
with a strong, lemon-like odor. The nitrile can Of the bicyclic terpene hydrocarbons, the
be prepared from citronellal oxime in the same pinenes are by far the most important industri-
way as geranic acid nitrile. ally. Camphene and 3-carene are used as starting
Trade Name. Agrunitril (DRAGOCO). materials for fragrance compounds.

α-Pinene β-Pinene

2.3. Cyclic Terpenes

2.3.1. Hydrocarbons
Camphene 3-Carene
Cyclic terpene hydrocarbons occur in essential
oils, sometimes in large amounts. They often Many cyclic sesquiterpenes of various struc-
serve as starting materials for the synthesis of tural types have been isolated from essential oils.
fragrance and flavor compounds. By themselves As in the case of the cyclic monoterpene hydro-
they generally contribute relatively little to fra- carbons, a number of the cyclic sesquiterpenes
grance and aroma. They are used mainly in are used as starting materials in the synthesis of
household perfumery and for reconstitution of fragrance and flavor compounds or for the re-
essential oils. constitution of essential oils. Typical examples
Of the various types of monocyclic terpene are as follows:
hydrocarbons, those with the p-menthadiene
structure are the most important. Examples are
as follows:

Caryophyllene (+)-Valencene
 Flavors and Fragrances 27

components of artificial essential oils. (IFRA

recommendation)

γ-Terpinene [99-85-4], 1,4-p-menthadiene,

Thujopsene α-Cedrene C10 H16 , M r 136.24, bp (101.3 kPa) 183 ◦ C, d 20
4
0.8493, n20
D 1.4747, is a colorless liquid with an
herbaceous citrus odor and can be prepared by
isomerization of limonene.

β-Cedrene Longifolene

Limonene [138-86-3], 1,8-p-menthadiene,

C10 H16 , M r 136.24, bp (101.3 kPa) 178 ◦ C, (−)-α-Phellandrene [4221-98-1], 1,5-p-
d 20 20 20
4 0.8411, nD 1.4726, [α] D + or − 126.3 ;
◦ menthadiene, C10 H16 , M r 136.24, bp (99 kPa)
(+)-limonene [5989-27-5] and (−)-limonene 172 ◦ C, d 20 20 20
4 0.8410, nD 1.4708, [α]D − 183 ,
◦

[5989-54-8] as well as the racemate (dipentene) is a colorless liquid with a citrus odor and a
[7705-14-8] occur abundantly in many essential slight peppery note. It is isolated, for example,
oils. The (+)-isomer is present in citrus peel oils from Eucalyptus dives oil.
at a concentration of over 90 %; a low concen-
tration of the (−)-isomer is found in oils from
the Mentha species and conifers.

Pinenes are widespread, naturally occurring

terpene hydrocarbons. The α- and β-forms oc-
Limonene is a liquid with lemon-like odor. It cur in varying ratios in essential oils.
is a reactive compound; oxidation often yields α-Pinene [80-56-8], 2-pinene, C10 H16 , M r
more than one product. Dehydrogenation leads 136.24, bp (101.3 kPa) 156 ◦ C, d 20
4 0.8553, nD
20
20 ◦
to p-cymene. Limonene can be converted into 1.4662, [α]D + or − 51.9 , is the most wide-
cyclic terpene alcohols by hydrohalogenation, spread pinene isomer. (+)-α-Pinene [7785-70-8]
followed by hydrolysis. Nitrosyl chloride adds occurs, for example, in oil from Pinus palus-
selectively to the endocyclic double bond; this trisMill. at a concentration up to 65 %; oil from
reaction is utilized in the manufacture of (−)- Pinus pinaster Soland. and American oil from
carvone from (+)-limonene (see page 35). Pinus caribaea contain 70 % and 70 – 80 %, re-
(+)-Limonene is obtained in large amounts spectively of the (−)-isomer [7785-26-4].
as a byproduct in the production of orange
juice; (−)-limonene is isolated in relatively
small quantities from essential oils. Racemic
limonenes, which are commercially available
under the name dipentene, are formed as
(by)products in many acid-catalyzed isomeriza- α-Pinene
tions of α- and β-pinene. Distillation of the so- α-Pinene undergoes many reactions, of
called dipentene fraction yields limonenes in which the following are used in the fragrance
varying degrees of purity. industry: Upon hydrogenation α-pinene is con-
The limonenes are used as fragrance mate- verted to pinane, which has become an important
rials for perfuming household products and as starting material in the industrial processes used
28 Flavors and Fragrances

in the fragrance and flavor industry. α-Pinene oil, and the santalols in sandalwood oil. Since
can be isomerized to β-pinene with high selec- these alcohols have not yet been synthesized on
tivity for β-pinene formation [73]. Hydration an industrial scale, they are described under the
with simultaneous ring opening yields terpineol oil in which they occur (Chap. 3). Some of their
and cis-terpin hydrate. Pyrolysis of α-pinene derivatives, however, are discussed in this sec-
yields a mixture of ocimene and alloocimene. tion.
Pure α-pinene is obtained by distillation of
turpentine oils (see page 118). As a fragrance Menthol, p-menthan-3-ol, C10 H20 O, M r
substance it is used to improve the odor of indus- 156.27, has three asymmetric carbon atoms in
trial products. However, it is far more important its cyclohexane ring and, therefore, occurs as
as a starting material in industrial syntheses, for four pairs of optical isomers. The configuration
example, terpineols (see page 33), borneol (see of four of these isomers is given below; the other
page 34), and camphor (see page 36). four are their mirror images.
β-Pinene [127-91-3], 2(10)-pinene, C10 H16 ,
M r 136.24, bp (101.3 kPa) 164 ◦ C, d 204 0.8712,
n20 20 ◦
D 1.4763, [α]D + or − 22.6 , occurs in many
essential oils. Optically active and racemic β-
pinenes are present in turpentine oils, although
in smaller quantities than α-pinene.
(−)-Menthol (+)-Neomenthol

β-Pinene
(+)-Isomenthol (+)-Neoisomenthol
β-Pinene is similar to α-pinene in its re-
actions. Pyrolytic cleavage of β-pinene to (−)-Menthol is the isomer that occurs most
myrcene, the starting material for acyclic ter- widely in nature. It is the main component of
penes, is used on an industrial scale. Addition of peppermint and cornmint oils obtained from the
formaldehyde results in the formation of nopol; Mentha piperita and Mentha arvensis species.
nopyl acetate is used as a fragrance material. Esterified menthol also occurs in these oils (e.g.,
β-Pinene is produced in large quantities by dis- as the acetate and isovalerate). Other menthol
tillation of turpentine oils. It is used as a fra- stereoisomers may be present in these oils as
grance material in household perfumery. How- well.
ever, most β-pinene is used in the production of Physical Properties. The eight optically ac-
myrcene. tive menthols differ in their organoleptic proper-
ties [74]. (−)-Menthol has a characteristic pep-
permint odor and also exerts a cooling effect.
2.3.2. Alcohols and Ethers The other isomers do not possess this cooling
effect and are, therefore, not considered to be
Although cyclic terpene alcohols occur widely “refreshing”. (±)-Menthol occupies an interme-
in nature, few have the physiological prop- diate position; the cooling effect of the (−)-
erties that make them important fragrance or menthol present is distinctly perceptible.
flavor compounds. Exceptions are α-terpineol The enantiomeric menthols have identical
and (−)-menthol, the latter because of its cool- physical properties (apart from their specific ro-
ing/refreshing effect. Of the bicyclic monoter- tation), but the racemates differ from the opti-
pene alcohols, borneol deserves mention. cally active forms in, for example, their melt-
Many cyclic sesquiterpene alcohols are key ing points. Although the differences between the
odor components in essential oils, for example, boiling points of the stereoisomers are small, the
cedrol in cedarwood oil, the vetiverols in vetiver four racemates can be separated from each other
 Flavors and Fragrances 29

by fractional distillation. Boiling points (in ◦ C is hydrogenated to form a mixture of mainly

at 101.3 kPa) are as follows: (−)-menthol and (+)- neomenthol; the (−)-
menthyl esters present (chiefly (−)-menthyl
Neomenthol 211.7
Neoisomenthol 214.6
acetate) are saponified. Additional (−)-
Menthol 216.5 menthol is then separated from other com-
Isomenthol 218.6 ponents by crystallization, distillation, or via
the boric acid esters.
Other physical constants of commer- 3) (−)-Menthol from (+)-Citronellal. This pro-
cially available levorotatory and racemic cess uses the readily occurring cyclization
menthols are: (−)-menthol [2216-51-5], mp of citronellal to isopulegol. (+)-Citronellal
43 ◦ C, n20 20 ◦
D 1.4600, [α]D − 50 ; (±)-menthol can be isolated with an optical purity of ca.
[15356-70-4], mp 38 ◦ C, n20D 1.4615. 80 % from citronella oil (see page 98). Al-
Chemical Properties. Hydrogenation of ternatively, it can be synthesized with a pu-
menthols yields p-menthane; oxidation with rity of 98 % from dialkylgeranylamine (ob-
chromic acid or catalytic dehydrogenation tained from myrcene and a dialkylamine)
yields menthones. Dehydration under mild con- by enantioselective isomerization to (+)-
ditions yields 3-p-menthene as the main prod- citronellaldialkylenamine followed by hy-
uct. Reaction with carboxylic acids or their drolytic cleavage to (+)-citronellal. Isomer-
derivatives yields menthyl esters, which are ization is effected in the presence of a chi-
used mainly as aroma substances and in phar- ral rhodium–phosphine complex as a cata-
maceutical preparations and formulations. The lyst [75]. (+)-Citronellal is cyclized in the
esterification of menthols with benzoic acid is presence of acidic catalysts (e.g., silica gel)
used on an industrial scale in the resolution of to give a mixture of optically active isopule-
racemic menthol. gol isomers containing ca. 20 % of the corre-
Production. Many industrial processes ex- sponding racemates:
ist for the production of menthols. For (−)-
menthol, isolation from peppermint oil (see Mint
Oils, page 107) competes with partial and total
syntheses. When an optically active compound
is used as a starting material, optical activity
must be retained throughout the synthesis, which
generally consists of several steps. Total synthe-
ses or syntheses starting from optically inactive
materials require either resolution of racemic
mixtures or asymmetric synthesis of an interme-
diate. Recently used processes are the following:
1) (−)-Menthol from Cornmint Oil. Mentha ar-
vensis oils, which may contain 70 – 80 %
free (−)-menthol, are cooled and the crystals
separated by centrifugation. Since the crys-
talline product contains traces of cornmint
oil, this menthol has a slightly herbaceous-
minty note. Pure (−)-menthol is obtained by
(−)-Isopulegol can be isolated from this mix-
recrystallization from solvents with low boil-
ture and hydrogenated to (−)-menthol. The
ing points.
remaining isopulegol stereoisomers can be
2) (−)-Menthol from Dementholized Corn-
partly reconverted into (+)-citronellal by py-
mint Oil. Dementholized cornmint oil, from
rolytic cleavage and reused in the cyclization
which (−)-menthol has been removed by
procedure [76].
crystallization and which still contains 40 –
The isopulegol mixture can also be hydro-
50 % free menthol, can be reused for pro-
genated to produce a mixture of menthols;
ducing (−)-menthol. The fairly large quan-
the individual stereoisomers are then sep-
tity of (−)-menthone in the oil (30 – 50 %)
30 Flavors and Fragrances

arated by distillation. To obtain optically

pure (−)-menthol, a resolution step involv-
ing a suitable crystalline derivative (such
as the benzoate) is required. The unde-
sired stereoisomeric menthols, mainly (+)-
neomenthol and (+)-isomenthol, are epimer-
ized to an equilibrium mixture (e.g., by heat-
ing in the presence of sodium menthylate). The remaining isomeric menthols, neo-
(−)-Menthol is then again separated from the menthol, isomenthol, and a trace of
mixture. neoisomenthol, can be epimerized, under
4) (−)-Menthol from (−)-Piperitone or Piperi- the conditions used for the thymol hydro-
tol. (−)-Menthol can also be prepared from genation, to give ca. 6 : 3 : 1 equilibrium
(−)-piperitone, the main component of Eu- mixture of (±)-menthol, (±)-neomenthol,
calyptus dives Typus oils. Hydrogenation in and (±)-isomenthol, respectively. (±)-
the presence of Raney nickel yields a mixture Menthol can, again, be distilled from the
of menthols, from which (−)-menthol can be equilibrium mixture.
separated by crystallization and saponifica- b) (±)-Menthol can be resolved into its opti-
tion of its chloroacetate. cal antipodes by several routes. A large-
Analogously, (+)-trans-piperitol (obtained scale industrial process utilizes selec-
from α- or β-phellandrene via piperityl chlo- tive crystallization of either (+)- or (−)-
ride [77]) can be hydrogenated to give a mix- menthyl benzoate by seeding saturated
ture of 97 % (+)-isomenthol and 3 % (+)- solutions or supercooled melts of (±)-
menthol. Pure (+)-isomenthol is obtained menthyl benzoates with crystals of (+)-
by crystallization and undergoes rearrange- or (−)-menthyl benzoate. Pure (+)- or
ment to give an equilibrium mixture of (+)- (−)-menthol is obtained following hydro-
neomenthol and (−)-menthol; the latter is lysis of the esters [79]. The undesired
separated by distillation. (+)-menthol can be reconverted into the
5) (−)-Menthol from (+)-3-Carene. An In- racemate. Biochemical resolution meth-
dian manufacturing process for (−)-menthol ods have also been developed [80].
starts from 3-carene, the major component
of Indian turpentine oil (55 – 65 %). (+)-3- Uses. Because of its cooling and refreshing
Carene isomerizes to (+)-2-carene, which effect, (−)-menthol is used in large quantities
can be pyrolyzed to (+)-trans-2,8-p-mentha- in cigarettes, cosmetics, toothpastes, chewing
diene. Isomerization of the latter yields gum, sweets, and medicines. (±)-Menthol can
(+)-isoterpinolene, which is hydrogenated be used in medicines and liniments.
to give > 50 % (+)-3-p-menthene. Epoxi-
dation and subsequent rearrangement lead Isopulegol, 8-p-menthen-3-ol, C10 H18 O,
to a menthone–isomenthone mixture, which M r 154.25, pure (−)-isopulegol [89-79-2], bp
gives a mixture of menthols when it is cat- (1 kPa) 74 ◦ C, d 26 26
4 0.9062, nD 1.4690, [α]D
26
◦
alytically hydrogenated. Fractional distilla- − 23.6 . Like menthol, isopulegol has three
tion and crystallization yield commercially asymmetric carbon atoms and, therefore, four
acceptable (−)-menthol [78]. stereoisomers, each occurring as a pair of opti-
6) (−)-Menthol from (±)-Menthol. (±)- cally active antipodes.
Menthol can be prepared via several routes
and subsequently resolved into the optical
isomers:
a) Racemic menthol can be synthesized by
hydrogenation of thymol. This yields a
mixture containing the four stereoiso-
meric menthols in various proportions.
The isopulegols occur in a large number of
(±)-Menthol is separated from the other
essential oils, often in optically active or part-
isomers by distillation.
 Flavors and Fragrances 31

ly racemic form. Since citronellal readily cy- of γ-terpineol. This mixture has a stronger lilac
clizes to isopulegol, the latter occurs frequently odor than does pure crystalline α-terpineol.
in citronellal-containing essential oils, in which Hydrogenation of α-terpineol yields p-
it is formed during the recovery of the oil. menthan-8-ol. Terpineol is readily dehydrated
Isopulegol produced industrially from (+)- by acids, yielding a mixture of unsaturated cy-
citronellal is a mixture of isomers containing clic terpene hydrocarbons. Under mildly acidic
a high percentage of (−)-isopulegol. The isop- conditions, terpin hydrate is formed. The most
ulegols are colorless liquids with a minty- important reaction for the fragrance industry is
herbaceous odor. They are converted into the esterification, particularly acetylation to terpinyl
corresponding menthols by means of hydrogen- acetate.
ation. Cyclization of citronellal, in the presence Production. Although α-terpineol occurs in
of acidic catalysts, yields a mixture of isomeric many essential oils, only small quantities are
isopulegols; (+)-citronellal obtained syntheti- isolated, e.g., by fractional distillation of pine
cally or from citronella oil is most frequently oils.
used as the starting material. A common industrial method of α-terpineol
Isopulegol is used in perfumery in various synthesis consists of the hydration of α-pinene
blossom compositions, as well as for geranium or turpentine oil with aqueous mineral acids to
notes. It is an important intermediate in (−)- give crystalline cis-terpin hydrate (mp 117 ◦ C),
menthol production. followed by partial dehydration to α-terpineol.
Suitable catalysts are weak acids or acid-
Terpineols are unsaturated monocyclic ter- activated silica gel [81].
pene alcohols and are formed by acid-catalyzed
hydration of pinenes; α-, β-, γ-, and δ-isomers
exist:

Selective conversion of pinene, 3-carene, and

limonene or dipentene to terpineol, without ter-
α- and β-Terpineol occur in optically ac- pin hydrate formation, is also used. Addition
tive forms and as racemates. α-Terpineol is of organic acids (weak acids require catalytic
an important commercial product. It occurs in amounts of mineral acids) produces terpinyl es-
a large number of essential oils, primarily as ters, which are subsequently hydrolyzed to ter-
(−)-α-terpineol (for example, in conifer and la- pineol, sometimes in situ.
vandin oils). Small quantities of (+)- and (±)-α- Uses. Terpineol with its typical lilac odor is
terpineol are found in many other essential oils; one of the most frequently used fragrance com-
β-, γ-, and δ-terpineol do not occur widely in pounds. It is stable and inexpensive, and is used
nature. in soaps and cosmetics.

α-Terpineol [98-55-5], 1-p-menthen-8-ol, 1-Terpinen-4-ol [562-74-3], 1-p-menthen-

C10 H18 O, M r 154.25, mp (pure enantiomers) 4-ol, C10 H18 O, M r 154.25, bp (101.3 kPa)
40 – 41 ◦ C, mp (racemate) 35 ◦ C, bp (101.3 kPa) 212 ◦ C, bp (500 Pa) 73.5 ◦ C, d 20 0.9315, n20 D
218 – 219 ◦ C, d 20
4 0.9357, n20 D 1.479, [α]D 1.4799, occurs as (+)-, (−)-, and racemic 1-
◦
+ 106.4 (solution in ether, 4 %) is a colorless, terpinen-4-ol in many essential oils (e.g., from
crystalline solid, smelling of lilac. The most im- Pinus and Eucalyptus species) and in lavender
portant commercial grade of terpineol consists oil. It is a colorless liquid with a spicy, nutmeg-
of a liquid mixture of isomers, that contains like, woody-earthy, and also lilac-like odor.
mainly α-terpineol and a considerable amount
32 Flavors and Fragrances

1-Terpinen-4-ol is a byproduct in the syn- often levorotatory ([α]20 ◦

D − 18 to − 28 in eth-
thesis of terpineol from terpin hydrate, and oc- anol), and contains (−)-borneol and up to 40 %
curs in commercial terpineol. Pure 1-terpinen- isoborneol.
4-ol can be prepared from terpinolene by pho- Borneol is oxidized to camphor with chromic
tosensitized oxidation, reduction of the re- or nitric acid; dehydration with dilute acids
sulting 1-methyl-4-isopropenyl-1-cyclohexene- yields camphene. Borneol is readily esterified
4-hydroperoxide, and selective hydrogenation with acids, but on an industrial scale bornyl es-
of the corresponding alcohol [82]. ters are prepared by other routes. For exam-
ple, levorotatory borneol is synthesized indus-
trially from levorotatory pinenes by Wagner-
Meerwein rearrangement with dilute acid, fol-
lowed by hydrolysis of the resulting esters [83].

It is used, for example, in artificial geranium

and pepper oils and in perfumery for creating Borneol is used in the reconstitution of the
herbaceous and lavender notes. essential oils in which it occurs naturally.

Borneol [507-70-0], 2-bornanol, C10 H18 O, Cedryl methyl ether [19870-74-7], 1H-
M r 154.25, mp (pure enantiomers) 208 ◦ C, mp 3a,7-methanoazulene, octahydro-6-methoxy-
(racemate) 210.5 ◦ C, d 20 20
4 1.011, [α] D + or
3,6,8,8-tetramethyl-(6β), and [67874-81-1],
− 37.7 ◦ , is a bicyclic terpene alcohol. Borneol 1H-3a,7-methanoazulene, octahydro-6-
is an endo isomer; the corresponding exo isomer methoxy-3,6,8,8-tetramethyl-(6α), C16 H18 O,
is isoborneol [124-76-5]: M r 236.40, d 25 20
25 0.974 – 0.979, nD 1.494 – 1.498,
is a colorless liquid with a fine cedarwood odor
and a distinct amber nuance. It is prepared by
methylation of cedrol and is used in perfumes,
soaps, and cosmetics.
Trade Name. Cedramber (IFF).
(−)-Borneol (+)-Isoborneol

Borneol occurs abundantly in nature as a sin-

gle enantiomer or, less frequently, as the race-
mate. (−)-Borneol [464-45-9] occurs particu-
larly in oils from Pinaceae species and in cit-
ronella oil. (+)-Borneol [464-43-7] is found, for
example, in camphor oil (Hon-Sho oil), in rose-
mary, lavender, and olibanum oils. 2.3.3. Aldehydes and Ketones
Borneol is a colorless, crystalline solid. (+)-
Borneol has a camphoraceous odor, with a Cyclic terpene aldehydes occur in essential oils
slightly sharp, earthy-peppery note, which is less only in low concentration. These aldehydes are
evident in (−)-borneol. Commercial borneol is seldom used as single fragrance compounds.
 Flavors and Fragrances 33

A few of the cyclic terpene ketones are com- The menthones are converted into the corre-
mercially important as fragrance and flavor sponding menthols by hydrogenation; for exam-
compounds, for example, menthone and car- ple, (−)-menthone yields (+)-neomenthol and
vone, which have the p-menthane skeleton, and (−)-menthol. (−)-Menthone can be obtained
the ionones, which have a (trimethylcyclohex- by distillation of dementholized cornmint oil
enyl)alkenone skeleton. The ionones and their or by oxidation of (−)-menthol (e.g., with
methyl-substituted homologues are some of the chromic acid). Dehydrogenation of (−)-menthol
most valuable fragrance materials. Some cy- (e.g., with copper chromite) yields a mixture
clic terpene ketones are the main components of (−)-menthone and (+)-isomenthone. (±)-
of essential oils (e.g., camphor in camphor oil); Menthone is prepared analogously from (±)-
others, although not main components, may be menthol. However, it can also be synthesized
essential for a fragrance (e.g., β-damascenone, by hydrogenation of thymol in the presence of
which is an important component of Bulgarian palladium–carbon catalysts [84].
rose oil; see Rose Oils, page 114). The cyclic Menthone and isomenthone are used for syn-
sesquiterpene ketone, nootkatone, is one of the thetic peppermint oils and bases.
characteristic components of grapefruit aroma.
Carvone, 1,8-p-menthadien-6-one, C10 H14 O,
Menthone, p-menthan-3-one, C10 H18 O, M r M r 150.22, bp (101.3 kPa) 230 ◦ C, d 204 0.960,
154.25, exists as two stereoisomers, menthone n20
D 1.499, [α] 18
D (+)-carvone + 64.3 ◦
, [α]20
D
◦
and isomenthone, each of which occurs as a pair (−)-carvone − 62.5 , occurs as (+)-carvone
of enantiomers, due to the two asymmetric cen- [2244-16-8], (−)-carvone [6485-40-1], or
ters present in the molecule. racemic carvone [22327-39-5]. The optical iso-
mers differ considerably in their organoleptic
properties. They occur in high percentages in
a number of essential oils. (+)-Carvone is the
main component of caraway oil (ca. 60 %) and
dill oil; (−)-carvone occurs in spearmint oil at a
concentration of 70 – 80 %.
(−)-Menthone (+)-Isomenthone Properties. The carvones are colorless to
slightly yellow liquids. (+)-Carvone has an
Both stereoisomers occur in many essen- herbaceous odor reminiscent of caraway and dill
tial oils, often as a single enantiomer species. seeds, whereas (−)-carvone has a herbaceous
A particularly high concentration (sometimes odor reminiscent of spearmint. Depending on
> 50 %) is found in oils from Mentha species. the reaction conditions, hydrogenation of car-
The menthones are colorless liquids that possess vone yields either carveols or dihydrocarvone,
a typically minty odor; the odor of isomenthone which are also used as flavor compounds. When
is slightly musty. They have a strong tendency treated with strong acids, carvone isomerizes to
to interconvert and are, therefore, difficult to ob- carvacrol.
tain in high purity. Industrial products are mix- Production. In the past, (+)- and (−)-
tures of varying composition. Physical constants carvones were isolated by fractional distillation
of industrially important menthone isomers are of caraway oil and spearmint oil, respectively.
listed in Table 1. However, these carvones are now prepared syn-

Table 1. Physical properties of industrially important menthone isomers

Compound CAS registry number bp (101.3 kPa), ◦ C d 20

t n20
D [α]D

(−)-Menthone [14073-97-3] 210 0.896∗ 1.450 − 28.5 ◦

(±)-Menthone [1074-95-9] 210 0.896∗ 1.450
(+)-Isomenthone [1196-31-2] 212 0.900∗∗ 1.453 + 95.0 ◦
(±)-Isomenthone [36977-92-1] 212 0.900∗∗ 1.453

∗t = 20 ◦ C; ∗∗t = 4 ◦ C
34 Flavors and Fragrances

thetically, the preferred starting material being Camphor is produced by fractional distil-
(+)- and (−)- limonenes, which are converted lation and crystallization of camphor oil (see
into the corresponding optically active carvones. page 90) or, synthetically, by dehydrogenation
Since optical rotation is reversed in the process, of isoborneol (from isobornyl acetate, see page
(+)-limonene is the starting material for (−)- 41) over a copper catalyst.
carvone. Due to its characteristic penetrating, slightly
The preferred industrial method of carvone minty odor, camphor is only used in perfuming
synthesis utilizes the selective addition of nitro- industrial products. It is far more important as a
syl chloride to the endocyclic double bond of plasticizer.
limonene. If a lower aliphatic alcohol is used as
solvent, limonene nitrosochloride is obtained in Fenchone [1195-79-5], 1,3,3-trimethylbicy-
high yield. It is converted into carvone oxime by clo[2.2.1]heptan-2-one, C10 H16 O, M r 152.24,
elimination of hydrogen chloride in the presence bp (101.3 kPa) 193 ◦ C, d 20 20
4 0.9484, nD 1.4628,
20 ◦
of a weak base. Acid hydrolysis in the presence [α]D + or − 66.8 , occurs as its (−)-isomer in
of a hydroxylamine acceptor, such as acetone, a number of fennel oils. It is a colorless, slightly
yields carvone [85]. viscous liquid with a camphoraceous odor.

(+)-Fenchone

(+)-Fenchone [7787-20-4] containing a small

amount of the (−)-isomer [4695-62-9] is pre-
pared by dehydrogenation of (−)-fenchol. (−)-
Fenchyl esters are obtained, along with other
compounds, by addition of carboxylic acids to
α-pinene. Hydrolysis of the esters yields (−)-
fenchol.
Fenchone is used to prepare artificial fennel
oils and to perfume household products.

Ionones and Homologous Compounds.

Uses. Both (+)- and (−)-carvone are used to The C13 ketones α- and β-ionone are cyclic
flavor a number of foods and beverages. (−)- terpenoids that occur in many essential oils.
Carvone is produced in much larger quantities However, being metabolites of the correspond-
and is also used in oral hygiene products. ing carotenoids [86], they occur in only small
amounts. A third isomer, γ-ionone, has not yet
Camphor [21368-68-3], 1,7,7-trimethyl- been observed in nature.
bicyclo[2.2.1]heptan-2-one, C10 H16 O, M r
152.24, (+)-camphor: bp (101.3 kPa) 204 ◦ C,
mp 178.8 ◦ C, [α]20 ◦
D + 44.3 ; both optical iso-
mers are found widely in nature, (+)-camphor
[464-49-3] being the more abundant. It is, for
example, the main component of oils obtained α-Ionone β-Ionone
from the camphor tree Cinnamomum camphora.

γ-Ionone

Both optical isomers of α-ionone are found in

(+)-Camphor nature. Generally, ionones have a trans config-
 Flavors and Fragrances 35

uration. trans-α-Ionone can be converted into Other ionone homologues are the methyl-
the cis-isomer by exposure to ultraviolet light. ionones, in which the oxoalkenyl group carries
Under the same conditions, trans-β-ionone re- an extra methyl substituent. The methylionones
arranges to the retro compound. also exist as α-, β-, and γ-isomers, each of which
The irones are ionone homologues that have can occur in the cis or trans form; the isomers
an additional methyl group adjacent to the twin may also be optically active. Their natural oc-
methyl groups in the cyclohexane ring. The currence is debated [87].
number of possible irone isomers is larger than All ionones, irones, and methylionones, as
that of the ionones due to the additional methyl well as the corresponding pseudocompounds
group on the ring. Some of these irone isomers (their synthetic acyclic precursors) are slightly
occur in essential oils from the roots of Orris viscous yellowish liquids. Commercial irones
species (see Orris Root Oil, page 111). and methylionones are mixtures of isomers that
are named according to their main component.
Their composition varies with the method used
to prepare and cyclize the pseudocompound and
fluctuates considerably between different manu-
facturers.
Physical and Chemical Properties. Physical
Irone, α-, β-, γ- n-Methylionone, α-, β-, γ-
and odor properties of the best known ionones
are listed in Table 2.
β-Ionone is converted into intermediates for
vitamin A synthesis (→ Vitamins, Chap. 2.7.2.).
The hydrogenation of ionones and methyl-
Isomethylionone, α-, β-, γ- ionones is of some importance. Dihydro or tet-
rahydro derivatives or ionols can be obtained de-
pending on reaction conditions.

Table 2. Physical properties of ionones

Name Formula CAS registry Mr bp ◦ C (p, kPa) d 20

4 n20
D Odor
number

α-Ionone C13 H20 O [127-41-3] 192.30 121 – 122 (1.3) 0.9319 1.4982 sweet-floral, reminiscent of violet
β-Ionone C13 H20 O [79-77-6] 192.30 121.5 (0.93) 0.9461 1.5202 reminiscent of cedarwood, violet-like
upon dilution
γ-Ionone C13 H20 O [79-76-5] 192.30 82 (0.16) 0.9317 1.4985 violet-like with woody-resinous
tonality (intermediate in the synthesis
of γ-dihydroionone, a component of
ambergris)
α-Irone C14 H22 O [79-69-6] 206.33 109 (0.36) 0.9340 1.4998 responsible for the fragrance of natural
orris oil
β-Irone C14 H22 O [79-70-9] 206.33 108 – 109 (0.21) 0.9465 1.5183 reminiscent of β-ionone, but slightly
more intense
α-n-Methyl- C14 H22 O [127-42-4] 206.33 97 (0.35) 0.9210 a 1.4938 b reminiscent of α-ionone, but milder
ionone and more delicate
β-n-Methyl- C14 H22 O [127-43-5] 206.33 102 (0.35) 0.9370 1.5155 β-ionone-like, but with a distinct
ionone leather note
α-Isomethyl- C14 H22 O [127-51-5] 206.33 130 – 131 (1.3) 0.9345 1.5019 reminiscent of orris and violets,
ionone possesses the finest odor of all ionones
β-Isomethyl- C14 H22 O [79-89-0] 206.33 94 (0.4) 0.9376 1.5053 interesting, powdery, orris-like odor
ionone with slightly woody aspects
Allylionone c C16 H24 O [79-78-7] 232.35 102 – 104 (0.02) 0.9289 1.5040 floral violet odor with a fruity
pineapple note and high tenacity
a
d 25
4
b
n25
D
c
Obtained by cyclization of allylpseudoionone (from citral and allylacetone)
36 Flavors and Fragrances

With Raney nickel–copper chromite cata-

lysts, methylionones are converted into tetra-
hydromethylionols, which are also used as fra-
grance materials [88].
Production. Ionones, irones, and methyl-
ionones, as well as allylionone, are all produced
by analogous routes. Special procedures must
be used to obtain a particular isomer, either pure
or as the main component. These are described
where appropriate.
In all processes an acyclic precursor, called
a pseudoionone, pseudoirone, etc., is prepared
by base-catalyzed condensation of citral or 6-
methylcitral with acetone, methyl ethyl ketone,
or allylacetone, as appropriate. In the methylionone synthesis, condensa-
tion of citral with methyl ethyl ketone results
in a mixture of n-methyl- and isomethylpseu-
doionone, each of which may occur as one of
four possible cis–trans-isomers.

In the synthesis of vitamin A, the dependence

on natural sources as well as steadily increasing
production via β-ionone as an intermediate have
led to the development of a method for synthe-
sizing citral from dehydrolinalool (see page 21).
More recent routes employ dehydrolinalool as
the starting material for pseudoionone. Dehy-
drolinalool is converted into pseudoionone by
using either diketene [89] or a suitably substi-
tuted acetoacetate (Carroll reaction) [90]:

The ratio of the major isomers in the mix-

ture depends on the condensation catalyst and
the reaction conditions. In the presence of com-
mon alkaline catalysts (e.g., sodium hydrox-
ide), straight-chain isomers are formed prefer-
entially. Strongly alkaline catalysts, such as qua-
ternary ammonium bases, favor the formation of
isomethylpseudoionone [92]. This compound is
a precursor for the highly valued fragrance sub-
stance α-isomethylionone and can be obtained
as the main component by reacting dehydroli-
nalool with the enol ether of methyl ethyl ke-
tone and methanol [93]. Acidic and Lewis cat-
alysts are employed in the cyclization of the
pseudocompounds to the cyclic ketones. The
A milder reaction for synthesizing pseu- primary cyclization products are α-ionone or
doionone from dehydrolinalool is transetherifi- its homologues, which are isomerized to the β-
cation with an alkoxyalkene [91]: compounds by strong acids. Concentrated sul-
 Flavors and Fragrances 37

furic acid converts pseudoionone almost ex-

clusively into β-ionone; 85 % phosphoric acid
yields α-ionone in ca. 80 % purity. γ-Ionone can
be obtained together with a small amount of α-
and β-ionone when boron trifluoride etherate is
used as the catalyst and dimethylformamide as
the solvent [94]; γ-ionone is of little commercial
importance. Since α- and β-ionone can be sepa-
rated on an industrial scale by fractional distilla-
tion in high-performance columns, other meth-
ods of separation are seldom used.
Uses. The volume of the production of β-
ionone, which serves as an intermediate in vita-
min A synthesis, shows that it is by far the most
important. The ionones and their homologues
are components of blossom and phantasy per-
fume compositions. The ionones and irones are
used in aroma compositions as well, although on
a much smaller scale. α-Ionone is a highly val-
ued fragrance material. The methylionones are β-Damascenone [23726-93-4], 1-(2,6,6-
among the most important fragrance substances, trimethyl-1,3-cyclohexadienyl)-2-buten-1-one,
α-isomethylionone being the most important. C13 H18 O, M r 190.28, is a constituent of Bul-
The irones, isomers of the methylionones, are garian rose oil, which has a powerful fragrance
produced in limited quantities, mainly due to although it is only present at a concentration of
their high cost. Likewise, allylionone is manu- 0.05 %.
factured in small amounts. It is used in small quantities in flavor and
perfume compositions to impart naturalness and
Damascones, 1-(2,6,6-trimethylcyclohex- brilliance. (IFRA recommendation)
enyl)-2-buten-1-ones, C13 H20 O, M r 192.30,
are ionone isomers. Damascone exists in α-,
β-, γ-, δ-, and ε-forms, depending on the po-
sition of the double bond in the cyclohexane
ring. Commercially important are α-damascone
[43052-87-5], β-damascone ( [23726-91-2] for
Nootkatone [4674-50-4], 5,6-dimethyl-
(E) and δ-damascone [57378-68-4] as mixtures
8-isopropenylbicyclo[4.4.0]-1-decen-3-one,
of their cis- and trans-isomers.
C15 H22 O, M r 218.33, mp 35 ◦ C, has been iso-
The α- and β-damascones have been identi-
lated from grapefruit peel and juice and iden-
fied as components of tea aroma. They are liq-
tified in other citrus oils as well. The com-
uids with a fruity, roselike odor. One synthetic
mercially available product is a colorless to
route to the damascones starts with an appropri-
yellowish liquid with a typical grapefruit odor.
ate cyclogeranic acid derivative (halide, ester,
Nootkatone can be prepared by oxidation of
etc.). This is reacted with an allyl magnesium
valencene, a sesquiterpene hydrocarbon isolated
halide to give 2,6,6-trimethylcyclohexenyl dial-
from orange oils. (IFRA recommendation)
lyl carbinol, which on pyrolysis yields the de-
sired 1-(2,6,6-trimethylcyclohexenyl)-3-buten-
1-one. Damascone is otained by rearrangement
of the double bond in the side-chain [95].
The damascones are used in perfume compo-
sitions, especially rose perfumes, and in flavor
compositions, to which they impart naturalness
and body. (IFRA recommendation) Nootkatone is used for flavoring beverages.
38 Flavors and Fragrances

Cedryl methyl ketone, C17 H26 O, M r (±)-Menthyl acetate [29066-34-0] occurs

246.39, is a long-lasting wood fragrance which in essential oils. It is synthesized by esterifica-
is prepared by acetylation of cedarwood oil tion of racemic menthol. Its odor is crisper and
fractions that contain sesquiterpene hydrocar- less fruity than that of (−)-menthyl acetate. It
bons, mainly α-cedrene and thujopsene (for is used for essential oil compositions and occa-
structures, see Section 2.3.1). Acetylation is sionally in household perfumery.
carried out in the presence of an acidic cata-
lyst (e.g., polyphosphoric acid). Commercially p-Menthanyl acetate, C12 H22 O2 , M r
available cedryl methyl ketone is a multicom- 198.30, bp (200 Pa) 67 – 70 ◦ C, d 25 25 0.931 –
ponent mixture. The main component is 1- 0.937, n20
D 1.446 – 1.451, is commercially avail-
(2,6,6,8-tetramethyltricyclo[5.3.1.01,5 ]undec- able as a cis–trans mixture of p-menthan-1-yl
8-en-9-yl)ethan-1-one [32388-55-9]. One acetate [26252-11-9] (1) and p-menthan-8-yl ac-
of its odor-determining compounds is 1- etate [80-25-1] (2). It is a colorless liquid with a
(2,2,8-trimethyltricyclo[6.2.2.01,6 ]dodec-5-en- citrus-fresh, pine-needle odor and a secondary,
5-yl)ethan-1-one [32388-56-0]: slightly herbaceous note. Menthanyl acetate is
produced by hydrogenation of terpinyl acetates
(mixtures of isomers) (e.g., in the presence of
Raney nickel [96]) or by esterification of a mix-
ture of isomeric p-menthanols.

Trade Names. Lignofix (Dragoco), Lixetone

(Quest), Vertofix (IFF).

2.3.4. Esters

Esters derived from cyclic terpene alcohols, es-

pecially the acetates, are common fragrance and The ester mixture is highly stable and is,
flavor components. Menthanyl, menthenyl, bi- therefore, used in perfumery for detergents and
cyclic bornyl acetates, and a few acetates of other household products.
sesquiterpene alcohols are extensively used in
perfume and aroma compositions. α-Terpinyl acetate [80-26-2], 1-p-
menthen-8-yl acetate, C12 H20 O2 , M r 196.29, bp
(−)-Menthyl acetate [2623-23-6], (−)-p- (5.3 kPa) 140 ◦ C, d 20 21 20
4 0.9659, nD 1.4689, [α]D
menthan-3-yl acetate, C12 H22 O2 , M r 198.30, bp ◦
of the enantiomers + or − 79 ; the enantiomers
(3 kPa) 116 ◦ C, d 20 20
4 0.9253, nD 1.4467 – 1.4468, and the racemate occur in many essential oils
20 ◦
[α]D − 81.1 , occurs in peppermint oils. It is a (e.g., Siberian pine needle oil and cypress oil),
colorless liquid with a fresh-fruity, peppermint but generally not as the main component. Pure
odor. α-terpinyl acetates are colorless liquids with
(−)-Menthyl acetate is prepared by acety- a fresh bergamot-lavender odor. Commercially
lation of (−)-menthol (e.g., with acetic anhy- available terpinyl acetate consists mainly of α-
dride). It is used mainly in peppermint flavors terpinyl acetate, but also contains a number of
and reconstituted peppermint oils, but also to a other isomeric compounds. It can be prepared by
small extent in perfumery. acetylating the terpineol mixture obtained from
terpin hydrate, using a customary procedure for
tertiary alcohols.
Because of its odor properties, stability, and
low price, large quantities of terpinyl acetate are
used in perfumery for lavender and bergamot
types, as well as in essential oil reconstitutions.
 Flavors and Fragrances 39

Isobornyl acetate [125-12-2], 2-exo-

bornanyl acetate, C12 H20 O2 , M r 196.29, bp
(1.6 − 1.7 kPa) 102 – 103 ◦ C, d 20 4 0.9841, nD
20

1.4640, has been identified in a number of es-

sential oils. It is a colorless liquid with a pleasant,
pine-needle odor. Isobornyl acetate is prepared
from camphene and acetic acid in the presence
Nopyl acetate [35836-72-7], (−)-2-(6,6- of acidic catalysts (e.g., sulfuric acid) [97], or
dimethylbicyclo[3.1.1]hept-2-en-2-yl)ethyl ac- ion-exchange resins (e.g., sulfonated styrene–
etate, C13 H20 O2 , M r 208.30, bp (1.5 kPa) divinylbenzene polymers) [98].
122 ◦ C, d 20 20
4 0.9811, nD 1.4733, [α]D − 30.9
◦

(CAS registry no. of racemate [128-51-8], is

not found in nature and has a fresh-fruity-
woody odor. (−)-Nopyl acetate is prepared by
acetylation of (−)-nopol with acetic anhydride.
(−)-Nopol is obtained from (−)-β-pinene and
paraformaldehyde in a Prins reaction. Nopyl ac-
etate is used in perfumes for soap and household
products. Isobornyl acetate is used in large amounts for
perfuming soap, bath products, and air freshen-
ers. However, the major use of isobornyl acetate
is as an intermediate in the production of cam-
phor.

Guaiyl acetate, C17 H28 O2 , M r 264.41, bp

(300 Pa) 118 – 123 ◦ C, d 2525 0.965 – 0.990, nD
20

Bornyl acetate, 2-endo-bornanyl acetate, 1.489 – 1.495, is obtained by esterification of

C12 H20 O2 , M r 196.29, bp (101.3 kPa) 223 – guaiac wood oil with acetic anhydride and con-
224 ◦ C, d 20 20 20
4 0.9838, nD 1.4630, [α] D + or
sists of the acetates of the natural sesquiterpene
◦ ◦
− 44.4 , mp (+)- and (−)-form 29 C, occurs alcohols guaiol and bulnesol (see Guaiac Wood
in its optically active forms and as a racemate in Oil, page 103). Guaiyl acetate is a yellow to
many essential oils. amber-yellow liquid with a weak but lasting,
woody odor. It is used in perfumery for tea-rose
and wood nuances.

Cedryl acetate [77-54-3], C17 H28 O2 , M r

264.41, bp (400 Pa) 146 – 150 ◦ C, d 2525 0.966 –
1.012, n20
D 1.495 – 1.506, occurs in cedarwood
(−)-Bornyl acetate
oils. The pure compound is crystalline (mp
(−)-Bornyl acetate [5655-61-8] is a charac- 80 ◦ C). Commercial cedryl acetate is a color-
teristic component of most conifer oils. It has less to amber-yellow liquid, with a cedarwood-
a camphoraceous, pine-needle-like odor. Both like odor. It is prepared by esterification of the
(+)-bornyl acetate [20347-65-3] and (−)-bornyl cedrol-rich fraction from cedarwood oil and is
acetate form colorless crystals; the racemate used in perfumery for wood and leather notes,
[36386-52-4] is a colorless liquid. Bornyl ac- and as a fixative.
etate is prepared by esterification of borneol with
acetic anhydride or via the process described un-
der borneol (see page 34).
Due to its characteristic pine needle odor,
bornyl acetate is frequently used in conifer nee-
dle compositions, soap, bath products, room
sprays, and pharmaceutical products.
40 Flavors and Fragrances

Vetiveryl acetate [62563-80-8], bp (300 Pa) This powerful fragrance and flavor substance
125 – 128 ◦ C, d 25 20
25 0.979 – 1.015, nD 1.5050 – is used in perfume and aroma compositions.
1.5180, is not a single compound; its main com-
ponent is khusimyl acetate [61474-33-7]. Ve- 1-p-Menthene-8-thiol [71159-90-5],
tiveryl acetate is prepared by esterification of C10 H18 S, M r 170.31, bp (45 Pa) 40 ◦ C, d 20 4
the sesquiterpene alcohols isolated from vetiver 0.948, n20D 1.503, has been identified in grape-
oils. fruit juice. It is a liquid with an extremely pow-
erful, obnoxious odor; when diluted it has the
typical aroma of fresh grapefruit juice. Its odor
threshold value is extremely low: 2×10−5 µg/kg
for the (+)-R and 8×10−5 µg/kg for the (−)-S
isomer [100].
Khusimyl acetate

Vetiveryl acetate is a light yellow liquid with a

dry, fresh-woody odor. It is a popular fragrance
mixture that is frequently used in luxury per-
fumery; it is also used as a fixative in many fine
fragrances. (Limiting IFRA recommendation)

2.3.5. Miscellaneous Compounds 2.4. Other Cycloaliphatic Compounds

Of the few known terpene compounds that In addition to cyclic terpenoids, several other
contain heteroatoms such as nitrogen or sul- cycloaliphatic compounds have above-average
fur, the thiol 8-mercapto-p-menthan-3-one de- importance as fragrance materials; some of them
scribed below has qualitatively important ap- are structurally related to the terpenes. Ketones
plications as a fragrance and flavor substance. are most widely represented and include cyclo-
The second thiol, 1-p-menthene-8-thiol, is de- pentanone derivatives, such as the jasmin fra-
scribed because its odor threshold value is far grance compounds, and cyclic ketones with 15 –
lower than that of most other fragrance and fla- 17-membered carbon rings, such as muscone
vor compounds. [541-91-3] and civetone [542-46-1], which are
constituents of the extremely expensive animal
8-Mercapto-p-menthan-3-one [38462-22- products, musk and civet.
5], C10 H18 OS, M r 186.31, bp (13 Pa) 57 ◦ C,
is an essential odoriferous constituent of buchu
leaf oil. The commercial product is synthesized
from pulegone and is a liquid mixture of cis–
trans-isomers with a typical blackcurrant odor. Muscone Civetone
8-Mercapto-p-menthan-3-one is prepared by re-
acting pulegone with hydrogen sulfide in the Many syntheses have been devised for these
presence of a base (e.g., triethylamine) [99]: macrocyclic ketones. However, due to the many
steps involved and poor yields, they are not
used widely on an industrial scale. Cyclopen-
tadecanone, a natural musk fragrance, and the
unsaturated 5-cyclohexadecen-1-one, which has
not yet been found in nature, are more easily
synthesized. Their odor characteristics are sim-
ilar to those of muscone and civetone and are,
therefore, used instead of them.
A few alicyclic aldehydes are valuable per-
fume materials and are obtained by Diels – Alder
 Flavors and Fragrances 41

reactions using terpenes and acrolein. Esters de- Compound 3 can be used either in a pure state
rived from hydrogenated aromatic compounds, or as a mixture with its byproduct 4 in perfume
such as tert-butylcyclohexyl and decahydro-β- compositions and soap perfumes.
naphthyl acetates, are also used in large amounts Trade Name. Sandalore (Givaudan Roure).
as fragrance materials.
2-Ethyl-4-(2,2,3-trimethyl-3-cyclopenten-
1-yl)-2-buten-1-ol [8219-61-6], C14 H26 O,
2.4.1. Alcohols M r 208.35, bp (3 kPa) 114 – 116 ◦ C, d 20 4
0.9160 – 0.9168, n20D 1.4870 – 1.4880, is an-
Some alicyclic alcohols are important as syn- other sandelwood-like fragrance also derived
thetic sandalwood fragrances. The annual world from campholenic aldehyde. Aldol condensa-
production of natural sandalwood oil is about tion of this aldehyde with butyric aldehyde gives
100 t with a current price of about $ 400 per kilo- an α,β-unsaturated carbonyl compound that can
gram. Due to the limitations of the harvest and be reduced to an unsaturated alcohol.
this highly fluctuating price, chemists have been
searching for cheap synthetic substitutes for this
important perfumery ingredient. Since the 1970s
a new class of sandalwood products has been de-
veloped, which all originate from campholenic
aldehyde, an easily available product of the re-
arrangement of α-pinene epoxide, catalyzed by
zinc chloride or zinc bromide.

5-(2,2,3-Trimethyl-3-cyclopenten-1-yl)-
3-methylpentan-2-ol [65113-99-7] (3),
C14 H26 O, M r 210.36, d 20 4 0.896 – 0.904, n20
D
1.470 – 1.476, is a fragrance ingredient that does
not occur in nature. It is prepared by condensa-
tion of campholenic aldehyde with methyl ethyl
ketone, followed by selective hydrogenation of
the resulting unsaturated ketone [101]. Trade Names. Bacdanol (IFF), Bangalol
(Quest), Sandolene (Haarmann & Reimer), San-
dranol (DRAGOCO).
In addition some other materials of this type
are on the market:

Trade Name. Brahmanol (DRAGOCO).

Trade Name. Polysantol (Firmenich).

Trade Name. Ebanol (Givaudan Roure).

42 Flavors and Fragrances

tent of 3-trans-isocamphylcyclohexanol [102].

Moreover, the process starting from guaia-
col has been improved by converting the
Trade Names. Madrol (DRAGOCO), Sandelice main component formed in the first step, p-
(Cognis). isocamphylguaiacol (5), into a mixed ether
(6) by reaction with diethyl sulfate. Nucle-
3-trans-Isocamphylcyclohexanol [3407- ophilic cleavage of the ether with alcoholates
42-9], C16 H28 O, M r 236.40, does not occur or Grignard reagents results in a high yield
in nature. A synthetic mixture of terpenylcy- of m-isocamphylguethol (7), which is hydro-
clohexanol isomers has a sandalwood odor. A genated catalytically, with concomitant loss of
commercially available mixture containing 3- the ethoxy group, to give a high yield of 3-trans-
trans-isocamphylcyclohexanol is prepared by isocamphylcyclohexanol (8) [103].
reacting camphene and guaiacol in the presence
of an acidic catalyst (e.g., boron trifluoride),
followed by catalytic hydrogenation of the re-
sulting terpenylguaiacols. In the alkylation re-
action, camphene rearranges to the isobornyl,
isofenchyl, and isocamphyl skeletons. These
substituents may be introduced in guaiacol at
four positions. In the subsequent hydrogenation
with simultaneous elimination of the methoxy
group, additional possibilities for isomerism
arise because the hydroxyl group may be either
axial or equatorial to the terpenyl moiety. There-
fore, the actual content of the desired isomer, The mixture is used as such in large amounts
3-trans-isocamphylcyclohexanol, is low in most as a replacement for sandalwood oil in soaps,
products. The other isomers are either weak in cosmetics, and perfume compositions.
odor or odorless. Trade Names. Sandela (Givaudan Roure),
Sandel H + R (Haarmann & Reimer), San-
diff (IFF), Rhodanthial (Rhodia), Santalex
(Takasago).

2.4.2. Aldehydes
2,4-Dimethyl-3-cyclohexene carboxalde-
hyde [68039-49-6], C9 H14 O, M r 138.21, bp
(4 kPa) 94 – 96 ◦ C, n25
D 1.4696, is prepared as a
mixture of its cis- and trans-isomers by a Diels –
Alder reaction of 2-methyl-1,3-pentadiene and
acrolein. It is a liquid with a strongly green,
slightly herbaceous, citrus note. It is used for per-
fuming cosmetic preparations as well as house-
hold products.

Trade Names. CyclalC (Givaudan Roure),

A process starting from catechol, instead of Ligustral (Quest), Triplal (IFF), Vertocitral
guaiacol, yields a mixture with a higher con- (Haarmann & Reimer).
 Flavors and Fragrances 43

4-(4-Methyl-3-penten-1-yl)-3-cyclohexene 2-heptylidenecyclopentanone, with subsequent

carboxaldehyde [37677-14-8], C13 H20 O, M r hydrogenation of the double bond.
192.30, is prepared, together with its 3-isomer,
by a Diels – Alder reaction of myrcene and
acrolein. The mixture has a fresh-fruity, slightly
citrus-like odor and is used to perfume house-
hold products. 2-Heptylcyclopentanone and its lower
mass homologues 2-pentyl- and 2-hexylcyclo-
pentanone are used in, for example, jasmin,
honeysuckle, and lavender compositions.
Trade Names. Fleuramone (IFF), Projasmon P
Trade Names. Empetal (Quest), Myrac aldehyde (Haarmann & Reimer).
(IFF), Vertomugal (Haarmann & Reimer).
Dihydrojasmone [1128-08-1], 3-methyl-
2-pentyl-2-cyclopenten-1-one, C11 H18 O, M r
4-(4-Hydroxy-4-methylpentyl)-3-cyclo-
166.26, bp (2.7 kPa) 87 – 88 ◦ C, d 25 0.9157, n25
D
hexene carboxaldehyde [31906-04-4] (9),
1.4771, is a colorless, slightly viscous liquid
C13 H22 O2 , M r 210.32, bp (130 Pa) 120 –
with a typical jasmin odor, resembling that of
122 ◦ C, d 20 20
4 0.9941, nD 1.4915, is a fragrance the naturally occurring cis-jasmone. Dihydro-
substance that does not occur in nature. It is
jasmone can be synthesized by various routes.
a colorless, viscous liquid with a sweet odor
A preferred method is intramolecular aldol con-
reminiscent of lily of the valley. The aldehyde
densation of 2,5-undecanedione, which can be
can be prepared by a Diels – Alder reaction of
prepared from heptanal and 3-buten-2-one in
myrcenol and acrolein in the presence of a Lewis
the presence of a thiazolium salt, such as 5-
catalyst (e.g., zinc chloride) [104]:
(2-hydroxyethyl)-4-methyl-3-benzylthiazolium
chloride [106]:

Reaction of myrcenol with acrolein at ele-

vated temperatures, without a catalyst, yields a
70 : 30 mixture of the 4- and 3-substituted cy-
clohexene carboxaldehydes [105]. This mixture
is a commercial product. Compound 9 has ex-
cellent fixative properties and is used especially
in soap and cosmetics perfumery. Dihydrojasmone is used in perfumery in jas-
Trade Names. Lyral (IFF), Kovanol (Takasago). min bases and, more generally, in blossomy and
fruity fragrances.

2.4.3. Ketones cis-Jasmone [488-10-8], 3-methyl-2-(2-cis-

penten-1-yl)-2-cyclopenten-1-one, C11 H16 O,
2-Heptylcyclopentanone [137-03-1], M r 164.25, bp (1.6 kPa) 78 – 79 ◦ C, d 20 0.9423,
C12 H22 O, M r 182.31, bp (1.3 kPa) 130 ◦ C, n20
D 1.4989, occurs in jasmin absolute and con-
d 20 0.890, n20
D 1.4530, is a fragrance mate-
tributes to its typical jasmin odor. It is a pale
rial with a fruity, slightly herbaceous, jasmin yellow, viscous liquid with a strong jasmin
odor; it has not yet been found in nature. It is odor. Various stereospecific syntheses for cis-
a colorless, viscous liquid prepared by conden- jasmone have been reported. A patented method
sation of cyclopentanone with heptanal to give involves alkylation of 3-methyl-2-cyclopenten-
1-one with cis-2-pentenyl chloride in an alkaline
44 Flavors and Fragrances

medium in the presence of a phase-transfer cat- 1,2,3,5,6,7-Hexahydro-1,1,2,3,3-penta-

alyst (e.g., tricaprylmethylammonium chloride) methyl-4H-inden-4-one [33704-61-9],
[107]: C14 H22 O, M r 206.32, d 20 20
4 0.962, nD 1.500, has
not yet been found in nature. It is colorless to
pale yellow solid to semi-solid mass with a dif-
fusive, spicy, musk-like odor with strong floral
reinforcement and powdery, velvet nuances.
The indenone 18 can be prepared by hydro-
genation of pentamethylindan (16) and subse-
quent oxidation of the intermediate 17 with air
over copper acetate to yield the corresponding
cis-Jasmone is used in perfumery in fine jas-
ketone 18 [109, 110].
min bases and floral compositions.

1-(5,5-Dimethylcyclohex-1-en-1-yl)pent-
4-en-1-one [56973-85-4], and 1-(3,3-di-
methylcyclohex-1-en-1-yl)pent-4-en-1-one
[56973-84-3], C13 H20 O, M r 192.30, d 20 4 1.490,
n 20
20 0.930. The isomeric mixture is a colorless
to pale yellow liquid with an extremely power-
ful and diffusive odor reminiscent of galbanum,
with a pineapple and hyacinth character.
The cyclic ketone can be formed by dehy-
dratization of dehydrolinalool (10), subsequent
alkylation of 11 with allyl chloride to form 12,
acid-catalyzed cyclization of (12) and hydroly-
sis of the product 13 to give a mixture of 14 and
15 [108].
Trade Name. Cashmeran (IFF).

Cyclopentadecanone [502-72-7], C15 H28 O,

M r 224.39, mp 65 – 67 ◦ C, bp (7 Pa) 85 ◦ C, is a
musk fragrance found in the scent gland of the
male civet cat.

Trade Name. Dynascone (Firmenich). A number of syntheses have been developed

for its manufacture. In a more recent method,
 Flavors and Fragrances 45

1,12-dodecanedial is reacted with 1,3-bis(di- 5-Cyclohexadecen-1-one [37609-25-9],

methylphosphono)propan-2-one in the presence C16 H28 O, M r 236.40, bp (10 Pa) 121 ◦ C, n25
D
of a base, preferably in two steps via the inter- 1.4865, is commercially available as a 40 : 60
mediates 15-(dimethylphosphono)pentadec-12- mixture of its cis- and trans-isomers. It is a
en-14-on-1-al and 2,14-cyclopentadecadien-1- colorless liquid with an intense musk odor.
one. Subsequent hydrogenation yields cyclo- A three-step synthesis starts from cy-
pentadecanone [111]. clododecanone (19). Reaction with chlorine
Cyclopentadecanone is used in fine fra- gives 2-chlorocyclododecanone (20) which is
grances. reacted with 2 mol of vinylmagnesium chloride
Trade Name. Exalton (Firmenich). to give 1,2-divinylcyclododecan-1-ol (21). This
is finally converted into 5-cyclohexadecen-1-
3-Methylcyclopentadec-4/5-en-1-one, one by an oxy-Cope rearrangement [113]:
(E/Z) [82356-51-2], C16 H28 O, M r 236.40, d 20
20
0.925 – 0.935, has a powerful musk odor, remi-
niscent of musk ketone.

The synthesis of muscenone starts with a

condensation of cyclododecanone and dimethyl
methylsuccinate, followed by cyclization with
polyphosphoric acid. Hydrogenation and elim-
ination yields methylbicyclo[10.3.0]-pentadec-
1(12)-ene. Ozonolyses results in a diketone,
which is converted via hydrogenation and elim-
ination to the unsaturated muscone [112].

5-Cyclohexadecen-1-one can be added to

perfume compositions as a substitute for the nat-
ural macrocyclic ketone musks.
Trade Name. TM II SP (Soda Aromatic), Am-
bretone (Takasago).

2,3,8,8-Tetramethyl-1,2,3,4,5,6,7,8-octa-
hydro-2-naphthalenyl methyl ketone
[54464-57-2] (22), C16 H26 O, M r 234.38, bp
(370 Pa) 134 – 135 ◦ C, n20
D 1.4975 – 1.500, is a
synthetic amber fragrance. It is prepared by a
Diels – Alder reaction of myrcene and 3-methyl-
3-Methylcyclopentadec-4/5-en-1-one is used 3-penten-2-one in the presence of aluminum
as nitromusk replacer, at low dosage (0.05 – chloride and cyclization of the substituted cy-
0.5 %) as a fragrance enhancer, at higher dosage clohexenyl methyl ketone intermediate with
it is “used for its musky character in addition to phosphoric acid. Some 3-acetyl isomer is also
its boosty effect”. formed [114].
Trade Name. Muscenone (Firmenich).
46 Flavors and Fragrances

2-tert-butylphenol. It is highly stable and is used

for perfuming soap as well as bath and house-
hold products.

Trade Names. Agrumex (Haarmann & Reimer),

Verdox (IFF).
The ketone is used in perfume bases for soaps, 4-tert-Butylcyclohexyl acetate [32210-23-
eaux de cologne, and detergent compositions. 4], C12 H22 O2 , M r 198.30, bp (1 kPa) 89 – 95 ◦ C,
Trade Name. Iso E Super (IFF). d 25 20
25 0.933 – 0.939, nD 1.450 – 1.454, does not
3-Methyl-2-cyclopenten-2-ol-1-one occur in nature and exists in cis and trans forms.
[80-71-7], C6 H8 O2 , M r 112.13, mp (mono- The trans-isomer has a rich, woody odor, while
hydrate) 106 ◦ C, occurs in beechwood tar and the odor of the cis-isomer is more intense and
has a caramel-like odor. It has been identified as more flowery. Considerable variations in cis–
a flavor component in food. Crystals of the com- trans ratios in commercial mixtures have little
pound usually contain 1 mol of water. Synthetic effect on the physical constants. Therefore, the
routes of production are of limited importance composition of mixtures should be determined
in comparison with isolation from beechwood by gas chromatography.
tar.

The ester is prepared by catalytic hydrogen-

The compound is frequently used in flavor ation of 4-tert-butylphenol followed by acety-
compositions for its caramel note, e.g., in bev- lation of the resulting 4-tert-butylcyclohexanol
erages and in confectionery. It is rarely used in [115]. If Raney nickel is used as the catalyst, a
perfumery, and then mainly as an intensifier. high percentage of the trans-isomer is obtained.
A rhodium–carbon catalyst yields a high per-
centage of the cis-isomer. The trans alcohol can
2.4.4. Esters be isomerized by alkaline catalysts; the lower-
boiling cis alcohol is then removed continuously
2-tert-Butylcyclohexyl acetate [88-41-5],
from the mixture by distillation [116].
C12 H22 O2 , M r 198.30, mp (pure cis-isomer)
4-tert-Butylcyclohexyl acetate is used partic-
34.5 – 35.4 ◦ C; commercial product: d 25
25 0.938 –
ularly in soap perfumes.
0.944, n20
D 1.4500 – 1.4560; this compound does
Trade Names.4-tert-Butylcyclohexylacetate
not occur in nature and exists in cis and trans
(Degussa), Oryclon extra (Haarmann &
forms. Pure 2-cis-tert-butylcyclohexyl acetate
Reimer), Vertenex (IFF).
is a crystalline solid, with a fruity, agrumen-
like odor. The commercial product is a color-
less liquid and consists of a mixture of cis and Decahydro-β-naphthyl acetate [10519-11-
trans-isomers, which contains 60 – 95 % of the 6], C12 H20 O2 , M r 196.29, bp (650 Pa) 120 ◦ C,
cis ester. With an increasing percentage of the d 25 1.005 – 1.015, n25
D 1.475 – 1.482, is a fra-
trans-isomer, the odor becomes more woody- grance substance that does not occur in nature.
camphory. It consists of a mixture of several stereoisomers
The acetate is prepared by esterification of 2- and is a colorless liquid with a sweet-fruity-
tert-butylcyclohexanol, which is obtained from herbaceous odor and a slight jasmin note.
 Flavors and Fragrances 47

Decahydro-β-naphthyl acetate is prepared by clopenten-1-one (23), followed by hydrolysis

esterification of technical-grade decahydro-β- and decarboxylation of the resulting 2-pentyl-
naphthol (e.g., with acetic anhydride). The ac- 3-oxocyclopentyl malonate (24), and esterifi-
etate is used for perfuming household products. cation of the (2-pentyl-3-oxocyclopentyl)acetic
acid (25) [117]. Dealkoxycarbonylation of 24
can also be accomplished directly with water at
elevated temperature [118].

4,7-Methano-3a,4,5,6,7,7a-hexahydro-
5(or 6)-indenyl acetate [2500-83-6] (or
[5413-60-5]), C12 H16 O2 , M r 192.26, bp (1 kPa)
119 – 121 ◦ C, d 25 25
4 1.0714, nD 1.4935, is a col-
orless liquid with a herbal, fresh-woody odor. It
consists of a mixture of isomers that is obtained
by addition of acetic acid to dicyclopentadiene
in the presence of an acid catalyst. It is used for
perfuming soaps, detergents, and air fresheners.

Methyl dihydrojasmonate is used in per-

fumery for blossom fragrances, particularly in
Trade Names. Cyclacet (IFF), Herbaflorat
jasmin types.
(Haarmann & Reimer), Verdylacetate (Givau-
Trade Names. Hedione (Firmenich).
dan Roure).
cis-Methyldihydrojasmonate [24851-98-7],
Allyl 3-cyclohexylpropionate [2705-87-5],
methyl (3-oxo-2-pentylcyclopentyl)acetate,
C12 H20 O2 , M r 196.29, bp (130 Pa) 91 ◦ C, has
C13 H22 O3 , M r 226.32, bp (7 Pa) 180 ◦ C,
not yet been found in nature. It is a colorless
d 20
20 1.001 – 1.009, has an extremely powerful
liquid with a sweet-fruity odor, reminiscent of
hedionic, jasminic odor.
pineapples. The ester is prepared by esterifi-
cation of 3-cyclohexylpropionic acid (obtained
by hydrogenation of cinnamic acid) with allyl
alcohol. It is used in perfumery to obtain fruity
top notes as well as pineapple and chamomile
nuances. (Limiting IFRA recommendation) Although cis-methyldihydrojasmonate is the
minor isomer of hedione (see page 49), it is
the much more intensive one. Its odor thresh-
old is about 20 times lower than that of the
trans-isomer. Several attempts have been made
to synthesize the pure cis-isomer. One approach
Methyl dihydrojasmonate [24851-98-7], is heating of the trans-isomer with sodium car-
methyl (3-oxo-2-pentylcyclopentyl)acetate, bonate followed by fractional distillation [119,
C13 H22 O3 , M r 226.32, bp (1 Pa) 85 – 90 ◦ C, 120]:
d 21.6
4 1.003, n20.2
D 1.4589, is a jasmin fra-
grance that is closely related to methyl jas-
monate, which occurs in jasmin oil. Methyl
dihydrojasmonate has been identified in tea.
It is a liquid with a typical fruity, jasmin-like
blossom odor. Methyl dihydrojasmonate is pre-
pared as cis/trans-isomeric mixture by Michael
addition of malonic esters to 2-pentyl-2-cy-
48 Flavors and Fragrances

A cis : trans ratio of 96 : 4 was obtained by cyclopentanone. Hydrolysis, decarboxylation,

catalytic asymmetric hydrogenation of the acid and esterification of the resulting monocarbox-
in the presence of the chiral ruthenium catalyst ylic acid with methanol yields the desired es-
DuPhos (26): ter [121]. Trialkyl propane-1,1,3-tricarboxylates
can be prepared by Michael addition of dialkyl
malonates to alkyl acrylates.
Compound 27 is used in perfumery in floral
compositions.
Trade Name. Jasmopol (Haarmann & Reimer).

2.5. Aromatic Compounds

2.5.1. Hydrocarbons
Due to its thermodynamic instability cis- A few alkyl- and aralkyl-substituted aromatic
methyldihydrojasmonate is only stable in media hydrocarbons find limited use in perfumery. Ex-
having a pH value of 5.5 to 6.5. amples include p-cymene [99-87-6], which is
Trade Names. Hedione HC (Firmenich), Cepi- a component of many essential oils and when
onate (Nippon Zeon). pure has a weak, citrus odor, as well as diphenyl-
methane [101-81-5] which has an odor like gera-
Methyl 2-hexyl-3-oxocyclopentanecar- nium:
boxylate [37172-53-5] (27), C13 H22 O3 , M r
226.32, bp (8 Pa) 85 ◦ C, n20 D 1.4562, is a col-
orless liquid with a long-lasting, floral, jasmin-
like odor, that has only little of the fatty aspect
characteristic of many jasmin fragrances. The
product has not yet been found in nature.
p-Cymene Diphenylmethane

2.5.2. Alcohols and Ethers

Phenethyl alcohol is qualitatively and quantita-
tively one of the most important fragrance sub-
stances that belongs to the class of araliphatic
alcohols. Its lower homologue (benzyl alcohol)
and higher homologue (dihydrocinnamic alco-
hol) also have characteristic odor properties, but
are more frequently used in the form of their es-
ters. Cinnamic alcohol, the most important un-
saturated araliphatic alcohol, is valuable for both
fragrances and flavors.
The araliphatic alcohols mentioned above oc-
cur in many natural fragrances and flavors, but
are generally not the main components. These al-
cohols are nearly always prepared synthetically
for use in compositions. The branched-chain ho-
mologues of phenethyl and dihydrocinnamic al-
cohols (dimethyl benzyl carbinol and dimethyl
Compound 27 can be prepared by condensing
phenethyl carbinol, respectively) are used in
an alkyl α-bromocaprylate with a trialkyl pro-
fairly large amounts as fragrance materials, but
pane-1,1,3-tricarboxylate to give a substituted
have not been found in nature.
 Flavors and Fragrances 49

Benzyl alcohol [100-51-6], C7 H8 O, M r Formation of byproducts, such as 1,2-

108.14, bp (101.3 kPa) 205.4 ◦ C, d 20 4 1.0419, diphenylethane, is largely avoided by using
n20
D 1.5396, occurs in many essential oils and an excess of benzene and low temperature.
foods. It is a colorless liquid with a weak, slightly Special purification procedures are required
sweet odor. For further details on the chemi- to obtain a pure product that is free of chlo-
cal properties and synthesis of benzyl alcohol, rine and suitable for use in perfumery.
see→ Benzyl Alcohol, Chap. 3. Hydrogenation of Styrene Oxide.
According to a patent, excellent yields of
phenethyl alcohol are obtained when styrene
oxide is hydrogenated at low temperature, us-
ing Raney nickel as a catalyst and a small
Because of its relatively weak odor, benzyl amount of sodium hydroxide [122].
alcohol is used in fragrance and flavor compo-
sitions mainly as a solvent and for dilution. It is
the starting material for a large number of benzyl
esters, which are important fragrance and flavor
substances.

Phenethyl alcohol [60-12-8], 2-phenylethyl Uses. Phenethyl alcohol is used frequently

alcohol, C8 H10 O, M r 122.17, bp (101.3 kPa) and in large amounts as a fragrance compound.
219.8 ◦ C, d 20 20
4 1.0202, nD 1.5325, is the main
It is a popular component in rose type composi-
component of rose oils obtained from rose blos- tions, but it is also used in other blossom notes.
soms. It occurs in smaller quantities in neroli It is stable to alkali and, therefore, ideally suited
oil, ylang-ylang oil, carnation oil, and geranium for use in soap perfumes.
oils. Since the alcohol is rather soluble in water,
losses occur when essential oils are produced by Phenethyl methyl ether [3558-60-9],
steam distillation. C9 H12 O, M r 136.19, bp (94.6 kPa) 185 –
Properties. Phenethyl alcohol is a colorless 186 ◦ C, d 27 0.9417, n24
D 1.4970, is a colorless
liquid with a mild rose odor. It can be dehydro- liquid with a sharp, rosy-green odor. It is used
genated catalytically to phenylacetaldehyde and in oriental type perfumes as well as in artificial
oxidized to phenylacetic acid (e.g., with chromic keora oil.
acid). Its lower molecular mass fatty acid esters
as well as some alkyl ethers, are valuable fra-
grance and flavor substances.
Production. Many synthetic methods are
known for preparing phenethyl alcohol; the fol-
lowing are currently of industrial importance: Phenethyl isoamyl ether [56011-02-0],
C13 H20 O, M r 192.30, d 2525 0.901 – 0.904, nD
20
Friedel–Crafts Reaction of Benzene and 1.481 – 1.484, is a colorless liquid with a green,
Ethylene Oxide. sweet-flowery odor of chamomile blossoms and
In the presence of molar quantities of alu- a secondary, soapy note; it is used in perfumes.
minum chloride, ethylene oxide reacts with
benzene to give an addition product, which
is hydrolyzed to phenethyl alcohol:

Trade Name. Anther (Quest).

1-Phenylethyl alcohol [98-85-1], styrallyl

alcohol, C8 H10 O, M r 122.17, mp 20 ◦ C, bp
(101.3 kPa) 203 ◦ C, d 20 20
4 1.0135, nD 1.5275, has
been identified as a volatile component of food
(e.g., in tea aroma and mushrooms). The alco-
hol is a colorless liquid with a dry, roselike odor,
50 Flavors and Fragrances

slightly reminiscent of hawthorn. It can be pre-

pared by catalytic hydrogenation of acetophe-
none. 1-Phenylethyl alcohol is used in small
quantities in perfumery and in larger amounts
for the production of its esters, which are more 4-Phenyl-2-methyl-2-butanol [103-05-9],
important as fragrance compounds. α,α-dimethylphenethyl carbinol, C11 H16 O, M r
164.25, bp (1.9 kPa) 124 – 125 ◦ C, d 20.7
4 0.9626,
n20.7
D 1.5077, is a colorless liquid with a dry-
flowery, lily-like odor. It has been identified in
cocoa aroma and is prepared by a Grignard re-
action of benzylacetone and methylmagnesium
chloride. It is used in blossom compositions.
Dihydrocinnamic alcohol [122-97-4],
3-phenylpropanol, hydrocinnamic alcohol,
C9 H12 O, M r 136.19, bp (100 kPa) 237.5 ◦ C,
d 20 20
4 1.008, nD 1.5278, occurs both in free and
esterified form in resins and balsams (e.g., ben-
zoe resin and Peru balsam). It has been identified 1-Phenyl-3-methyl-3-pentanol [10415-87-
in fruit and cinnamon. 9], phenethyl methyl ethyl carbinol, C12 H18 O,
Hydrocinnamic alcohol is a slightly viscous, M r 178.28, bp (1.7 kPa) 129 – 130 ◦ C, d 25 4
colorless liquid with a blossomy-balsamic odor, 0.9582, n20
D 1.509 – 1.513, has not yet been
slightly reminiscent of hyacinths. Esterification found in nature. It is a colorless liquid with a
with aliphatic carboxylic acids is important be- delicate peony, slightly fruity odor. Phenethyl
cause it leads to additional fragrance and flavor methyl ethyl carbinol can be prepared from ben-
compounds. zylacetone and ethylmagnesium chloride by a
Grignard reaction. It is used to perfume soap,
cosmetics, and detergents.

Hydrocinnamic alcohol is prepared by hy-

drogenation of cinnamaldehyde. A mixture of
hydrocinnamic alcohol and the isomeric 2-phe-
nylpropanol can be obtained from styrene by a
modified oxo synthesis. The two isomers can be Cinnamic alcohol [104-54-1], 3-phenyl-
separated by distillation [123]. 2-propen-1-ol, C9 H10 O, M r 134.18; trans-
Hydrocinnamic alcohol is used in blossom isomer [4407-36-7]: mp 34 ◦ C, bp (101.3 kPa)
compositions for balsamic and oriental notes. 257.5 ◦ C, d 20 20
4 1.0440, nD 1.5819; this alcohol
can exist in cis and trans forms. Although both
α,α-Dimethylphenethyl alcohol [100-86- isomers occur in nature, the trans-isomer is far
7], 1-phenyl-2-methyl-2-propanol, α,α-di- more abundant and is present, for example, in
methyl benzyl carbinol, DMBC, C10 H14 O, M r styrax oil. trans-Cinnamic alcohol is a colorless,
150.22, mp 24 ◦ C, bp (101.3 kPa) 214 – 216 ◦ C, crystalline solid with a hyacinth-like balsamic
d 20 20
4 0.9840, nD 1.5170, has not yet been found odor.
in nature. The alcohol has a floral-herbaceous
odor, reminiscent of lilac, and is prepared by a
Grignard reaction of benzylmagnesium chloride
and acetone. It is used in perfumery for various trans-Cinnamic alcohol
flower notes (e.g., lilac, hyacinth, mimosa). The
Cinnamic alcohol can be dehydrogenated
alcohol is stable to alkali and, thus, is suited
to give cinnamaldehyde and oxidized to
for soap perfumes. It is used to prepare a num-
give cinnamic acid. Hydrogenation yields 3-
ber of esters, which are also used as fragrance
phenylpropanol and/or 3-cyclohexylpropanol.
compounds.
Reaction with carboxylic acids or carboxylic
 Flavors and Fragrances 51

acid derivatives results in the formation of cin- their odor is slightly different and significantly
namyl esters, some of which are used as fra- weaker.
grance compounds. The simplest araliphatic aldehyde, benzalde-
Production. Cinnamic alcohol is prepared on hyde and its 4-isopropyl homologue, cuminalde-
an industrial scale by reduction of cinnamalde- hyde, are used to a limited extent as fragrance
hyde. Three methods are particularly useful: and flavor compounds. However, both com-
pounds are used in large quantity for the pro-
1) In the Meerwein–Ponndorf reduction, cin- duction of cinnamic and dihydrocinnamic alde-
namaldehyde is reduced to cinnamic alcohol hydes, respectively.
(yield, ca. 85 %) with isopropyl or benzyl al-
cohol in the presence of the corresponding Benzaldehyde [100-52-7], C7 H6 O, M r
aluminum alcoholate. 106.12, bp (101.3 kPa) 178.1 ◦ C, d 15 20
4 1.0415, nD
2) A 95 % yield of cinnamic alcohol is obtained 1.5463, is the main, characteristic component of
by selective hydrogenation of the carbonyl bitter almond oil. It occurs in many other essen-
group in cinnamaldehyde with, for example, tial oils and is a colorless liquid with a bitter
an osmium–carbon catalyst [124]. almond odor. For further details on the chem-
3) High yields of cinnamic alcohol can be ical properties and synthesis of benzaldehyde,
obtained by reduction of cinnamaldehyde see → Benzaldehyde, Chap. 3.
with alkali borohydrides. Formation of di-
hydrocinnamic alcohol is thus avoided [125].
Uses. Cinnamic alcohol is valuable in per-
fumery for its odor and fixative properties. It is Benzaldehyde is used in aroma compositions
a component of many flower compositions (lilac, for its bitter almond odor. It is the starting mate-
hyacinth, and lily of the valley) and is a starting rial for a large number of araliphatic fragrance
material for cinnamyl esters, several of which and flavor compounds.
are valuable fragrance compounds. In aromas,
the alcohol is used for cinnamon notes and for
Phenylacetaldehyde [122-78-1], C8 H8 O,
rounding off fruit aromas. It is used as an in-
M r 120.15, bp (101.3 kPa) 195 ◦ C, d 20
4 1.0272,
termediate in many syntheses (e.g., for pharma-
n20
D 1.5255, has been identified in many essential
ceuticals such as the antibiotic chloromycetin).
oils and as a volatile constituent of foods. It is
(Limiting IFRA recommendation)
a colorless liquid with a sweet-green odor, rem-
iniscent of hyacinth. Since it readily undergoes
oxidation and polymerizes, it must be stabi-
2.5.3. Aldehydes and Acetals
lized by addition of antioxidants and by dilution
with, for example, diethyl phthalate before use
Many of the aldehydes discussed in this section
in compositions.
are treated in detail elsewhere (→ Aldehydes,
Aliphatic and Araliphatic).
Several araliphatic aldehydes are of special
commercial importance as fragrance and fla-
vor materials. These include cinnamaldehyde Phenylacetaldehyde can be obtained in high
and its homologues in which the side-chain yield by vapor-phase isomerization of styrene
carries an alkyl substituent; α-amyl- and α- oxide, for example, with alkali-treated silica–
hexylcinnamaldehyde are particularly impor- alumina [126]. Another process starts from
tant. Other important members of this group phenylethane-1,2-diol, which can be converted
are the substituted phenylpropanals, 4-isopro- into phenylacetaldehyde in high yield. The reac-
pyl- and 4-tert-butyl-α-methyldihydrocinnam- tion is performed in the vapor phase in the pres-
aldehyde. Arylacetaldehydes and arylpropion- ence of an acidic silica–alumina catalyst [127].
aldehydes are, in comparison, seldom used in Phenylacetaldehyde is used in perfume com-
compositions. The corresponding acetals are positions, in particular for hyacinth and rose
more stable and are used as well, although notes. (IFRA recommendation)
52 Flavors and Fragrances

Phenylacetaldehyde dimethyl acetal

[101-48-4], C10 H14 O2 , M r 166.22, bp
(100.2 kPa) 219 – 221 ◦ C, d 18 1.004, is a col-
orless liquid with a strong, rose-petal odor. The
dimethyl acetal is more stable than phenylacet-
aldehyde itself. It imparts a herbal green note to 4-Methylphenylacetaldehyde [104-09-6],
many flower compositions. C9 H10 O, M r 134.18, bp (101.3 kPa) 221 –
222 ◦ C, d 20 20
4 1.0052, nD 1.5255, which has been
identified in corn oil, is a colorless liquid with a
strong green odor. It can be prepared by reaction
of 4-methylbenzaldehyde with chloroacetates,
Trade Names. Lilas Vert (Firmenich), Viridine followed by hydrolysis of the resulting glyci-
(Givaudan Roure). dates and decarboxylation. The aldehyde is used
in flower compositions for green notes.
Dihydrocinnamaldehyde [104-53-0], 3-
phenylpropanal, C9 H10 O, M r 134.18, bp
(2.7 kPa) 112 ◦ C, d 20 20
4 1.019, nD 1.5266, oc-
curs in Sri Lanka cinnamon oil, among others.
The aldehyde is a colorless liquid with a strong,
Cyclamenaldehyde [103-95-7], 2-methyl-
flowery, slightly balsamic, heavy hyacinth-like
3-(4-isopropylphenyl)propanal, C13 H18 O, M r
odor. It tends to undergo self-condensation.
190.28, bp (300 Pa) 108 – 108.5 ◦ C, d 20
4 0.9502,
Dihydrocinnamaldehyde can be obtained
n20
D 1.5068, has been reported in nutmeg [128].
with scarcely any byproducts by selective hy-
The commercially available racemate is a color-
drogenation of cinnamaldehyde. It is used in per-
less to yellowish liquid with an intense flowery
fumery for hyacinth and lilac compositions.
odor reminiscent of Cyclamen europaeum (cy-
clamen, sowbread).
Production. Two main processes are used for
the industrial synthesis of cyclamenaldehyde:
1) Alkaline condensation of 4-isopropylbenz-
Hydratropaldehyde [93-53-8], 2-phenyl- aldehyde and propanal results, via the aldol
propanal, C9 H10 O, M r 134.18, bp (1.5 kPa) 28, in the formation of 2-methyl-3-(4-isopro-
92 – 94 ◦ C, d 20 20
4 1.0089, nD 1.5176, is a colorless pylphenyl)-2-propenal (29). The unsaturated
liquid with a green hyacinth odor. Hydratrop-
aldehyde can be hydrogenated to hydratropic
alcohol, which is also used to a limited extent
as a fragrance compound. Hydratropaldehyde is
obtained from styrene by oxo synthesis; small
quantities of the isomeric dihydrocinnamalde-
hyde are formed as a byproduct. Hydratropalde-
hyde is used in perfumery in blossom composi-
tions.

Hydratropaldehyde dimethyl acetal

[90-87-9], C11 H16 O2 , M r 180.25, n20
D 1.4938, is
a liquid with a mushroom-like, earthy odor. It is
used for green nuances in flower compositions.
 Flavors and Fragrances 53

aldehyde is hydrogenated selectively to the butyl-α-methyldihydrocinnamic alcohol, which

saturated aldehyde in the presence of potas- is subsequently dehydrogenated to the desired
sium acetate and a suitable catalyst, such as aldehyde [131].
palladium–alumina [129]: see previous page.
2) Friedel–Crafts reaction of isopropyl-
benzene and 2-methylpropenal diacetate
(methacrolein diacetate) in the presence
of titanium tetrachloride/boron trifluoride
etherate gives cyclamenaldehyde enolac-
etate, which is hydrolyzed to the aldehyde
[130]:

The compound is more stable than cyclamen-

aldehyde and is a popular component of flower
compositions, particularly lily of the valley and
linden types, because of its mild, pleasant, blos-
som fragrance. Large quantities are used in soap
Uses. Cyclamenaldehyde is an important and cosmetic perfumes.
component for obtaining special blossom notes Trade Names. Lilestral (IFF), Lilial (Givaudan
in perfume compositions, particularly the cycla- Roure).
men type. Because of its fresh-flowery aspect, it
is also used as the top note in many other blos- Cinnamaldehyde [14371-10-9], 3-phenyl-
som fragrances. 2-propenal, C9 H8 O, M r 132.16, trans-isomer bp
(101.3 kPa) 253 ◦ C, d 20 20
4 1.0497, nD 1.6195, is
4-tert-Butyl-α-methyldihydrocinnam- the main component of cassia oil (ca. 90 %) and
aldehyde [80-54-6], 2-methyl-3-(4-tert- Sri Lanka cinnamon bark oil (ca. 75 %). Smaller
butylphenyl)propanal, C14 H20 O, M r 204.31, bp quantities are found in many other essential oils.
(800 Pa) 126 – 127 ◦ C, d 20 20
4 0.9390, nD 1.5050, In nature, the trans-isomer is predominant.
is a homologue of cyclamenaldehyde, but is not trans-Cinnamaldehyde is a yellowish liquid
found in nature. The racemic compound is a with a characteristic spicy odor, strongly remi-
colorless to slightly yellow liquid with a mild- niscent of cinnamon. Being an α,β-unsaturated
flowery odor, reminiscent of cyclamen and lily aldehyde, it undergoes many reactions, of which
of the valley. hydrogenation to cinnamic alcohol, dihydro-
The aldehyde is prepared by the same routes cinnamaldehyde, and dihydrocinnamic alcohol
as cyclamenaldehyde (see under Cyclamenalde- are important. Cinnamic acid is formed by au-
hyde, page 54). toxidation.
A patent describes the following preparation On an industrial scale, cinnamaldehyde is
from α-methylcinnamaldehyde. α-Methylcin- prepared almost exclusively by alkaline conden-
namaldehyde (from benzaldehyde and propion- sation of benzaldehyde and acetaldehyde. Self-
aldehyde) is hydrogenated to α-methyldi- condensation of acetaldehyde can be avoided by
hydrocinnamic alcohol. The alcohol is alkylated using an excess of benzaldehyde and by slowly
with tert-butyl chloride or isobutene to 4-tert- adding acetaldehyde [132].
54 Flavors and Fragrances

Cinnamaldehyde is used in many composi- 2.5.4. Ketones (→ Ketones)

tions for creating spicy and oriental notes (e.g.,
soap perfumes). It is the main component of arti- The aromatic ketones that occur or are used as
ficial cinnamon oil. In addition, it is an important fragrance and flavor materials are predominantly
intermediate in the synthesis of cinnamic alco- aryl methyl ketones, which include acetophe-
hol and dihydrocinnamic alcohol. nones and β-naphthyl methyl ketone. Several
acetylpolymethylindanes and -tetralins are com-
mercially important as musk fragrances. Musk
ketone, a substituted nitroacetophenone, is dis-
cussed in page 62.

α-Amylcinnamaldehyde [122-40-7], 2- Acetophenone [98-86-2], methyl phenyl ke-

pentyl-3-phenyl-2-propenal, C14 H18 O, M r tone, C8 H8 O, M r 120.15, mp 20.5 ◦ C, bp
202.30, bp (0.7 kPa) 140 ◦ C, d 20 4 0.9710, nD
20
(101.3 kPa) 202.0 ◦ C, d 20 20
4 1.0281, nD 1.5372, is
1.5381. Its natural occurrence as a genuine prod- a naturally occurring component of a large num-
uct is debatable. It is a light yellow liquid with a ber of foods and essential oils. It is a colorless
flowery, slightly fatty odor, which becomes rem- liquid with a penetrating sweet odor, reminiscent
iniscent of jasmin when diluted. The aldehyde of orange blossom.
is relatively unstable and must be stabilized by Acetophenone can be hydrogenated catalyti-
antioxidants. cally to 1-phenylethanol. It is obtained as a by-
It is prepared from benzaldehyde and hep- product in the Hock phenol synthesis and is pu-
tanal in the same way as cinnamaldehyde. rified from the high-boiling residue by distil-
lation (→ Ketones, Chap. 7.1.). The quantitites
obtained from this source satisfy the present de-
mand.
Acetophenone is used for perfuming deter-
gents and industrial products and is an interme-
α-Amylcinnamaldehyde is a very popular diate in the synthesis of other fragrance com-
fragrance substance for creating jasmin notes. pounds.
It is stable to alkali and long-lasting; large quan-
tities are used, particularly in soap perfumes.

α-Hexylcinnamaldehyde [101-86-0], 2-
hexyl-3-phenyl-2-propenal, C15 H20 O, M r
216.32, bp (2 kPa) 174 – 176 ◦ C, d 24 0.9500,
n25
D 1.5268, has not yet been identified in nature. 4-Methylacetophenone [122-00-9], p-tolyl
It is a yellow liquid with a mild, slightly fatty, methyl ketone, C9 H10 O, M r 134.18, mp 28 ◦ C,
flowery, somewhat herbal odor and a distinct bp (101.3 kPa) 226 ◦ C, d 20 20
4 1.0051, nD 1.5335,
jasmin note. Like the α-amyl homologue, α- has been identified in Brazilian rosewood oil
hexylcinnamaldehyde must be protected against and in pepper. It occurs as colorless crystals
oxidation by the addition of stabilizers. It is pre- with a flowery-sweet odor that is milder than
pared in a manner similar to α-amylcinnamalde- that of acetophenone. 4-Methylacetophenone is
hyde by alkaline condensation of excess ben- prepared from toluene and acetic anhydride or
zaldehyde with octanal (instead of heptanal). α- acetyl chloride by a Friedel–Crafts reaction. It is
Hexylcinnamaldehyde is widely used in flower used for blossom notes in mimosa and hawthorn
compositions (e.g., jasmin and gardenia) and, type perfumes, especially in soap perfumes.
because of its stability to alkali, in soap per-
fumes.
 Flavors and Fragrances 55

Benzylacetone [2550-26-7], 1-phenyl-3-bu- 6-Acetyl-1,1,2,3,3,5-hexamethylindane

tanone, C10 H12 O, M r 148.20, bp (101.3 kPa) [15323-35-0], C17 H24 O, M r 244.38, mp 35 ◦ C,
233 – 234 ◦ C, d 22 22
4 0.9849, nD 1.5110, has been is a synthetic musk fragrance. It is prepared by
identified as a volatile component of cocoa. Ben- Friedel–Crafts acetylation of 1,1,2,3,3,5-hexa-
zylacetone is a sweet-flowery smelling liquid, methylindane, which can be obtained as a 70 : 30
which can be prepared by selective hydrogen- mixture with 1,1,3,5-tetramethyl-3-ethylindane
ation of benzylidene acetone (from benzalde- by reacting α,p-dimethylstyrene with amylenes
hyde and acetone). It is used in soap perfumes. or 2-methyl-2-butanol in a mixture of acetic acid
and concentrated sulfuric acid [133]:

Methyl β-naphthyl ketone [93-08-3],

C12 H10 O, M r 170.21, bp (1.7 kPa) 171 –
173 ◦ C, mp 56 ◦ C, d 20 20
4 1.171, nD 1.6752, has
been identified in some essential oils. It smells
like orange blossom and is a colorless crystalline
solid. It is usually prepared by Friedel–Crafts
acetylation of naphthalene (with acetylchloride,
acetic anhydride, etc.) in the presence of alu-
minum chloride. In polar solvents (e.g., nitro-
benzene), the percentage of the simultaneously
formed α-isomer is lower. Methyl β-naphthyl
ketone is used in eaux de cologne, soap per-
fumes, and detergents. It is a good fixative.

The indane ketone is a musk fragrance that is

stable to light and in soap. It is used in perfumes
and cosmetics for its fixative properties as well
as its fragrance.
Benzophenone [119-61-9], diphenyl ke- Trade Name. Phantolide (Haarmann & Reimer).
tone, C13 H10 O, M r 182.22, bp (6.3 kPa)
200.5 ◦ C, mp 48.1 ◦ C, d 50 1.976, has been
4-Acetyl-1,1-dimethyl-6-tert-butylindane
identified as a flavor component of grapes. It
[13171-00-1], C17 H24 O, M r 244.38, mp 76.7 –
is a colorless crystalline solid with a rosy,
77.2 ◦ C, is a musk fragrance that does not oc-
slightly geranium-like odor. It can be prepared
cur in nature. It is prepared by reacting tert-
in several ways (→ Ketones, Chap. 7.3.), for
example, by Friedel–Crafts reaction of ben-
zene and benzoyl chloride with aluminum chlo-
ride, or of benzene and carbon tetrachloride,
and subsequent hydrolysis of the resulting α,α-
dichlorodiphenylmethane. Benzophenone can
also be prepared by oxidation of diphenyl-
methane. It is used in flower compositions and
as a fixative.
56 Flavors and Fragrances

butylbenzene with isoprene in the presence of 6-Acetyl-1,1,2,4,4,7-hexamethyltetralin

sulfuric acid, followed by acetylation of the re- [1506-02-1], C18 H26 O, M r 258.40, mp 55.5 ◦ C,
sulting 1,1-dimethyl-6-tert-butylindane [134]: bp (250 Pa) 119 ◦ C, is a synthetic musk
see previous page. fragrance. It is prepared from 1,1,2,4,4,7-
The indane is light-stable and is mainly used hexamethyltetralin, which is obtained by one
for perfuming soaps and cosmetics. of the following routes:
Trade Names. Celestolide (IFF), Crysolide (Gi-
vaudan Roure). 1) Reaction of α,p-dimethylstyrene with
tetramethylethene [136] or 2,3-di-
5-Acetyl-1,1,2,6-tetramethyl-3-isopropyl- methylbutan-2-ol [133] in an acetic acid–
indane [68140-48-7], C18 H26 O, M r 258.40, sulfuric acid mixture yields the desired hex-
bp (130 Pa) 144 – 146 ◦ C, n20
D 1.5301, is also a
amethyltetralin, in addition to polymerized
musk fragrance that does not occur in nature. It starting materials:
is prepared from toluene and isobutyryl chloride
by a Friedel–Crafts reaction that yields p-tolyl
isopropyl ketone; the ketone is reduced to the
corresponding alcohol. Chlorination and treat-
ment with 2-methyl-2-butene yield 1-isopropyl-
2,3,3,5-tetramethylindane, which by a Friedel–
Crafts reaction with acetyl chloride gives the
title compound [135]:

2) Reaction of p-cymene with 2,2-dimethyl-3-

butene (neohexene) and a tertiary alkylhalide
(as a hydrogen scavenger) in the presence
of catalytic amounts of anhydrous aluminum
halide in inert solvents produces a high yield
of the hexamethyltetralin [137].

1,1,2,4,4,7-Hexamethyltetralin is subse-
quently acetylated to 6-acetyl-1,1,2,4,4,7-
hexamethyltetralin, e.g., with acetyl chloride
and aluminum chloride (see next page).
The product is a light-stable, versatile musk fra-
grance that is used in soap and cosmetics.
It is used in perfume compositions for soaps Trade Names. Fixolide (Givaudan Roure),
and detergents. Tonalide (Haarmann & Reimer).
Trade Name. Traseolide (Quest).
 Flavors and Fragrances 57

catalyst) or by reaction of benzyl chloride with

sodium acetate (→ Benzyl Alcohol, Chap. 8.2.).
In terms of volume, benzyl acetate is one of the
most important fragrance and flavor chemicals.
Benzyl propionate [122-63-4], R = CH2 CH3 ,
C10 H12 O2 , M r 164.20, bp (101.3 kPa) 219 –
220 ◦ C, d 20 20
4 1.0335, nD 1.4996, is a liquid with
a sweet-fruity odor, which is used in perfumery
for floral-fruity notes and in fruit flavor compo-
sitions.
Benzyl isovalerate [103-38-8],
R = CH2 CH(CH3 )2 , C12 H16 O2 , M r 192.26, bp
(101.3 kPa) 245 ◦ C, d 20 20
4 0.9900, nD 1.4878, is
a liquid with a heavy, flowery odor, which is
used in perfumery for oriental and heavy blos-
2.5.5. Esters of Araliphatic Alcohols and som odors.
Aliphatic Acids
Phenethyl Esters. The most commonly used
Esters of araliphatic alcohols and aliphatic acids phenethyl esters are the following:
are interesting as flavors and fragrances because
of their characteristic odor properties. Acetates
are the most popular esters. Benzyl acetate is
particularly important commercially and occu-
pies a prominent position in the fragrance and Phenethyl acetate [103-45-7], R = CH3 ,
flavor industry. C10 H12 O2 , M r 164.20, bp (101.3 kPa) 232.6 ◦ C,
Esters of other fatty acids are used to a lesser d 20 20
4 1.0883, nD 1.5171, occurs in a number of es-
extent. In addition to benzyl esters and phenethyl sential oils and is a volatile aroma component of
esters, isomeric homologues with substituted many fruits and alcoholic beverages. Phenethyl
side-chains are used in fairly large amounts in acetate is a colorless liquid with a fine rose scent
perfume compositions because of their special and a secondary, sweet, honey note. It is used in
blossom odors. Not all have yet been found in perfumery as a modifier of phenethyl alcohol,
nature. The esters are prepared from the cor- e.g., in rose and lilac compositions. In addition,
responding alcohols via the customary routes it is used in a large number of aromas, in keeping
(→ Esters, Organic). with its natural occurrence.
Phenethyl isobutyrate [103-48-0],
Benzyl esters of lower molecular mass fatty R = CH(CH3 )2 , C12 H16 O2 , M r 192.26, bp
acids occur widely in nature. The following are (2 kPa) 122 – 124 ◦ C, d 15 0.9950, n20 D 1.4871,
important fragrance and flavor materials: occurs in peppermint oils. It has a heavy, fruity,
blossom odor and is used accordingly in perfume
and flavor compositions.
Phenethyl isovalerate [140-26-1],
R = CH2 CH(CH3 )2 , C13 H18 O2 , M r 206.28, bp
(7.2 kPa) 141 – 145 ◦ C, d 15 0.9845, n20D 1.4855,
Benzyl acetate [140-11-4], R = CH3 , has been identified as a volatile aroma compo-
C9 H10 O2 , M r 150.18, bp (101.3 kPa) 215 ◦ C, nent of peppermint oils. The fruitiness of its odor
d 20 20
4 1.0550, nD 1.5232, is the main component is even more pronounced than that of the isobu-
of jasmin and gardenia oils. It occurs as a minor tyrate. It is used in small quantities for the same
component in a large number of other essential purposes as phenethyl isobutyrate.
oils and extracts. It is a colorless liquid with 1-Phenylethyl acetate [93-92-5], styrallyl
a strong, fruity, jasmin odor. Benzyl acetate is acetate, C10 H12 O2 , M r 164.20, bp (1.3 kPa)
prepared by esterification of benzyl alcohol with 92.5 ◦ C, d 20 20
4 1.0277, nD 1.4954, is a liquid with
acetic anhydride (e.g., with sodium acetate as a a dry, fruity-green, blossom odor, reminiscent
58 Flavors and Fragrances

of gardenia. It can occur in the form of opti- 2.5.6. Aromatic Acids

cally active enantiomers, but only the racemate
is used in perfumery. Styrallyl acetate is a key Aromatic acids (e.g., benzoic acid) and ar-
ingredient in gardenia fragrances and is added to aliphatic acids (e.g., phenylacetic, cinnamic, and
many other blossom compositions, particularly dihydrocinnamic acids) occur in numerous es-
for dry top notes. sential oils and have also been identified in the
aromas of many foods. However, phenylacetic
acid is the only acid that is used in significant
quantities as a fragrance and flavor substance.

Phenylacetic acid [103-82-2], C8 H8 O2 , M r

136.15, bp (101.3 kPa) 265.5 ◦ C, mp 78 ◦ C,
α,α-Dimethylphenethyl Esters. The fol- d 79.8 1.0809, occurs in Japanese peppermint oil,
4
lowing α,α-dimethylphenethyl esters are com- in neroli oil, and in traces in rose oils. It is a
mercially important: volatile aroma constituent of many foods (e.g.,
honey). It forms colorless crystals that have a
honey odor. For further details on chemical prop-
erties and synthesis, see → Phenylacetic Acid.
Because of its intense odor, phenylacetic acid
α,α-Dimethylphenethyl acetate [151-05-3],
is added to perfumes in small quantities for
R = CH3 , C12 H16 O2 , M r 192.26, mp ca. 30 ◦ C,
rounding off blossom odors. Addition to fruit
bp (400 Pa) 90 ◦ C, d 25 25 0.998 – 1.000, nD
20
aromas imparts a sweet honey note.
1.4923, is a colorless liquid with a flowery-
woody odor. The ester is used in blossom com-
positions, e.g., lily of the valley, rose, and gera-
nium.
α,α-Dimethylphenethyl butyrate [10094-34-
5], R = (CH2 )2 CH3 , C14 H20 O2 , M r 220.31, bp
(400 Pa) 96 ◦ C, d 25 20
25 0.971 – 0.974, nD 1.4860 – 2.5.7. Esters Derived from Aromatic and
1.4900, is a colorless liquid with a slightly Araliphatic Acids
herbal, strongly fruity odor, reminiscent of prune
and apricot. It is used in perfumery as a modifier The acid moiety generally determines the odor
of the alcohol and for oriental notes. of esters derived from aromatic or araliphatic
acids. Unless stated otherwise, the esters are
Cinnamyl acetate [103-54-8], C11 H12 O2 , prepared from the corresponding acids or acid
M r 176.21, bp (1.3 kPa) 139 – 140 ◦ C, d 22 derivatives and alcohols by the customary meth-
1.0520, n20
D 1.5420, is the only ester of cinnamic ods (→ Esters , Organic).
alcohol of any importance. trans-Cinnamyl ac-
etate occurs in cassia oil and is a colorless liquid
with a sweet-flowery-fruity, slightly balsamic 2.5.7.1. Benzoates
odor. It is a good fixative and is used in blos-
som compositions (e.g., lilac and jasmin) and The following benzoates are used in fairly large
for oriental notes. In aroma compositions, it is quantities as perfumery materials.
used for cinnamon-fruity effects.

Methyl benzoate [93-58-3], R = CH3 ,

C8 H8 O2 , M r 136.15, bp (101.3 kPa) 199.6 ◦ C,
d 20 20
4 1.0888, nD 1.5164, has been found in essen-
tial oils (e.g., ylang-ylang and tuberose blossom
 Flavors and Fragrances 59

oil). It is a colorless liquid with a strong, dry- Phenethyl phenyl acetate [102-20-5],
fruity, slightly phenolic odor. For further proper- R = CH2 CH2 C6 H5 , C16 H16 O2 , M r 240.30, bp
ties and synthesis, seeBenzoic Acid and Deriva- (600 Pa) 177 – 178 ◦ C, mp 26.5 ◦ C, d 25
25 0.880,
tives, Chap. 8.5. . n20
D 1.5496 – 1.5504, has not yet been identified
Methyl benzoate is used in perfume bases, in natural sources. It occurs as a colorless liq-
such as ylang-ylang and tuberose types. uid or crystals, which have a heavy, sweet, rose
or hyacinth odor and a distinct honey note. The
Hexyl benzoate [6789-88-4], R=(CH2 )5 CH3 , ester is used particularly in flowery fragrance
C13 H18 O2 , M r 206.28, bp (102.6 kPa) 272 ◦ C, compositions and as a fixative.
is a liquid with a balsamic-green, melon-like
odor. It is used in perfumery.
2.5.7.3. Cinnamates
Benzyl benzoate [120-51-4], R = CH2 C6 H5 ,
C14 H12 O2 , M r 212.25, bp (2.0 kPa) 170 – Three cinnamates are of some importance in per-
171 ◦ C, mp 21 – 22 ◦ C, d 25 20 fumery:
4 1.1121, nD 1.5680,
is the main component of Peru balsam. It occurs
in fairly large amounts in a number of blossom
concretes and absolutes (e.g., tuberose and hy-
acinth). It forms either a viscous liquid or solid
flakes and has a weak, sweet-balsamic odor. For Methyl cinnamate [103-26-4], R = CH3 ,
further properties and synthesis, see Benzoic C10 H10 O2 , M r 162.19, bp (101.3 kPa) 261.9 ◦ C,
Acid and Derivatives, Chap. 8.5. mp 36.5 ◦ C, d 20 21
4 1.0911, nD 1.5766, occurs in
Benzyl benzoate is used in perfumery as a essential oils, mostly as the trans-isomer. It is
fixative and as a modifier in heavy blossom fra- the main component of oils isolated from Alpinia
grances. species (content up to 80 %) and Ocimum canum
varieties (> 50 %). It has also been identified as
a volatile aroma component of cinnamon and
2.5.7.2. Phenyl acetates strawberries.
Methyl cinnamate is a colorless crystalline
Of the phenyl acetates, the following are particu- solid with a fruity, sweet-balsamic odor. In ad-
larly important fragrance and flavor substances: dition to the common esterification methods, it
can be prepared by Claisen condensation of ben-
zaldehyde and methyl acetate in the presence of
sodium. Methyl cinnamate is used in soap per-
fumes, as well as in blossom and oriental per-
Ethyl phenyl acetate [101-97-3], fumes, and is sometimes added to aromas.
R = CH2 CH3 , C10 H12 O2 , M r 164.20, bp
(101.3 kPa) 227 ◦ C, d 20 20
4 1.0333, nD 1.4980, is
Benzyl cinnamate [103-41-3],
a volatile aroma component of fruit and honey. R = CH2 C6 H5 , C16 H14 O2 , M r 238.29, mp 35 –
It is a colorless liquid with a strong, sweet odor 36 ◦ C, occurs in balsams and balsam oils. It
reminiscent of honey. Small amounts are used forms white, sweet-balsamic-smelling crystals.
in flower perfumes and in fruit flavors. Benzyl cinnamate is used as a fixative in per-
fumes and as a component of heavy, oriental
Geranyl phenyl acetate [102-22-7], perfumes.
R =CH2 CH=C(CH3 )CH2 CH2 CH=C(CH3 )2 ,
C18 H24 O2 , M r 272.39, has not been found in Phenethyl cinnamate [103-53-7],
nature. It is a yellow liquid with a mild rose R = CH2 CH2 C6 H5 , C17 H16 O2 , M r 252.31, mp
odor and a secondary honey note. It is used 65 – 68 ◦ C, occurs in extracts from Populus bal-
as a fixative in rose compositions and heavy samifera buds. It is a crystalline solid with a
perfumes. heavy, rosy-balsamic odor. It is used as a fix-
ative in blossom fragrances.
60 Flavors and Fragrances

2.5.8. Miscellaneous Compounds

Of the few aromatic, nitrogen-containing fra-

grance substances, the nitro musks are by far the
most important. They are still considerably im-
portant commercially as substitutes for the nat-
ural macrocyclic musks that are difficult to syn-
thesize, but nitro musks are being increasingly
replaced by lightfast musk fragrances. Methyl
anthranilate and its N-methyl derivative are also
aromatic, nitrogen-containing compounds that
are used as fragrances and flavors in fairly large
amounts. A number of aromatic nitriles have
been introduced; they are stable to alkali and, Musk ketone is widely used as a fixative in
therefore, are used in soap perfumes. blossom and phantasy compositions.

Musk xylol [81-15-2], 2,4,6-trinitro-1,3-di- Cinnamonitrile [4360-47-8], C9 H7 N, M r

methyl-5-tert-butylbenzene, C12 H15 N3 O6 , M r 129.16, bp (1.7 kPa) 135 – 135.5 ◦ C, mp
297.27, mp 114 ◦ C, does not occur in nature. 23.5 – 24 ◦ C, d 25 1.0244, n25
D 1.6001; trans-
It forms yellow crystals with a persistent musk cinnamonitrile is a colorless crystalline solid or
odor. Musk xylol is prepared by alkylation of m- a colorless viscous liquid with a spicy, slightly
xylene with isobutene and subsequent nitration flowery odor.
with a sulfuric acid–nitric acid mixture. Cinnamonitrile can be prepared by one of the
common routes to nitriles, e.g., by dehydration
of cinnamaldoxime. It is stable to alkali and is
used for perfuming soap and detergents.

Trade Name. Cinnamalva (IFF).

5-Phenyl-3-methyl-2-pentenonitrile
[93893-89-1], C12 H13 N, M r 171.24, bp (20 Pa)
82 – 88 ◦ C, d 25 0.979, n20
D 1.5340, is a color-
less liquid with a citrus-fruity, slightly balsamic
odor. The commercial product is a 2 : 3 mixture
of the cis and trans-isomers.
Musk xylol is used in large quantities in inex- The nitrile is prepared by condensation of
pensive perfumes for soap and household prod- benzylacetone with cyanoacetic acid in the pres-
ucts. ence of pyridine and by elimination of carbon
dioxide. The mixture is used as such in soap and
Musk ketone [81-14-1], 3,5-dinitro- detergent perfumes [140].
2,6-dimethyl-4-tert-butylacetophenone,
C14 H18 N2 O5 , M r 294.31, mp 137 ◦ C, does
not occur in nature. It forms yellowish crys-
tals with a sweet, very persistent, slightly an-
imal musk odor. Musk ketone is prepared by
Friedel–Crafts acetylation of 1,3-dimethyl-5- Trade Name. Citronitril (Haarmann & Reimer).
tert-butylbenzene, and nitration of the resulting
2,6-dimethyl-4-tert-butylacetophenone with ni- Methyl anthranilate [134-20-3],
tric acid. C8 H9 NO2 , M r 151.16, bp (2 kPa) 135.5 ◦ C,
 Flavors and Fragrances 61

mp 24 – 25 ◦ C, d 19 20
4 1.1682, nD 1.5815, occurs 2.6.1. Phenols, Phenyl Esters, and Phenyl
in a large number of blossom essential oils (e.g., Ethers
neroli, ylang-ylang, and jasmin oils), grapes, and
citrus oils. It occurs as white crystals or a yel- Of the phenols and phenyl ethers used
lowish liquid, that show blue fluorescence and as fragrance and flavor compounds, 4-allyl-
have an orange blossom odor. Methyl anthrani- (30, R = H) and 4-propenylphenols (31 and
late is prepared by esterification of anthranilic 32, R = H) and their methyl ethers (30 – 32,
acid with methanol or by reaction of isatoic R = CH3 ) occur particularly frequently in essen-
anhydride with methanol [141]. tial oils.

It is used in a large number of blossom fra-

grances. However, its use in perfumes for soaps
and cosmetics is limited because it causes discol- A second hydroxyl or methoxyl substituent
oration. It is used in aroma compositions (e.g., is often present; 2-methoxy-4-allylphenol and
in grape and citrus flavors). 2-methoxy-4-propenylphenol are the most im-
portant compounds belonging to this category.
Methyl N-methylanthranilate [85-91-6],
C9 H11 NO2 , M r 165.19, bp (1.6 kPa) 130 – Diphenyl ether [101-84-8], C12 H10 O, M r
131 ◦ C, d 20 20
4 1.1295, nD 1.5796, is the main com- 170.21, bp (1.34 kPa) 121 ◦ C, mp 26.8 ◦ C, d 20
ponent of petitgrain oil from mandarin leaves 1.0748, has not been observed in nature. It is
and is also found in mandarin peel oil. It is a a colorless liquid or a crystalline solid with an
pale yellow, fluorescent liquid with a delicate odor reminiscent of geranium leaves. Diphenyl
mandarin odor. The ester can be prepared by ether is obtained as a byproduct in the pro-
methylation of methyl anthranilate. It is used in duction of phenol by high-pressure hydrolysis
soap and cosmetic perfumes as well as in aro- of chlorobenzene. For further details of prop-
mas, particularly for mandarin flavors. (IFRA erties and synthesis, see → Phenol Derivatives,
recommendation) Chap. 6.3. Because of its stability and low price,
diphenyl ether is used in large quantities in soap
perfumes. However, its main application is as
a heat-transfer medium (eutectic mixture with
diphenyl).

Some Schiff’s bases of methyl anthrani-

late are interesting fragrance materials, e.g.,
those formed with hydroxydihydrocitronellal
[89-43-0] and 2,4-dimethyl-3-cyclohexene car-
Thymol [89-83-8], 2-isopropyl-5-methyl-
boxaldehyde [68845-02-3]. Both have a heavy
phenol, C10 H14 O, M r 150.22, bp (101.3 kPa)
blossom odor and a high tenacity.
232.5 ◦ C, mp 51.5 ◦ C, d 20 20
4 0.9756, nD 1.5227,
is the main constituent of thyme and some orig-
anum oils; it also occurs in many other essential
2.6. Phenols and Phenol Derivatives oils. It forms colorless crystals with a spicy-
herbal, slightly medicinal odor reminiscent of
For a detailed description of phenols and their thyme. For further details of properties and syn-
derivatives, see → Phenol, → Phenol Deriva- thesis, see → Phenol Derivatives, Chap. 1.5.3.
tives.
62 Flavors and Fragrances

Thymol is used as a dry top note in laven-

der compositions, in men’s fragrances, and as a
disinfectant in oral hygiene products. It is also
important as a starting material for the produc-
tion of racemic menthol (see page 30).
Since isolation from oils does not always
satisfy demand, synthetic processes starting
from anisole have been developed.
4) Synthesis from Anisole and Propionic Acid
Derivatives. Anisole is converted into 4-
methoxypropiophenone by Friedel–Crafts
acylation with propionyl chloride or propi-
Anethole [104-46-1], 1-methoxy-4- onic anhydride. The ketone is hydrogenated
propenylbenzene, C10 H12 O, M r 148.20, trans- to the corresponding alcohol with a copper
isomer: bp ◦ C, d 20 20
4 0.9883, nD 1.5615, occurs
chromite catalyst. The alcohol is dehydrated
both as its cis- and trans-isomers in nature; how- in the presence of acidic catalysts to a mix-
ever, trans-anethole is always the main isomer. ture of cis- and trans-anethole [142].
Anethole occurs in anise oil (80 – 90 %), star
anise oil (> 90 %), and fennel oil (80 %).

trans-Anethole [4180-23-8] forms colorless

crystals (mp 21.5 ◦ C) with an anise-like odor and
a sweet taste. Anethole is oxidized to anisalde-
hyde (e.g., with chromic acid); when hydro-
genated it is converted into 1-methoxy-4-pro- 5) Synthesis from Anisole and Propanal.
pylbenzene. Anisole is converted into a mixture of
Production. Isolation of anethole from ane- 1,1-bis(4-methoxyphenyl)propane and small
thole-rich essential oils has lost its significance amounts of isomeric compounds by conden-
in favor of isolation from sulfate turpentine oils sation with propionaldehyde in the presence
(see page 118). of catalytic amounts of acid. 1,1-Bis(4-meth-
oxyphenyl) propane is cleaved when heated
1) Anethole can be crystallized from oils in to give anethole and anisole [143].
which it occurs as a major component (anise,
star anise, and fennel oils). Uses. Anethole is used in large quantities in
2) A fraction of American sulfate turpentine the alcoholic beverage industry (Pernod, Ouzo)
oil (0.5 % of the total) consists mainly and in oral hygiene products. Some crude ane-
of an azeotropic mixture of anethole and thole is converted into anisaldehyde.
caryophyllene. trans-Anethole can be iso-
lated from this mixture by crystallization. 2-Phenoxyethyl isobutyrate [103-60-6],
3) Another fraction of American sulfate tur- C12 H16 O3 , M r 208.26, bp (530 Pa) 125 –
pentine oil (1 % of the total) consists essen- 127 ◦ C, d 25 20
25 1.044 – 1.050, nD 1.492 – 1.496, is
tially of an azeotropic mixture of estragole a fragrance compound that does not occur in na-
(1-methoxy-4-allylbenzene, bp (101.3 kPa) ture. It is a colorless liquid with a sweet, flowery-
216 ◦ C) and α-terpineol. Treatment with fruity odor.
potassium hydroxide yields a mixture of ane-
thole isomers and α-terpineol, which can be
separated by fractional distillation.
 Flavors and Fragrances 63

The ester is prepared by esterification of 2- because it is thermodynamically more stable.

phenoxyethanol with isobutyric acid and is used Isoeugenol is a yellowish, viscous liquid with
as a fixative in perfumes (rose and lavender a fine clove odor, that of the crystalline trans-
types) as well as for fruity notes. isomer being the more delicate.
Trade Name. Phenirat (Haarmann & Reimer). Isoeugenol can be hydrogenated catalytically
to form dihydroeugenol. Vanillin was formerly
β-Naphthyl Alkyl Ethers. The β-naphthyl prepared by oxidation of isoeugenol. Additional
alkyl ethers described below are used in per- fragrance compounds are prepared by esterifica-
fumery, especially in soap perfumes. The ethers tion or etherification of the hydroxyl group.
are prepared by O-alkylation of β-naphthol. Production. Starting materials for the synthe-
They have not been observed in nature. sis of isoeugenol are eugenol and guaiacol.
1) Synthesis from Eugenol. The sodium or
potassium salt of eugenol is isomerized to
isoeugenol by heating. Isomerization can
β-Naphthyl methyl ether [93-04-9], R = CH3 , also be carried out catalytically in the pres-
C11 H10 O, M r 158.20, bp (1.3 kPa) 138 ◦ C, mp ence of ruthenium [144] or rhodium [145]
73 – 74 ◦ C, forms white crystals with an intense compounds.
orange blossom odor.
β-Naphthyl ethyl ether [93-18-5], R = CH2 CH3 ,
C12 H12 O, M r 172.23, bp (1.3 kPa) 148 ◦ C, mp
37 – 38 ◦ C, forms white crystals with a mild,
long-lasting, orange blossom fragrance.
β-Naphthyl isobutyl ether [2173-57-1], 2) Synthesis from Guaiacol. Guaiacol is ester-
R = CH2 CH(CH3 )2 , C14 H16 O, M r 200.28, mp ified with propionic acid, and the result-
33 – 33.5 ◦ C, forms white crystals with a fruity, ing guaiacyl propionate rearranges in the
orange blossom odor. presence of aluminum chloride to give 4-
hydroxy-3-methoxypropiophenone. Reduc-
Hydroquinone dimethyl ether [150-78-7], tion of the ketone to the corresponding sec-
1,4-dimethoxybenzene, C8 H10 O2 , M r 138.17, ondary alcohol and dehydration finally yield
bp (2.7 kPa) 109 ◦ C, mp 57 – 58 ◦ C, occurs in isoeugenol [146–148].
hyacinth oil and has also been identified in tea.
It is a white crystalline solid with an intensely
sweet, somewhat herbal, nutlike odor.
Hydroquinone dimethyl ether is prepared by
etherification of hydroquinone and is used in
soap perfumes.

Isoeugenol [97-54-1], 2-methoxy-4-(1-

propenyl)phenol, C10 H12 O2 , M r 164.22;
cis-isomer [5912-86-7]: bp (1.7 kPa) 134 –
135 ◦ C, d 20 20
4 1.0837, nD 1.5726; trans-isomer
[5932-68-3]: mp 33 – 34 ◦ C, bp (1.7 kPa) 141 –
142 ◦ C, d 20 20
4 1.0852, nD 1.5784. Isoeugenol
occurs in many essential oils, mostly with Uses. Isoeugenol is used in perfumery in a
eugenol, but not as the main component. Com- large number of blossom compositions, mostly
mercial isoeugenol is a mixture of cis- and trans- for clove and carnation types, but also in orien-
isomers, in which the trans-isomer dominates tal perfumes. (Limiting IFRA recommendation)
64 Flavors and Fragrances

Small amounts are employed in aromas and in Eugenol methyl ether [93-15-2],
reconstituted essential oils. C11 H14 O2 , M r 178.23, bp (1.5 kPa) 127 –
129 ◦ C, d 20 20
4 1.0396, nD 1.5340, occurs in nu-
Isoeugenol methyl ether [93-16-3], merous essential oils, sometimes at a very high
C11 H14 O2 , M r 178.23, cis-isomer [6380-24-1]: concentration; leaf and wood oil from Dacry-
bp (900 Pa) 137 – 137.5 ◦ C, d 20 4 1.0530, nD
20
dium franklinii Hook. (Huon pine oil) contain
1.5628; trans-isomer [6379-72-2]: bp (700 Pa) more than 90 %. The ether is an almost colorless
126 ◦ C, d 20 20
4 1.0556, nD 1.5699, occurs in small liquid with a mild-spicy, slightly herbal odor. It is
quantities in several essential oils. It is a color- prepared by methylation of eugenol and is used
less to pale yellow liquid with a mild clove odor. in perfumery (e.g., in carnation and lilac com-
positions) and in flavor compositions.

Isoeugenol methyl ether is used in perfumery

in clove and carnation bases and as a fixative in
spicy-floral compositions. Eugenyl acetate [93-28-7], C12 H14 O3 , M r
206.24, bp (400 Pa) 120 – 121 ◦ C, mp 29 ◦ C, d 204
Eugenol [97-53-0], 2-methoxy-4-allylphe- 1.0806, n20
D 1.5205, occurs in clove oil, together
nol, C10 H12 O2 , M r 164.20, bp (1.3 kPa) 121 ◦ C, with eugenol. It is a crystalline solid or yellowish
d 20 20
4 1.0652, nD 1.5409, is the main component liquid with a slightly fruity, clove odor. Eugenyl
of several essential oils; clove leaf oil and cinna- acetate is prepared by acetylation of eugenol
mon leaf oil may contain > 90 %. Eugenol oc- with acetic anhydride and is used in clove com-
curs in small amounts in many other essential positions to accentuate flowery character.
oils. It is a colorless to slightly yellow liquid
with a spicy, clove odor.

Propenylguethol [94-86-0], 2-ethoxy-5-(1-

Catalytic hydrogenation (e.g., in the presence propenyl)phenol, C11 H14 O2 , M r 178.23, exists
of noble-metal catalysts) yields dihydroeugenol. in cis (mp 35 – 36 ◦ C) and in trans (mp 86 ◦ C)
Isoeugenol is obtained from eugenol by shift- forms. The trans-isomer has a sweet vanilla-
ing the double bond (see Isoeugenol, page like odor. Propenylguethol can be prepared from
65). Esterification and etherification of the hy- isosafrole by reaction with methylmagnesium
droxyl group of eugenol yield valuable fragrance chloride or by ethylation of isoeugenol followed
and flavor materials (e.g., eugenyl acetate and by selective demethylation with alkali [149].
eugenyl methyl ether).
Production. Since sufficient eugenol can be
isolated from cheap essential oils, synthesis is
not industrially important. Eugenol is still pref-
erentially isolated from clove leaf and cinnamon
leaf oil (e.g., by extraction with sodium hydrox-
ide solution). Nonphenolic materials are then
removed by steam distillation. After the alka-
line solution is acidified at low temperature, pure
eugenol is obtained by distillation.
Uses. Eugenol is used in perfumery in clove
and carnation compositions as well as for orien- It is used in perfumery, for example, in soaps
tal and spicy notes. It is a common component and cosmetics, to create or enhance vanilla notes.
of clove and other aroma compositions. In den-
tistry, it is used as an antiseptic.
 Flavors and Fragrances 65

p-Cresyl phenylacetate [101-94-0], derivatives of protocatechu aldehyde (3,4-di-

C15 H14 O2 , M r 226.27, is prepared by esterifica- hydroxybenzaldehyde) are well-known repre-
tion of p-cresol with phenylacetic acid. It forms sentatives. The monomethyl ether of protocat-
crystals (mp 75 – 76 ◦ C) with a narcissus odor echu aldehyde, vanillin, is perhaps the most
and a honey note. It is used in blossom compo- widely used flavor compound. Other important
sitions with a slight animal note. derivatives of this aldehyde are veratraldehyde
(dimethyl ether) and piperonal (formaldehyde
acetal derivative); they are not only used as fra-
grance and flavor substances, but also are inter-
mediates in many industrial processes.

p-Anisaldehyde [123-11-5], 4-methoxy-

2.6.2. Phenol Alcohols and their Esters benzaldehyde, C8 H8 O2 , M r 136.15, bp
In comparison with the araliphatic alcohols dis- (1.85 kPa) 132 ◦ C, d 25 25
4 1.1192, nD 1.5703, oc-
cussed in Section 2.5.5, very few phenol alco- curs in many essential oils, often together with
hols are used as fragrance and flavor materials. anethole. It is a colorless to slightly yellowish
None of the alcohol derivatives of vanillin, ethyl- liquid with a sweet, mimosa, hawthorn odor.
vanillin, and heliotropin or their esters have spe- p-Anisaldehyde can be hydrogenated to anise
cial organoleptic properties. Anise alcohol and alcohol and readily oxidizes to anisic acid when
its acetate are the only products that are used exposed to air. Synthetic routes to anisaldehyde
to some extent in perfume and aroma composi- usually involve the oxidation of p-cresyl methyl
tions. ether. Manganese dioxide and sulfuric acid are
usually used for oxidation. In a Russian process,
Anisyl alcohol [105-13-5], 4-methoxybenzyl p-cresyl methyl ether is oxidized with alkali per-
alcohol, C8 H10 O2 , M r 138.17, bp (1.3 kPa) oxysulfates in the presence of silver salts [150].
136 ◦ C, d 20 25
4 1.1140, nD 1.5420, occurs in vanilla
pods and in anise seeds. It is a colorless liquid
with a sweet-flowery, slightly balsamic odor.
Pure anise alcohol for perfumery and fla-
vor purposes is prepared by hydrogenation of
anisaldehyde. It is used in perfumery in blossom
compositions (e.g., lilac and gardenia types) and Other industrial processes are the liquid-
in flavors for confectionery and beverages. phase oxidation in the presence of cobalt cat-
alysts [151] and the electrochemical oxidation
in the presence of lower aliphatic alcohols via
the corresponding anisaldehyde dialkyl acetal
[152].
Anisyl acetate [104-21-2], C10 H12 O3 , M r p-Anisaldehyde is frequently used in sweet
180.20, bp (1.5 kPa) 133 ◦ C, d 20 4 1.1084, has
blossom compositions (e.g., in lilac and
been found in several types of berries. It is a hawthorn types) as well as in flavor compo-
colorless liquid with a fruity, slightly balsamic sitions for confectioneries and beverages. p-
blossom odor and is used occasionally in sweet- Anisaldehyde is an intermediate in many indus-
flowery compositions, but more frequently in trial processes. Its hydrogensulfite derivative is
flavor compositions for fruity notes. used as a brightener for metals in galvanic baths.

Vanillin [121-33-5], 4-hydroxy-3-meth-

2.6.3. Phenol Aldehydes oxybenzaldehyde, C8 H8 O3 , M r 152.15, bp
Phenol aldehydes are generally pleasant- (1.3 kPa) 155 ◦ C, mp 82 – 83 ◦ C, d 20
4 1.056,
smelling products. Some of them are par- is found in many essential oils and foods, but
ticularly important as fragrance and fla- is often not essential for their odor or aroma.
vor compounds. Anisaldehyde and certain However, it does determine the odor of essen-
66 Flavors and Fragrances

tial oils and extracts from Vanilla planifolia and ence of catalysts. When the reaction is
V . tahitensis pods, in which it is formed during completed, the solid wastes are removed.
ripening by enzymatic cleavage of glycosides. Vanillin is extracted from the acidified so-
lution with a solvent (e.g., butanol or ben-
zene) and reextracted with sodium hydro-
gen sulfite solution. Reacidification with sul-
furic acid followed by vacuum distillation
Annually about 12 000 t vanillin are produced yields technical-grade vanillin, which must
synthetically and about 20 t originate from nat- be recrystallized several times to obtain food-
ural sources [153]. grade vanillin. Water, to which some ethanol
Properties. Vanillin is a colorless crystalline may be added, is used as the solvent in the
solid with a typical vanilla odor. Because it pos- last crystallization step.
sesses aldehyde and hydroxyl substituents, it Preparation from Guaiacol and Glyoxylic
undergoes many reactions. Additional reactions Acid.
are possible due to the reactivity of the aro- Several methods can be used to introduce an
matic nucleus. Vanillyl alcohol and 2-methoxy- aldehyde group into an aromatic ring. Con-
4-methylphenol are obtained by catalytic hydro- densation of guaiacol with glyoxylic acid
genation; vanillic acid derivatives are formed followed by oxidation of the resulting man-
after oxidation and protection of the phenolic delic acid to the corresponding phenylgly-
hydroxyl group. Since vanillin is a phenol al- oxylic acid and, finally, decarboxylation con-
dehyde, it is stable to autoxidation and does tinues to be a competitive industrial process
not undergo the Cannizzaro reaction. Numerous for vanillin synthesis.
derivatives can be prepared by etherification or Currently, guaiacol is synthesized from cat-
esterification of the hydroxyl group and by aldol echol, which is prepared by acid-catalyzed
condensation at the aldehyde group. For exam- hydroxylation of phenol with hydrogen per-
ple, several of these derivatives are intermediates oxide. Glyoxylic acid is obtained as a by-
in the synthesis of pharmaceuticals. product in the synthesis of glyoxal from acet-
Production. Most commercial vanillin is ob- aldehyde and can also be produced by oxi-
tained by processing waste sulfite liquors; the dation of glyoxal with nitric acid. Conden-
remainder is synthesized from guaiacol. Prepa- sation of guaiacol with glyoxylic acid pro-
ration by oxidation of isoeugenol is of historical ceeds smoothly at room temperature and in
interest only. weakly alkaline media. A slight excess of
guaiacol is maintained to avoid formation
Preparation from Waste Sulfite Liquors: of disubstituted products; excess guaiacol is
The starting material for vanillin produc- recovered. The alkaline solution containing
tion is the lignin present in sulfite wastes 4-hydroxy-3-methoxymandelic acid is then
from the cellulose industry (→ Lignin). The oxidized in air in the presence of a cata-
concentrated mother liquors are treated with lyst until the calculated amount of oxygen is
alkali at elevated temperature and pres- consumed [155]. Crude vanillin is obtained
sure in the presence of oxidants. The by acidification and simultaneous decarbox-
vanillin formed is separated from the byprod- ylation of the (4-hydroxy-3-methoxyphenyl)
ucts, particularly acetovanillone (4-hydroxy- glyoxylic acid solution. Commercial grades
3-methoxyacetophenone), by extraction, dis- are obtained by vacuum distillation and sub-
tillation, and crystallization. sequent recrystallization as described under
A large number of patents describe vari- method (1).
ous procedures for the (mainly) continu- This process has the advantage that, un-
ous hydrolysis and oxidation processes, as der the reaction conditions, the glyoxyl rad-
well as for the purification steps required ical enters the aromatic guaiacol ring al-
to obtain high-grade vanillin [154]. Lignin most exclusively para to the phenolic hy-
is degraded either with sodium hydroxide droxyl group. Tedious separation procedures
or with calcium hydroxide solution and si- are thus avoided.
multaneously oxidized in air in the pres-
 Flavors and Fragrances 67

Piperonal [120-57-0], heliotropin, 3,4-

methylenedioxybenzaldehyde, C8 H6 O3 , M r
150.13, bp (1.6 kPa) 139.4 ◦ C, mp 37 ◦ C, d 43.2
4
1.2792, occurs in a number of essential oils, but
never as the main component. It forms white
crystals with a sweet-flowery, slightly spicy,
heliotrope-like odor.
Production. Piperonal is produced by two
main routes:
From Isosafrole.
Uses. The main application of vanillin is the For many years, oxidative cleavage of isosaf-
flavoring of foods (e.g., ice cream, chocolate, role was the only route applicable on an in-
bakery products, and confectioneries). Small dustrial scale. Examples of oxidants that give
quantities are used in perfumery to round and fix good yields of piperonal are chromium(VI)
sweet, balsamic fragrances. Vanillin is also used salts, oxygen, and ozone.
as a brightener in galvanotechnical processes
and is an important intermediate in, for example,
the production of pharmaceuticals such as l-3,4-
dihydroxyphenylalanine (l-DOPA) and methyl-
dopa.

Veratraldehyde [120-14-9], 3,4-dimeth- This method is still used currently because

oxybenzaldehyde, C9 H10 O3 , M r 166.18, occurs safrole (the starting material for isosafrole)
in a few essential oils and is a crystalline solid can be isolated from essential oils relatively
(mp 44.5 – 45 ◦ C) with a woody, vanilla-like inexpensively and in sufficient quantity.
odor. From Catechol. Several routes have been
Veratraldehyde can be prepared by methyla- developed for the synthesis of piperonal
tion of vanillin. It is used in oriental and warm- from catechol. In one such route, catechol is
woody fragrances, as well as in flavor composi- converted into 3,4-dihydroxymandelic acid
tions for vanilla notes. It is an intermediate in, with glyoxylic acid in an alkaline medium
for example, the synthesis of pharmaceuticals. in the presence of aluminum oxide. 3,4-
Dihydroxymandelic acid is oxidized to the
corresponding keto acid (e.g., with cop-
per(II) oxide), which is decarboxylated to
3,4-dihydroxybenzaldehyde [156]. The lat-
ter product is converted into piperonal, for
Ethylvanillin [121-32-4], 3-ethoxy-4-
hydroxybenzaldehyde, C9 H10 O3 , M r 166.18,
mp 77 – 78 ◦ C, does not occur in nature. Its odor
resembles that of vanillin but is approximately
three times as strong. Ethylvanillin can be pre-
pared by method (2) as described for vanillin,
using guethol instead of guaiacol as the starting
material.
Ethylvanillin is used extensively in the choco-
late industry. It gives a sweet, balsamic note to
flowery and fruity perfume compositions.
68 Flavors and Fragrances

example, by reaction with methylene chlo- 1-(4-Hydroxyphenyl)-3-butanone [5471-

ride in the presence of quaternary ammonium 51-2], raspberry ketone, C10 H12 O2 , M r 164.20,
salts [157]. mp 82 – 83 ◦ C, is a highly characteristic com-
In another route, catechol is first reacted ponent of raspberry aroma. It forms colorless
with methylene chloride and converted into crystals with a sweet-fruity odor strongly remi-
1,2-methylenedioxybenzene [157]. Reaction niscent of raspberries.
with glyoxylic acid in strongly acidic me-
dia yields 3,4-methylenedioxymandelic acid
[158]. Subsequent oxidation and decarbox-
ylation with nitric acid affords piperonal.

Raspberry ketone is prepared by alkali-

catalyzed condensation of the alkali salt of
4-hydroxybenzaldehyde and acetone, followed
by selective hydrogenation of the double
bond in the resulting 4-hydroxybenzalacetone.
Other syntheses start from phenol which is
converted into 1-(4-hydroxyphenyl)-3-butanone
with methyl vinyl ketone (e.g., in the presence
of phosphoric acid) [159] or with 3-oxo-1-buta-
nol in the presence of concentrated sulfuric acid
[160].
The ketone is used in fruit flavors, particu-
Uses. Piperonal is used in many flowery-
larly in raspberry compositions.
spicy fine fragrances and is also an important
Trade Names. Frambinon (DRAGOCO),
ingredient of flavor compositions.
Oxyphenylon (IFF).

2.6.4. Phenol Ketones

2.6.5. Phenol Carboxylates
Few of the phenol derivatives that have a keto
Alkyl and aralkyl salicylates, as well as methyl
substituent in their side-chain are of interest as
3-methylorsellinate (an oakmoss fragrance) are
fragrance or flavor substances. A number of phe-
important phenol carboxylates that are used in
nols and phenyl ethers acetylated in the ben-
flavors and fragrances. The following salicylates
zene ring have been identified as volatile com-
are used in perfume and flavor compositions
ponents of foods. 4-Methoxyacetophenone is
and can be prepared by esterification of salicylic
of some interest as a fragrance compound. 4-
acid.
Hydroxybenzylacetone, a higher mass phenol
ketone, has a characteristic raspberry aroma.

4-Methoxyacetophenone [100-06-1], ac-

etanisole, C9 H10 O2 , M r 150.18, d 41 1.0818,
n41
D 1.5470, occurs in anise oil. It forms white Methyl salicylate [119-36-8], R = CH3 ,
crystals (mp 38 ◦ C) with a sweet odor, remi- C8 H8 O3 , M r 152.15, bp (1.6 kPa) 98 ◦ C, d 25
4
niscent of hawthorn. 4-Methoxyacetophenone 1.1782, n25
D 1.5350, is the main component of
is prepared by Friedel–Crafts acetylation of wintergreen oil and occurs in small quantities
anisole and is used in soap perfumes. in other essential oils and fruit. It is a color-
less liquid with a sweet, phenolic odor. Methyl
salicylate is used in perfumery as a modifier in
blossom fragrances and as a mild antiseptic in
oral hygiene products.
 Flavors and Fragrances 69

Isoamyl salicylate [87-20-7], mixture of this ketone and 5-chlorohexan-3-

R = CH2 CH2 CH(CH3 )2 , C12 H16 O3 , Mr one) to give a substituted 3-hydroxy-2-cyclo-
208.26, bp (2 kPa) 151 – 152 ◦ C, d 204 1.0535, hexenone (33). Aromatization, in good yield,
n20
D 1.5065, has been found in a number of fruit is achieved by reaction of the hydroxycyclo-
aromas. It is a colorless liquid with a sweet, hexenone with a suitable N-haloamide. The
clover-like odor and is used in perfumery for intermediate 3-hydroxy-2-cyclohexenone can
floral and herbal notes, particularly in soap per- also be obtained by condensation of methyl
fumes. 3-oxopentanoate with methyl crotonate [162].

Hexyl salicylate [6259-76-3],

R = (CH2 )5 CH3 , C13 H18 O3 , M r 222.28, bp
(1.6 kPa) 167 – 168 ◦ C, d 25 25
25 1.035, nD 1.5049,
has been reported in carnation flower absolute
[161]. It is a colorless liquid with a green,
flowery-spicy odor, reminiscent of azaleas. It is
used for blossom and herbal notes in perfumes,
e.g., in soap, personal hygiene products, and de-
tergents.

cis-3-Hexenyl salicylate [65405-77-8],

R = cis-(CH2 )2 CH=CHCH2 CH3 , C13 H16 O3 ,
M r 220.27, bp (150 Pa) 125 ◦ C, d 2525 1.0589,
n20
D 1.5210, has been identified in carnation
flower absolute. It is a colorless liquid with a
long-lasting, sweet, green balsamic odor. It is Another route to methyl 3-methylorsellinate
used in fine fragrances and for scenting soaps, starts from β-orcinol, which is converted into a
cosmetics, and detergents. carboxylic acid derivative by reaction with car-
bon dioxide (Kolbe synthesis). The acid is ester-
Benzyl salicylate [118-58-1], R = CH2 C6 H5 , ified (e.g., with dimethyl sulfate) [163].
C14 H12 O3 , M r 228.25, bp (1.3 kPa) 186 –
188 ◦ C, d 20 20
4 1.1799, nD 1.5805, which occurs in
several essential oils, is a colorless, viscous liq-
uid with a weak, sweet, slightly balsamic odor.
Benzyl salicylate is used as a fixative in flowery-
spicy perfume compositions and in flavors.

Phenethyl salicylate [87-22-9],

R = CH2 CH2 C6 H5 , C15 H14 O3 , M r 242.27, mp
44 ◦ C, which has not been reported to occur in
nature, is a crystalline solid with a weak, long-
lasting, balsamic, blossom odor, reminiscent of
rose and hyacinth. It is used in perfumery for
spicy and balsamic blossom compositions. Methyl 3-methylorsellinate is used as a sub-
stitute for oakmoss extract in fine fragrances,
Methyl 3-methylorsellinate [4707-47-5], soaps, and cosmetics.
methyl 2,4-dihydroxy-3,6-dimethylbenzoate, Trade Name. Evernyl (Givaudan Roure), Ver-
C10 H12 O4 , M r 196.20, mp 145 ◦ C, is an odor- amoss (IFF).
determining constituent of oakmoss extract and
forms colorless crystals with a mossy-earthy
odor. It can be prepared from acyclic com-
pounds. In an industrial process, dimethyl mal-
onate is condensed with 4-hexen-3-one (or a
70 Flavors and Fragrances

2.7. O- and O, S-Heterocycles

2.7.1. Cyclic Ethers
2,5-Diethyltetrahydrofuran [41239-48-9],
Cyclic ethers used as fragrances include a num- fruity, herbal-minty note
ber of terpenoid compounds. Some of them,
such as 1,4-cineole [470-67-7] and 1,8-cineole,
occur in essential oils in significant quantities.
Others are only minor components; examples
are rose oxide, nerol oxide [1786-08-9], and
rose furan [15186-51-3], which contribute to the 2-Methyl-4-propyl-1,3-oxathiane [67715-
specific fragrance of rose oil, and caryophyl- 80-4], typical sulfury note of tropical fruit
lene oxide [1139-30-6], which has a woody,
slightly ambergris-like odor. α-Cedrene oxide 1,8-Cineole [470-82-6], 1,8-epoxy-p-
[11000-57-0] is another wood-fragrance com- menthane, eucalyptol, C10 H18 O, M r 154.25, bp
pound, that can be easily prepared by epoxida- (101.8 kPa) 176 – 177 ◦ C, fp 1 ◦ C, d 20
4 0.9267,
tion of cedarwood oil hydrocarbons. n20
D 1.4586, occurs in many terpene-containing
Except for some of the above-mentioned essential oils, sometimes as the main compo-
compounds, only a few other cyclic ethers are nent. For example, eucalyptus oils contain up to
important, for instance, 4,6,6,7,8,8-hexamethyl- 85 % 1,8-cineole and laurel leaf oil contains up
1,3,4,6,7,8-hexahydropenta[g]benzopyran, a to 70 %. It is a colorless liquid with a character-
musk fragrance that is used in large amounts. istic odor, slightly reminiscent of camphor.
Numerous furan and pyran derivatives, many
of which originate from heat treatment of car-
bohydrates, largely determine the odor of pro-
cessed foods. Of this group, 2,5-dimethyl-4-
hydroxy-2H-furan-3-one and maltol are used in
fairly large quantities in flavors. The following
compounds are used in relatively small amounts
in flavor compositions: 1,8-Cineole is one of the few fragrance ma-
terials that is obtained exclusively by isola-
tion from essential oils, especially eucalyptus
oils. Technical-grade 1,8-cineole with a purity
of 99.6 – 99.8 % is produced in Spain in large
2-Furaldehyde [98-01-1], freshyl baked quantities by fractional distillation of Eucalyp-
bread odor tus globulus Labillardière. A product essentially
free from other products can be obtained by crys-
tallization of cineole-rich eucalyptus oil frac-
tions.
1,8-Cineole has a fresh odor and is used in
2-Acetylfuran [1192-62-7], sweet balsamic large quantities in fragrances as well as in fla-
odor vors (e.g., in oral hygiene products).

4-Methyl-2-(2-methyl-1-propenyl)tetra-
hydropyran [16409-43-1], rose oxide,
Methyl 2-furoate [611-13-2], fruity, C10 H18 O, M r 154.25, bp (1.6 kPa) 70 ◦ C, d 20 4
mushroom-like odor 0.875, n20
D 1.4570, [α]D for the optically pure
(−)-cis form − 58.1 ◦ , occurs in small quantities,
mainly the levorotatory cis form, in essential
oils (e.g., Bulgarian rose oil and geranium oil).
Commercial synthetic products are either opti-
2-Methylfuran-3-thiol [28588-74-1], roast cally active or inactive mixtures of the cis- and
beef aroma
 Flavors and Fragrances 71

trans-isomers. Their physical constants, partic- Rose oxide is used in rose and geranium per-
ularly the optical rotation, depend on the starting fumes.
material and the method of synthesis. They are Trade Name.Rose oxide (DRAGOCO).
colorless liquids with a strong odor reminiscent
of geranium oil and carrot leaves. Rose oxide Menthofuran [494-90-6], 3,6-dimethyl-
is usually prepared from citronellol (see page 4,5,6,7-tetrahydrobenzofuran, C10 H14 O, M r
19), which can be converted into a mixture of 150.22, bp (1.3 kPa) 78 – 79 ◦ C, d 20 4 0.9676,
two allyl hydroperoxides (e.g., by photosensi- n20 20 ◦
D 1.4855, [α] D + 94.6 , occurs mainly as
tized oxidation with oxygen). Reduction of the the (+)-isomer, in numerous essential oils (e.g.,
hydroperoxides with sodium sulfite yields the Mentha oils). It is a colorless liquid with a minty
corresponding diols [164]. Treatment with dilute odor.
sulfuric acid results in allylic rearrangement and (+)-Menthofuran [17957-94-7] is isolated
spontaneous cyclization of one of the isomers; a from Mentha oils or is prepared synthetically,
mixture of diastereoisomeric rose oxides is thus for example, by treatment of (+)-pulegone with
formed. The unreacted diol isomer is separated fuming sulfuric acid in acetic anhydride and
by distillation. (−)-Citronellol as the starting pyrolysis of the resulting sultone.
material yields approximately a 1 : 1 mixture of
(−)-cis- and (−)-trans-rose oxide.

Menthofuran is used mainly in peppermint

oil reconstitutions.

Linalool oxide, 2-methyl-2-vinyl-5-(α-

hydroxyisopropyl)tetrahydrofuran, C10 H18 O2 ,
M r 170.25, bp (101.3 kPa) 188 ◦ C, d 204 0.939 –
0.944, n20D 1.451 – 1.455, has been identified
in essential oils and in fruit aromas. Commer-
cial linalool oxide is a mixture of the cis and
trans forms, [5989-33-3] and [34995-77-2], re-
spectively. It is a liquid with an earthy-flowery,
slightly bergamot-like odor.

Linalool oxide

Linalool oxide is prepared by oxida-

tion of linalool (see page 16). The iso-
meric compound 2,2,6-trimethyl-6-vinyltetra-
hydro-2H-pyran-3-ol [14049-11-7], which also
occurs in nature, is formed as a byproduct:
72 Flavors and Fragrances

Linalool oxide is used in perfumery (e.g., for

lavender notes) and for reconstitution of essen-
tial oils.
A dehydrated linalool oxide, 2-methyl-2-
vinyl-5-isopropenyltetrahydrofuran [13679-86-
2], occurs naturally; it has a minty eucalyptol
odor and is used in perfumery.

3a,6,6,9a-Tetramethyldodecahydronaph-
tho-[2,1-b]furan [6790-58-5] (34), C16 H28 O,
M r 236.40, mp 75 – 76 ◦ C, is a crystalline autox- In another process, a dialkyl α-methyl-
idation product of ambrein (see Ambergris, page diglycolate (formed from an alkyl lactate and an
87) with a typical ambergris odor. It is prepared alkyl monochloroacetate) is reacted with dialkyl
from sclareol, a diterpene alcohol obtained from oxalate in the presence of a sodium alkoxide and
plant waste in the production of clary sage oil dimethylformamide. The reaction product is cy-
(see Sage Oils, page 115). Oxidative degrada- clized, alkylated, hydrolyzed, and decarboxyl-
tion to a lactone, hydrogenation of the latter to ated [166].
the corresponding diol and dehydration yield
(34).

The compound is used in the flavoring of

foods.
Trade Name. Furaneol (Firmenich).

Maltol [118-71-8], 3-hydroxy-2-methyl-

The product is used in perfumery for creating 4H-pyran-4-one, C6 H6 O3 , M r 126.11, mp 162 –
ambergris notes. 164 ◦ C, occurs in pine needles and the bark of
Trade Names. Ambrox (Firmenich), Ambroxan young larch trees. It is produced when cellulose
(Cognis). or starch are heated and is a constituent of wood
tar oils. It forms crystals with a caramel-like
2,5-Dimethyl-4-hydroxy-2H-furan-3-one
odor, reminiscent of freshly baked cakes.
[3658-77-3], C6 H8 O3 , M r 128.13, is a con-
Although many routes are known for its syn-
stituent of pineapple aroma and is also found
thesis, maltol is still isolated mainly from beech-
in other foods. It forms colorless crystals (mp
wood tar. It is used in aroma compositions with
77 – 79 ◦ C) with a relatively weak, nonspe-
a caramel note and as a taste intensifier, for ex-
cific odor. Dilute solutions develop a pineap-
ample, in fruit flavors (particularly in strawberry
ple, strawberry-like odor. It can be prepared by
flavor compositions).
cyclization of hexane-2,5-diol-3,4-dione in the
presence of an acidic catalyst [165]. The dione
is the ozonization product of 2,5-hexynediol,
which is obtained by ethynylation of acetalde-
hyde.
 Flavors and Fragrances 73

3-Pentyltetrahydro-2H-pyran-4-ol acetate
[18871-14-2], C12 H22 O3 , M r 214.30, bp
(0.13 kPa) 102 – 103 ◦ C, d 25 20
25 0.974 – 0.978, nD
1.448 – 1.451, is a colorless to pale yellow liq-
uid with a sweet-floral, fruity, slightly woody,
jasmin-like odor. It is prepared by a Prins reac-
tion of 1-octene with formaldehyde and acetic
acid and is used in perfumes for various flower
types, especially jasmin.

Trade Names. Jasmophyll (Haarmann &

Reimer), Jasmopyran (Quest), Jasmal (IFF).

4,6,6,7,8,8-Hexamethyl-1,3,4,6,7,8-hexa- 4,4a,5,9b-Tetrahydroindeno[1,2-d]-1,3-di-
hydrocyclopenta[g]benzopyran [1222-05-5] oxane [18096-62-3], C11 H12 O2 , M r 176.21, bp
(35), C18 H26 O, M r 258.40, bp (1.1 kPa) 129 ◦ C, (1.3 kPa) 134 ◦ C, mp 35 – 36 ◦ C, d 15.5
15.5 1.159,
d 20 20
4 1.0054, nD 1.5342, is a viscous liquid with n20 1.559, forms crystals with an indole-like
D
a musklike odor. It is one of the most frequently odor. It is prepared by a Prins reaction from in-
used synthetic, artificial musk fragrances. The dene and formaldehyde in the presence of dilute
starting material for its synthesis is 1,1,2,3,3- sulfuric acid [169]. It is used in perfumes for
pentamethylindane, which is prepared by cy- soaps and detergents.
cloaddition of tert-amylene to α-methylstyrene.
The pentamethylindane is hydroxyalkylated
with propylene oxide in a Friedel–Crafts reac-
tion using aluminum chloride as a catalyst (anal-
ogous to the synthesis of 2-phenethyl alcohol Trade Names. Indoflor (Haarmann & Reimer),
from benzene and ethylene oxide, see page 51). Indolarom (IFF).
Ring closure of the resulting 1,1,2,3,3-penta- The 2,4-dimethyl homologue [27606-09-3] is
methyl-5-(β-hydroxyisopropyl)indane to (35) prepared by using acetaldehyde instead of form-
is accomplished with paraformaldehyde and a aldehyde. Its odor is reminiscent of geranium
lower aliphatic alcohol via the acetal [167] or and magnolia [171].
with paraformaldehyde and a carboxylic acid
anhydride via the acylate [168].
The commercial product is diluted with sol-
vents (e.g., diethyl phthalate, isopropyl myris-
tate, benzyl benzoate) to make it less viscous.
It is alkali-stable and does not discolor in light.
Therefore, it is a popular ingredient of perfume Trade Name. Magnolan (Haarmann & Reimer).
compositions for soaps, detergents, and cosmet-
ics and is used in large amounts. 2,4,6-Trimethyl-4-phenyl-1,3-dioxane
Trade Names. Galaxolide (IFF). [5182-36-5], C13 H18 O2 , M r 206.28, bp (300 Pa)
100 ◦ C, d 20 20
4 1.159, nD 1.504, is a colorless to
pale yellow liquid. This cyclic acetal has a smell
of grapefruit with herbal and fresh aspects.
74 Flavors and Fragrances

2,4,6-Trimethyl-4-phenyl-1,3-dioxane can 5,5,7,9,9,13-Hexamethyl-4,6-dioxatetra-

be produced by a Prins reaction of methylstyrene cyclo[6.5.1.1,10 03,7 ]tetradecane [211299-54-
with acetaldehyde. 6], cedrene acetonide, C18 H30 O2 , M r 278.44,
mp 157 – 158 ◦ C, is a fragrance compound with
a powdery-woody, long-lasting amber note. Its
industrial synthesis starts with the epoxidation of
cedarwood oil fractions that contain sesquiter-
pene hydrocarbons, mainly α-cedrene. Acid-
catalyzed ring opening and acetalization leads
to cedrene acetonide [172].
Trade Name. Vertacetal (DRAGOCO), Floropal The pure compound is crystalline and is fre-
(Haarmann & Reimer). quently used in soaps, cosmetics and perfumery
compositions as a fixative with high substantiv-
Isolongifolanone ethylene glycol acetal ity.
[154171-77-4], C17 H28 O2, M r 264.41, bp
(3 kPa) 142 – 143 ◦ C, d 20 20
4 1.0510, nD 1.5051 is
commercially available as a colorless liquid with
strong woody odor with flowery-fresh effects
and with a velvety moss/ambra accent. It has an
extremely long lasting odor and acts as fixative.
Isolongifolanone ethylene glycol acetal is fre-
quently used in soaps, cosmetics, and perfumery
compositions.
For the production of isolongifolanone acetal
(40), longifolene (36), which is a main compo-
nent of Indian turpentine oil, is first isomerized
to isolongifolene (37). The epoxide (38), ob-
tained by epoxidation of isolongifolene, is sub-
sequently transformed to isolongifolanone (39), Trade Name. Ambrocenide 10 (DRAGOCO).
which is reacted with ethylene glycol to the cy-
clic isolongifolanone ethyleneglycolacetal (40)
[170]. 2.7.2. Lactones
Naturally occurring organoleptically important
lactones are mainly saturated and unsaturated
γ- and δ-lactones, and to a lesser extent macro-
cyclic lactones. The occurrence of these types
of lactones reflects their ready formation from
natural acyclic precursors.
The γ- and δ-lactones are the intramolecu-
lar esters of the corresponding hydroxy fatty
acids. They contribute to the aroma of butter and
various fruits. 3,4-Dimethyl-5-pentylidenedi-
hydro-2(5H)-furanone [774-64-1] is an unsat-
urated γ-lactone with a distinct nutty flavor. 15-
Pentadecanolide is responsible for the musklike
odor of angelica root oil. Of the naturally occur-
ring bicyclic lactones, phthalides are responsible
for the odor of celery root oil, and coumarin for
Trade Name. Ysamber-K (DRAGOCO). woodruff.
The macrocyclic esters hold a special posi-
tion among the industrially produced lactone fra-
 Flavors and Fragrances 75

grance compounds. Like the well-known macro- fruity flower odors and in aroma compositions,
cyclic ketones (see Section 2.4), they have out- particularly peach flavors.
standing odor properties as musks. However, the
lactones can be prepared more easily than the γ-Undecalactone [104-67-6], (n = 6), “so-
ketones, for example, by depolymerization of called aldehyde C14 ” C11 H20 O2 , M r 184.28, bp
the corresponding linear polyesters. Since re- (2.0 kPa) 167 – 169 ◦ C, d 20 20
4 0.944, nD 1.4514,
placement of a methylene unit by oxygen af- occurs in foods and is an almost colorless liquid
fects the odor of these compounds very lit- with a peachlike odor. In addition to preparation
tle, oxalactones with 15 – 17-membered rings by radical addition of 1-octanol to acrylic acid,
are commercially produced in addition to 15- γ-undecalactone is also prepared by intramolec-
pentadecanolide. Several cyclic diesters pre- ular cyclization of 10-undecylenic acid with 70 –
pared from long-chain α,ω-dicarboxylic acids 80 % sulfuric acid with migration of the double
and glycols are also valuable musk fragrances. bond.
The γ-lactones described below can be pre- γ-Undecalactone has many applications in
pared in good yield in a one-step process by rad- perfume and aroma compositions, similar to
ical addition of primary fatty alcohols to acrylic those of γ-decalactone.
acid, using di-tert-butyl peroxide as a catalyst. Trade Name. Pêche pure (Givaudan Roure).
A patent claims a high yield when the reaction is
carried out in the presence of alkali phosphates δ-Decalactone [705-86-2], C10 H18 O2 , M r
or alkali sulfates [173]. 170.25, bp (3 Pa) 117 – 120 ◦ C, d 27.5
4 0.9540, n26
D
1.4537, is a flavor constituent of many types of
fruit, cheese, and other dairy products. It is a
colorless, viscous liquid with a creamy-coconut,
peachlike aroma.
δ-Decalactone can be prepared by peracid ox-
idation of 2-pentylcyclopentanone. It is used in
perfumes and for cream and butter flavorings.
γ-Octalactone [104-50-7], (n = 3),
C8 H14 O2 , M r 142.20, bp (1.3 kPa) 116 –
117 ◦ C, d 20 25
4 0.977, nD 1.4420, occurs as an
aroma constituent in many processed and un-
processed foods. It is a pale yellow liquid with
a fruity-coconut-like odor and is used both in 15-Pentadecanolide [106-02-5], ω-hy-
aroma compositions and in heavy blossom per- droxypentadecanoic acid lactone, C15 H28 O2 ,
fumes. M r 240.39, bp (1.3 – 1.4 kPa) 169 ◦ C, mp 37 –
38 ◦ C, d 40
4 0.940, occurs in small quantities in,
γ-Nonalactone [104-61-0], (n = 4), “so- for example, angelica root oil. It forms colorless
called aldehyde C18 ” C9 H16 O2 , M r 156.22, crystals with a delicate, musklike odor.
bp (1.7 kPa) 136 ◦ C, d 20 20 Production. The main industrial synthe-
4 0.9676, nD 1.446, oc-
curs in many foods and is a pale yellow liquid ses start from cyclododecatriene derivatives
with a coconut-like aroma. It has numerous ap- (→ Cyclododecatriene, Cyclooctadiene, and 4-
plications, similar to those of γ-octalactone, in Vinylcyclohexene). The 16-membered ring is
aroma compositions and perfumery. formed either by expansion of the 12-membered
Trade Names. Abricolin (Haarmann & Reimer), ring or by depolymerization of polyesters of ω-
Prunolide (Givaudan Roure). hydroxypentadecanoic acid.
Preparation by Ring Expansion of Cyclo-
γ-Decalactone [706-14-9], (n = 5), dodecanone. Radical addition of allyl al-
C10 H18 O2 , M r 170.25, bp (2.3 kPa) 156 ◦ C, cohol to cyclododecanone, for example,
d 21
4 0.952, nD
19.5
1.4508, is present in a wide with di-tert-butyl peroxide as a radical
variety of foods and is an almost colorless liq- initiator, yields 2-(γ-hydroxypropyl)cyclo-
uid with an intensely fruity odor, reminiscent dodecanone (41). This is converted into 13-
of peaches. It is used in perfumery for heavy, oxabicyclo-[10.4.0]hexadec-1(12)-ene (42)
76 Flavors and Fragrances

by acid-catalyzed dehydration [174]. Addi-

tion of hydrogen peroxide, in the presence of
sulfuric acid, gives 12-hydroperoxy-13-oxa-
bicyclo[10.4.0]hexadecane (43). Cleavage of
the peroxide by heating in xylene gives 15-
pentadecanolide as well as a small amount of
15-pentadec-11(and 12)-enolide and 11 12-
hydroxy-15-pentadecanolide [175].

The polyester of 15-hydroxypentadecanoic

acid is prepared by customary methods and
is cleaved under high vacuum in the presence
of transesterification catalysts.
Uses. 15-Pentadecanolide is a highly valu-
Preparation from Polyesters of 15- able fragrance material that is used in fairly large
Hydroxypentadecanoic Acid. amounts in fine fragrances as a fixative with a
In a Japanese process, the required ω-hy- delicate musk odor.
droxy acid is prepared from 1,12-dodecane- Trade Names. Cyclopentadecanolid (Haarmann
diol in several steps. The diol is added to & Reimer), Exaltolid (Firmenich), Pentalide
methyl acrylate in a radical reaction, using (Soda Aromatic).
di-tert-butyl peroxide as a catalyst. The free
hydroxyl group in the resulting ω-hydroxy- Oxacyclohexadec-12/13-en-2-one, (E/Z)
γ-pentadecalactone is acetylated with acetic [34902-57-3], C15 H26 O2 , M r 238, bp (40 Pa)
anhydride, and the resulting ω-acetoxy-γ- 88 – 93 ◦ C , d 20
20 0.961 – 0.971, possesses a
pentadecalactone is converted into 15-hy- musklike, ambrette, and animalic odor.
droxypentadecanoic acid by hydrogenolysis Production (see production of 15-
and hydrolysis [176] (see upper one of fol- pentadecanolide page 77). Cleavage of
lowing figures). 12-hydroperoxy-13-oxabicyclo[10.4.0]-hexa-
Another route to 15-hydroxypentadecanoic decane (43) in the presence of Cu(OAc)2 and
acid starts from 13-oxabicyclo[10.4.0]hexa- Fe(SO4 )2 gives 43 % of trans-pentadec-11-
dec-(1,12)-ene (42), see (1). Nitrosation to enolide, 26 % trans-pentadec-12-enolide, 18 %
12-oximino-15-pentadecanolide, followed cis-pentadec-11-enolide, 5 % cis-pentadec-12-
by a Wolff–Kishner reduction yields 15-hy- enolide, and 5 % pentadecanolide [178].
droxypentadecanoic acid [177]. The reaction Another synthesis uses a pyrolysis of an ace-
can be carried out without isolation of the toxy derivative of the lactone [179].
intermediate oxime.
 Flavors and Fragrances 77

d 60 40
4 1.0303, nD 1.4588, is a synthetic musk
that is prepared by thermal depolymerization of
the polyester obtained from 1,12-dodecanedioic
acid and ethylene glycol in the presence of a cat-
Uses. 15-Pentadec-11/12-enolide is a very alyst (e.g., stannous salts of aliphatic monocar-
powerful musk and combines the strength and boxylic acids) [180].
tenacity of the aromatic musks with the pleas-
antness and elegance of the macrocyclic musks.
Trade Names. Habanolide (Firmenich), Glob-
alide (Haarmann & Reimer).

12-Oxa-16-hexadecanolide [6707-60-4],
16-hydroxy-12-oxahexadecanoic acid lactone,
C15 H28 O3 , M r 256.38, does not occur in na- The compound is used in perfumery as a
ture. Its odor is comparable to that of 15- musk fragrance, but is not as long-lasting as
pentadecanolide, but less intense. It is prepared the following homologous compound, ethylene
by reacting methyl ω-bromoundecanoate with brassylate.
the monosodium salt of 1,4-butanediol. The Trade Name. Arova 16 (Degussa).
resulting methyl 16-hydroxy-12-oxapalmitate
is condensed to the corresponding polyester, α,ω-Tridecanedioic acid ethylene ester
which is subsequently depolymerized. [105-95-3], ethylene brassylate (44 ,n = 11),
C15 H26 O4 , M r 270.37, bp (1.3 kPa) 140 ◦ C, d 60
4
1.0180, n20D 1.4702, is an artificial fragrance
compound, with a sweetish, slightly fatty, musk
odor. Like α,ω-dodecanedioic acid ethylene es-
ter, the ester is obtained by depolymerization
of the corresponding polyester. Brassylic acid
(α,ω-tridecanedioic acid) is prepared by ozonol-
ysis of erucic acid [181]:

12-Oxa-16-hexadecanolide as well as the

stronger smelling 11-oxa isomer [3391-83-1],
which is obtained in the same way from the cor-
responding hydroxyoxa acid, are used as substi-
tutes for 15-pentadecanolide in fine fragrances. Ethylene brassylate is used in large amounts
in perfumery as a fixative and for rounding off
sweet-flowery odor notes.
Trade Name. Musk T (Takasago), Ethylene
Brassylate (Degussa).

Coumarin [91-64-5], 2H-1-benzopyran-2-

Trade Names. 12-Oxa-16-hexadecanolide = one, C9 H6 O2 , M r 146.15, bp (1.33 kPa)
Cervolide (Quest), 11-Oxa-16-hexadecanolide 153.9 ◦ C, mp 70.6 ◦ C, d 20
4 0.935, occurs widely
= Musk R 1 (Quest). in nature and determines, for example, the odor
of woodruff. It forms white crystals with a hay-
α,ω-Dodecanedioic acid ethylene ester like, spicy odor. When treated with dilute alkali,
[54982-83-1], (44, n = 10), C14 H24 O4 , M r coumarin is hydrolyzed to the corresponding
256.34, mp 18 ◦ C, bp (2.7 kPa) 139 – 141 ◦ C, coumarinic acid salt ( cis-2-hydroxycinnamic
78 Flavors and Fragrances

acid). Heating with concentrated alkali or with The hydroxyl group of o-cresol is protected
sodium ethanolate in ethanol results in the by a carbonate or phosphate group, and the
formation of o-coumaric acid salts (trans-2- ester can be converted into the corresponding
hydroxycinnamic acid). 3,4-Dihydrocoumarin benzal chloride derivative by chlorination of
is obtained by catalytic hydrogenation, for ex- the methyl group. Reaction of this intermedi-
ample, with Raney nickel as a catalyst; octa- ate with acetic anhydride yields O-acetylsal-
hydrocoumarin is obtained if hydrogenation is icylaldehyde and acetyl chloride. Ring clo-
carried out at high temperature (200 – 250 ◦ C). sure of the aldehyde with acetic anhydride
Production. Coumarin is currently produced gives coumarin.
by Perkin and Raschig syntheses. Since the odor of coumarin is relatively weak,
strong-smelling byproducts (e.g., vinylphe-
Synthesis from Salicylaldehyde by the Perkin
nol) must be removed. Many purification
Reaction.
methods have been reported and patented.
In the presence of sodium acetate, salicylal-
dehyde reacts with acetic anhydride to pro- Uses. Coumarin is one of the most widely
duce coumarin and acetic acid. The reaction used fragrance compounds. It is used in fine fra-
is carried out in the liquid phase at elevated grances as well as in soap perfumes for spicy
temperature. green notes. It is also used in galvanization as a
brightener.

Dihydrocoumarin [119-84-6], 3,4-dihydro-

2H-benzopyran-2-one, C9 H8 O2 , M r 148.16, bp
(2.3 kPa) 145 ◦ C, mp 24 ◦ C, n25
D 1.5528, occurs
in a few essential oils and forms colorless crys-
tals with a sweet-herbal odor. Dihydrocoumarin
is prepared by hydrogenation of coumarin, for
example, in the presence of a Raney nickel cat-
alyst. Another process employs the vapor-phase
dehydrogenation of hexahydrocoumarin in the
In a special process, the sodium acetate cat- presence of Pd or Pt–Al2 O3 catalysts [183].
alyst is retained in the reactor by a built-in Hexahydrocoumarin is prepared by cyanoethy-
filter and is reused [182]. lation of cyclohexanone and hydrolysis of the
Synthesis from o-Cresol by the Raschig Pro- nitrile group, followed by ring closure to the lac-
cess. tone [184].

Dihydrocoumarin is used in woodruff-type

flavor compositions. (Limiting IFRA recom-
mendation)
 Flavors and Fragrances 79

2.7.3. Glycidates 2.7.4. Miscellaneous Compounds

A number of glycidates are important interme- 2-Furylmethanethiol [98-02-2], furfuryl

diates in the synthesis of fragrance compounds. mercaptan, C5 H6 OS, M r 114.16, bp (101.3 kPa)
They are prepared either by epoxidation of the 160 ◦ C, d 20 20
4 1.1319, nD 1.5329, is an impor-
corresponding acrylates or by condensation of tant constituent of the aroma of roasted coffee.
aldehydes or ketones with α-chloro substituted It is a liquid with an unpleasant odor, which
fatty acid esters ( Darzens reaction). becomes like coffee when diluted. Furfuryl
mercaptan is prepared from furfuryl alcohol,
thiourea, and hydrogen chloride. The resulting
S-furfurylisothiouronium chloride is cleaved
with sodium hydroxide to give furfuryl mercap-
tan.

Ethyl 3-phenylglycidate [121-39-1], “so-

called special aldehyde C16 ”, C11 H12 O3 , M r
192.21, bp (40 Pa) 104 ◦ C, d 20 4 1.1023, nD
30

1.5095, is a colorless liquid with a strawberry-

like odor; it is not known to occur in nature.
It is prepared by treating ethyl cinnamate with
peracetic acid [185] or by condensation of ben-
zaldehyde with ethyl chloroacetate (in the above
Darzens reaction, R = H). The glycidate is used The thiol is used in coffee aromas.
as a long-lasting fragrance compound for creat-
ing harmonic, fruity notes in household and fine
fragrances.
2.8. N- and N, S-Heterocycles

Many nitrogen- and sulfur-containing heterocy-

cles have been identified in the aroma fractions
of foods [187]. In roasted products (e.g., cof-
fee) and heat-treated foods (e.g., baked bread
Ethyl 3-methyl-3-phenylglycidate or fried meat), these heterocycles are formed
[77-83-8], “so-called aldehyde C16 ”, from reducing sugars and simple or sulfur-con-
C12 H14 O3 , M r 206.24, bp (2.4 kPa) 153 – taining amino acids by means of Maillard reac-
155 ◦ C, d 25
25 1.506 – 1.513, occurs in two op- tions [188, 189]. Their odor threshold values are
tically active pairs of cis- and trans-isomers; often extremely low and even minute amounts
each isomer has a characteristic odor [186]. may significantly contribute to the aroma qual-
The commercial product is a racemic mixture ity of many products [190, 191]. Therefore, N-
of all four isomers and has a strong, sweetish, and N, S-heterocyclic fragrance and flavor sub-
strawberry odor. The cis : trans ratio obtained stances are produced in far smaller quantities
in the Darzens condensation of acetophenone than most of the products previously described.
(R = CH3 ) and ethyl chloroacetate depends on Pyrroles, indoles, pyridines, quinolines, and
the base used in the reaction. pyrazines are examples of N-heterocycles that
are produced as fragrance and flavor com-
pounds. Thiazoles and dithiazines are examples
of nitrogen- and sulfur-containing heterocycles.
These heterocyclic compounds are mainly used
The glycidate is used in household perfumery in aroma compositions, exceptions are indoles
for fruity notes. and quinolines, which are important fragrance
Trade Name. Fraise pure (Givaudan Roure). substances.
80 Flavors and Fragrances

Representatives of the above-mentioned

classes are as follows:

2-Methoxy-3-isopropylpyrazine [25773-40-4],
green pea odor
2-Acetylpyrrole [1072-83-9], roast odor

2-Methoxy-3-isobutylpyrazine [24683-00-9],
green-pepper odor
2-Acetyl-3,4-dihydro-5H-pyrrole [85213-22-5],
characteristic odor of white bread crust

2,3-Dimethylpyrazine [5910-89-4], and its 2,5-

[123-32-0] and 2,6- [108-50-9] isomers, roast
odor, reminiscent of nuts
Indole [120-72-9], fecal odor, floral in high dis-
solution

Trimethylpyrazine [14667-55-1], roast odor,

reminiscent of coffee and cocoa

3-Methylindole, skatole [83-34-1], indole-like

odor
Mixture of 3-ethyl-2,5-dimethylpyrazine
[13360-65-1] and 2-ethyl-3,5-dimethylpyrazine
[13925-07-0], roast odor, reminiscent of nuts

2-Acetylpyridine [1122-62-9], roast odor

2,5-Dimethylthiazole [4175-66-0], meat-like
odor

6-Methylquinoline [91-62-3], blossom odor,

sweet-animalic upon dissolution
2-Isobutylthiazole [18640-74-9], tomato odor

6-Isobutylquinoline [68141-26-4], mossy-

earthy odor

2-Acetylpyrazine [22047-25-2], popcorn-like

odor
Alkyldimethyl-1,3,5-dithiazines, roast odor
 Flavors and Fragrances 81

3. Natural Raw Materials in the breeding of new varieties. New species are ob-
Flavor and Fragrance Industry tained either by alternation of generations or by
vegetative means in an attempt to improve yield,
3.1. Introduction oil quality, and resistance to disease and insects.
The production of some essential oils has de-
Although synthetic flavor and fragrance mate- creased to low levels or even been discontin-
rials are produced on an industrial scale, natu- ued due to competition from synthetic products.
rally occurring raw materials continue to be es- Nevertheless, the worldwide production of fla-
sential, important ingredients in the manufacture vor and fragrance materials of natural origin has
of flavor and fragrance compositions for several increased recently due to breeding successes,
reasons. First, the composition and organoleptic but their total market share has decreased.
nature of natural products are often too complex Annual worldwide sales currently amount to
to be reproduced by a combination of synthetic $ 600 × 106 [192].
fragrance substances. Second, the characteristic Raw materials derived from intensive agri-
flavor and fragrance substances of a particular cultural cultivation are usually relatively inex-
product often cannot be synthesized at a com- pensive. However, the prices of some natural
petitive price. Third, the use of natural materials materials may exceed $ 1000 per kilogram be-
in the production of certain flavor compositions cause cultivation and harvesting of these plants
is compulsory. Demand for perfumes based on are tedious and product yields are very low. Ex-
natural materials has increased. amples of extremely valuable ingredients of fra-
Raw materials for the flavor and fragrance in- grance and flavor creations include rose oil, jas-
dustry are obtained from more than 250 differ- mine absolute, tuberose absolute, orris root oil,
ent plant species, but only a handful of products ambrette seed oil, angelica root oil, and orange
originate from animals. flower oil.
Raw materials are isolated from various parts
of plants, e.g., blossoms, buds, fruit, peel, seeds,
leaves, bark, wood, roots, or from resinous ex- 3.2. Isolation of Natural Fragrance and
udates. Different parts of the same plant may Flavor Concentrates
yield products with different compositions. For
instance, steam distillation of the bark of the Three main methods are used to concentrate
cinnamon tree gives cinnamon bark oil, which plant flavor and fragrance substances:
contains mainly cinnamaldehyde, whereas cin-
namon leaf oil obtained from the leaves of the 1) distillation
tree contains eugenol as its major constituent. 2) mechanical separation (“pressing”)
The quality of natural products depends con- 3) solvent extraction
siderably on their geographic origin, even if they The qualitative and quantitative composition
are isolated from the same plant species. This and, thus, the organoleptic properties of the
may be partly due to variations in cultivation product depend on the isolation procedure. For
conditions, such as soil structure and climate, example, an extract contains large amounts of
but also results from the fact that different va- nonvolatile components that are not found in es-
rieties of the same plant species are cultivated sential oils obtained by distillation. Since these
in different areas. Thus, more than 500 natural components markedly influence odor develop-
raw materials are available for the creation of ment (complexing and fixing), the two prod-
perfumes and flavors. ucts may have completely different organoleptic
The flavor and fragrance industry has ex- properties, even though the compositions of their
panded so much that the plants required to sup- odorous volatile constituents are comparable.
ply the raw materials are now grown on a very In addition, the distillation of essential oils
large scale. Examples are the peppermint and at elevated temperature results in the transfor-
spearmint plantations in the United States and mation of thermolabile substances, and some
the lavandin plantations in southern France. typical components are only released from their
The economic importance of the cultivation precursors in the plants under distillation condi-
of aromatic plants has led to the systematic tions.
82 Flavors and Fragrances

Solvent extraction is generally applied in the that are important for the desired characteristic
separation of heat-labile plant materials or if an odor and taste are thus concentrated, and other
essential oil can be obtained only in very low components, which possess either an unpleas-
yield (e.g., from blossoms). It is also used if ant or very faint odor or are unsuitable for the
the nonvolatile components are desired for their application in question, are removed.
fixative properties (e.g., in the preparation of Individual compounds can be isolated from
resinoids from exudates). essential oils containing one or only a few ma-
jor components by distillation or crystallization.
Examples are eugenol from clove oil, menthol
3.2.1. Essential Oils from cornmint oil, citronellal from Eucalyptus
citriodora oil and citral from Litsea cubeba oil.
Production. Essential oils are obtained from These compounds are used as such or serve as
plant materials by distillation with water or starting materials for the synthesis of derivatives,
steam. After condensation of the vapor phase, which are also used as flavor and fragrance sub-
the oil separates from the aqueous phase and is stances. However, the importance of some of
removed. The yield of essential oil, based on the these oils has decreased substantially because of
starting plant material, generally ranges from a the development of selective synthetic processes
few tenths of 1 % to a few percent. The appara- for their components.
tus used in the production of natural fragrance Although essential oils or their fractions are
concentrates is described in [193]. mixtures of many substances, these oils are oc-
Essential oils consist of volatile, lipophilic casionally converted as a whole into derivatives.
substances that are mainly hydrocarbons or Examples of such derivatives are vetiveryl ac-
monofunctional compounds derived from the etate from vetiver oil, guaiyl acetate from gua-
metabolism of mono- and sesquiterpenes, iac wood oil, and acetyl cedrene from cedarwood
phenylpropanoids, amino acids (lower mass terpenes. These products are also employed as
aliphatic compounds), and fatty acids (long- fragrance substances.
chain aliphatic compounds). Unlike fatty oils,
essential oils do not leave a grease stain when
dabbed on filter paper. 3.2.2. Extracts
Essential oils are to be distinguished from
the so-called distillates, which are ethanol-con- Extracts of fragrance and flavor substances ob-
taining products that are obtained from plant ma- tained from plants are termed pomades, con-
terials by distillation with ethanol or with eth- cretes, absolutes, resinoids, or tinctures accord-
anol–water mixtures. Essence oils are defined ing to their method of preparation.
as essential oils that separate from the aque-
ous phase in the distillation receiver during the Pomades consist of fats that contain fra-
distillative concentration of fruit juices (usu- grance substances and are produced by the hot
ally citrus juices). Citrus peel oils are a special or cold enfleurage of flowers. Hot enfleurage is
type of essential oil. They are isolated by press- the oldest known procedure for preserving plant
ing the peel to release the volatile substances fragrance compounds. In this method, flowers
stored in the pericarp in small oil glands. The (or other parts of a plant) are directly immersed
resulting products are termed essential oils be- in liquid or molten wax.
cause they consist largely of highly volatile ter- In cold enfleurage, the volatile components
pene hydrocarbons. However, they also contain released by flowers into their sourroundings
small amounts of nonvolatile compounds, such are absorbed with fats over a longer period of
as dyes, waxes, and furocoumarins. time. This industrial procedure was developed
in southern France in the 19th century for the
Uses. Most essential oils are used directly as production of high-grade flower concentrates. It
starting materials in the production of flavor and involves the application of fresh flowers to a fat
fragrance compositions. However, some essen- layer, consisting of a mixture of specially refined
tial oils are fractionated or concentrated by dis- lard and beef tallow, which is spread on a glass
tillation, partitioning, or adsorption. Substances
 Flavors and Fragrances 83

plate in a closed container. This method, how- concentrates prepared from spices by solvent
ever, has been almost totally replaced by the less extraction. The solvent that is used depends on
tedious technique of solvent extraction. the spice; currently, these products are often ob-
tained by extraction with supercritical carbon
Concretes are prepared by extracting fresh dioxide. Pepper and ginger oleoresins contain
plant material with nonpolar solvents (e.g., ben- not only volatile aroma compounds, but also
zene, toluene, hexane, petroleum ether). On substances responsible for pungency.
evaporation, the resulting residue contains not
only volatile fragrance materials, but also a large Tinctures are alcoholic solutions that are
proportion of nonvolatile substances including prepared by treating natural raw materials with
waxy compounds. For this reason, concretes ethanol or ethanol–water mixtures. They can
(like pomades) are not completely soluble in al- also be obtained by dissolving other extracts in
cohol and, thus, find limited use as perfume in- these solvents. Tinctures are sometimes called
gredients. However, they can be employed in the infusions.
scenting of soaps.
Concretes, which are actually intermediate
products (see below), are prepared mainly from 3.3. Survey of Natural Raw Materials
flowers (rose, jasmine, tuberose, jonquil, ylang-
ylang, mimosa, boronia, etc.), but also from The following survey of the most important,
other plant materials (lavender, lavandin, gera- well-known raw materials used in the flavor and
nium, clary sage, violet leaves, oak moss, etc.). fragrance industry is by no means complete; the
A yield of ca. 0.3 % based on the starting flower materials are listed in alphabetical order. Phys-
material, is obtained in the production of jasmine ical standards for essential oils are described as
concrete. specified by the ISO or the Essential Oil Asso-
ciation of the United States (EOA). The phys-
Absolutes are prepared by taking up con- ical standards cited according to ISO are taken
cretes in ethanol. Compounds that precipitate from the most recent draft, because many stan-
on cooling are then removed by filtration. After dards are already very old but under discussion.
evaporation of the ethanol, a wax-free residue The ISO standard number remains the same; so
called an absolute is left behind. Absolutes are the reader can also check for the older data.
completely soluble in ethanol and, therefore, can EOA specifications were only cited in those
be freely used as perfume ingredients. They are cases where no ISO specifications are available.
usually formed in a yield of ca. 50 %, based on These become more and more the most widely
the concrete as starting material. distributed standards. Gas chromatograms are
In rare cases, absolutes can be obtained di- widely used for analysis and quality control, but
rectly by extracting the plant material with alco- have not been included due to lack of space. Fur-
hol (e.g., tonka absolute). ther details are given in the literature, e.g., [194],
and in ISO specifications, which now include gas
Resinoids are prepared by extracting plant chromatograms.
exudates (balsams, oleo gum resins, natural oleo The entire components of the individual prod-
resins, and resinous products) with solvents such ucts have not been listed for the same reason;
as methanol, ethanol, or toluene. Yields range further information is available in the literature,
from 50 to 95 %. The products are usually highly e.g., [187,195]. Physical data for extracts or con-
viscous and are sometimes diluted (e.g., with centrates consisting largely of nonvolatile mate-
phthalates or benzyl benzoate) to improve their rial are not given because the composition of
flow and processing properties. these products varies widely according to the
Resinoids mainly consist of nonvolatile, isolation and manufacturing procedure used.
resinous compounds and are primarily used for The botanical names of plants are cited in ac-
their excellent fixative properties. cordance with the International Code of Botan-
The resinoids described above should be dis- ical Nomenclature (ICBN) as described, for ex-
tinguished from prepared oleoresins (e.g., pep- ample, in [196].
per, ginger, and vanilla oleoresins), which are
84 Flavors and Fragrances

Allium oils are obtained from garlic and

onion (Liliaceae). Their quality is assessed on
the basis of their odor and aroma rather than
5-Tetradecen-14-olide Ambrettolide
their physical and chemical properties. The EOA
specifications given below are, therefore, of lim- Other components are acyclic aliphatic es-
ited value only. ters and terpenes, such as farnesol and farnesyl
1) Garlic oil is obtained by steam distillation acetate. Ambrette seed oil is one of the most ex-
of crushed bulbs of the common garlic, Al- pensive essential oils and, thus, is used mainly
lium sativum L.; it is a clear, reddish-orange in fine fragrances.
liquid, with a strong, pungent, characteristic
garlic odor. Amyris oil is obtained by steam distillation
d 25
25 1.040 – 1.090, nD
20
1.5590 – 1.5790 of the wood from the tree Amyris balsamifera L.
[197]. Diallyl disulfide [2179-57-9] is an (Rutaceae), which grows in the Caribbean area
essential odor component of garlic oil: and around the Gulf of Mexico. Annual produc-
CH2 =CHCH2 SSCH2 CH = CH2 tion worldwide is ca. 40 t. It is a pale yellow
2) Onion oil is obtained by steam distillation to amber-yellow, slightly viscous liquid with a
of the crushed bulbs of the common onion, mild wood odor.
Allium cepa L. It is an amber-yellow to am- d 20 20
20 0.946 – 0.978; nD 1.505 – 1.510; [α]D
20
◦ ◦
ber liquid with a strongly pungent, lasting, + 10 to + 60 ; solubility: 1 vol in 1 vol of 90 %
characteristic onion odor. ethanol at 20 ◦ C; solutions sometimes become
d 25
25 1.050 – 1.135; nD
20
1.5495 – 1.5695 opalescent on dilution; acid value: max. 3.0; es-
[198]. ter value (after acetylation): 180 – 198 [200].
Aliphatic sulfur compounds, in particular The oil is sometimes incorrectly called West
disulfides such as methyl propyl disulfide, Indian sandalwood oil. However, its composi-
dipropyl disulfide, and especially cis- and tion and odor are different from those of the
trans-propenyl propyl disulfide are mainly oils obtained from sandalwood species. The
responsible for the typical odor of onion oil. major components of amyris oil are sesquiter-
Garlic and onion oil are used in seasoning penoids such as valerianol [20489-45-6], elemol
mixtures for the food industry. [639-99-6], β-eudesmol [473-15-4], and epi-γ-
eudesmol [15051-81-7] [201].
Allspice oil, see Pimento Oils, page 113.

Ambergris (ambra), see Animal Secretions,

page 87.

Ambrette seed oil is obtained by steam dis-

epi-γ-Eudesmol
tillation of the dried, crushed seeds of Abel-
moschus moschatus Medik. (Hibiscus abel- Amyris oil is used in perfume compositions,
moschus L., Malvaceae), a flowering shrub mainly as a fixative.
growing in tropical areas. Due to its content of
long-chain fatty acids, the crude product is a Angelica oil is prepared from Angelica roots
waxy mass and, therefore, also called “Ambrette or seeds.
beurre.” Removal of the fatty acids with alkali
gives a clear yellow to amber-yellow liquid with 1) Angelica root oil is obtained by steam
the strong, musky odor of ambrettolide. distillation of the dried roots of Angelica
d 25 20
25 0.898 – 0.920; nD 1.4680 – 1.4850; [α]D
archangelica L. Apiaceae [Archangelica of-
◦  
− 2 30 to +3 ; acid value: max. 3; saponifica- ficinalis (Moench) Hoffm.], a plant occurring
tion value: 140 – 200 [199]. predominantly in Europe. The oil is a pale
The constituents responsible for the musk yellow to deep amber-yellow liquid with a
odor of the oil are ambrettolide, (Z)-7- green, herbaceous, peppery, musk-like odor
hexadecen-16-olide [123-69-3] and (Z)-5- and a bitter-sweet taste.
tetradecen-14-olide [63958-52-1]:
 Flavors and Fragrances 85

d 25
25 0.850 – 0.880, occasionally up to 0.930 Fresh ambergris is almost black, but it turns
for oils from stored roots; n20 D 1.4735 – light gray and develops a pleasant odor when
1.4870; [α]D 0 ◦ to + 46 ◦ ; acid value: max. exposed to light and seawater over a period
7; ester value: 10 – 65; solubility: 1 vol in at of time. The major components of ambergris
least 1 vol of 90 % ethanol, often with turbid- are epicoprosterol (up to 85 %) and the odor-
ity [202]. (Limiting IFRA recommendation) less triterpene alcohol, ambrein [473-03-0].
2) Angelica seed oil is similarly obtained from
fresh seeds of the plant. It is a light yellow
liquid with an odor that is sweeter and more
delicate than that of the root oil.
d 25 20
25 0.853 – 0.876; nD 1.4800 – 1.4880; [α]D
◦ ◦
+ 4 to + 16 ; acid value: max. 3; ester value:
14 – 32; solubility: 1 vol in at least 4 vol 90 %
ethanol, often with considerable turbidity Ambrein
[203].
Ambrein is the likely precursor of a number
Angelica root oil contains ca. 90 % ter-
of strongly odoriferous mono-, bi-, and tri-
penoids and sesquiterpenoids. α-Pinene, 3-
cyclic compounds that are formed by autox-
carene, limonene, and β-phellandrene are
idation or photooxidation [204]. Examples
the major components (together ca. 60 %).
are as follows:
In addition, the oil contains a large number
of oxygen-containing compounds, of which
the macrolides 15-pentadecanolide and 13-
tridecanolide are essential odor components.
The two angelica oils are used mainly in the
alcoholic beverage industry. γ-Dihydroionone [13720-12-2] (odor: tobacco)

Animal secretions are of minor commercial

importance because some of the animal species
from which they are obtained are virtually ex-
tinct, and the killing quota for others has been
sharply reduced. Few odoriferous secretions of 2-Methylene-4-(2,2-dimethyl-6-methylenecyclo-
mammals have actually been shown to possess hexyl)butanal [72892-63-8] (odor: seawater)
pheromone-like properties linked with repro-
duction. However, the odor of animal secretions
is known to be important for communication
and behavior of a particular species. Most of
the products described below contain strong-
smelling compounds with relatively high molec-
α-Ambrinol [41199-13-3] (odor: moldy, animal, fecal)
ular masses. Therefore, they are used as longlast-
ing fragrance complexes. Most of their odorifer-
ous constituents are now produced synthetically
and are used for the same purposes.
1) Ambergris ( ambra) is a secretion of the
sperm whale Physeter catodon (P. macro-
cephalus L.), that possibly results from 3a,6,6,9a-Tetramethyldodecahydronaphtho[2,1-b]furan
a pathological condition. Ambergris has a [6790-58-5] (odor: ambergris)
lower density than water and washes ashore
along the ocean coasts. The major quantity Together, these compounds largely represent
is obtained from killed animals, but only a the odor of ambergris. Ambergris is applied
low percentage contain ambergris in their in- as a 3 % tincture in 90 % ethanol, which is
testines. matured by standing over a period of time
86 Flavors and Fragrances

with occasional shaking. It is used in fine fra- liquid with a light yellow color. It darkens
grances. when exposed to light and takes on a consis-
2) Beeswax absolute is obtained by alcohol ex- tency like salve. In dilutions (e.g., as an al-
traction of beeswax. The yield is generally coholic tincture), civet has a pleasant, sweet-
less than 1 %. The yellowish-brown viscous ish odor. A resinoid prepared by extraction
product has a mild, honey-like odor and high with acetone is a dark brown-red mass; mp
tenacity; it is used almost exclusively in fine 20 – 25 ◦ C; acid value: 100 – 140; ester value:
fragrances. 20 – 40; carbonyl value: 15 – 25 [206]. Cive-
3) Castoreum is an unpleasantly sharp- tone (for formula, see Section 2.4) is the main
smelling, oily substance secreted by special odoriferous constituent of civet (2.5 – 3.4 %).
glands of beavers, Castor fiber L. (Castori- Civet contains other macrocyclic ketones
dae), living in Canada, Alaska, and Siberia. such as cyclohexa- and cycloheptadecanone
Both sexes secrete the substance, which ac- and 6-cis-cycloheptadecenone. Traces of in-
cumulates in an abdominal pouch, also called dole and skatole contribute to the animal
castoreum. Dilute castoreum (e.g., as a tinc- note.
ture in ethanol) smells pleasantly of birch tar Civet has a distinctly different odor from
and musk and is slightly fruity. musk and was formerly a versatile ingredi-
Castoreum is a byproduct of the fur industry. ent of fine fragrances.
The beaver pouches are dried in the air or 5) Musk is secreted exclusively by the male an-
over a wood fire; the color of their contents imals of Moschus moschiferus, a wild deer
then changes from yellow to dark brown, and living in the mountains of Nepal, Tibet, and
the consistency from a butter-like to resinous Mongolia. The light yellow secretion with a
character. salve consistency accumulates in an abdom-
In addition to alcoholic tinctures, castoreum inal pouch and probably serves to attract fe-
is available in the form of resinoids, which males. When the pouch is dried, the secretion
are prepared by extracting dried, commin- solidifies to form a brittle, brown mass with
uted pouches with acetone, benzene, or etha- a characteristic odor. Since several Moschus
nol; yields are 30 – 50 %, 20 – 25 %, and 45 – species occur, large variations exist in the
80 %, respectively. The resinoids have the quality and specifications of musk. Hunting
following specifications [205] of the animals has been prohibited; therefore,
only small quantities of musk are available at
Acid value 15 – 30 30 – 35 15 – 30
Ester value 145 – 200 145 – 200 145 – 200
extremely high prices.
Carbonyl value 55 – 70 40 – 60 10 – 20 (−)-Muscone and related macrocyclic ke-
tones are responsible for the odor of musk
The intense, for the Siberian beaver leathery, [207]. Like other animal secretions, musk is
odor of castoreum is caused largely by phe- preferentially used as an alcoholic tincture in
nolic compounds (e.g., 4-alkylphenols and fine fragrances.
catechol derivatives), which beavers take in
with their food and excrete into their ab- Anise oil is obtained by steam distillation of
dominal pouch. Castoreum is used mainly the fruits of Pimpinella anisum L. (Apiaceae). It
in fine fragrances for its characteristic, long- is a colorless to pale yellow liquid or crystalline
lasting odor, particularly for delicate leather mass with a powerful, sweet odor, characteristic
nuances. of anethole.
4) Civet is a glandular secretion produced by d 20 20
20 0.980 – 0.990; nD 1.552 – 1.561; [α] D
20

both sexes of the civet cat (Viverridae). Two − 2 ◦ to + 2 ◦ ; solubility: 1 vol in 3 vol of 90 %
species are known: Civetticitis civetta that ethanol at 20 ◦ C; fp 15 – 19.5 ◦ C [208].
inhabits Ethiopia, and Viverra zibetha that is The main component of anise oil is trans-ane-
found in India, Malaya, Indochina, and In- thole, which may be present at a concentration
donesia. up to 94 % and which determines the melting
The animals are kept in cages, and the fresh point of the oil.
secretion is taken from the pouches at regular The oil was formerly produced in many coun-
(about one-week) intervals. Civet is almost tries, mainly in eastern Europe, but has now been
 Flavors and Fragrances 87

replaced to a large extent by the less expensive methylchavicol (15 – 25 %). It is used for
star anise oil (see page 117), which also contains food flavoring and in perfumery.
a high percentage of anethole. Annual world-
wide production of both oils is ca. 500 t. Bay oil is obtained by steam distillation of
Anise oil is used for flavoring foods, bever- the leaves of Pimenta racemosa (Mill.) J. W.
ages, and oral hygiene products. Moore (Myrtaceae). It is a dark brown liquid
with a strong, spicy, clovelike odor.
Armoise oil is obtained by steam distillation d 20 20
20 0.943 – 0.984; nD 1.505 – 1.517; [α] D
20

of the herb Artemisia herba-alba Asso (Aster- ◦

close to 0 ; phenols content: min. 50 % [210].
aceae) that grows in Morocco. It is a light yel- Evergreen bay trees or bay-rum trees, which
low to yellow liquid with a light herbaceous odor are up to 12 m high, grow wild and are also culti-
characteristic of thujone. vated in northern South America and in the West
d 25
25 0.917 – 0.935; nD
20
1.4600 – 1.4720; Indies. The main cultivation area is the island of
20 ◦ ◦
[α] D − 25 to − 8 . Dominica.
The major components of armoise oil The major components of the oil are myrcene,
(Marrakesh-type) are the ketones camphor eugenol, and chavicol. The phenol content is de-
(40 %) and α- and β-thujone (35 % and 5 % re- termined largely by the latter two compounds.
spectively). Since Artemisia herba-alba exists Total production of bay oil is ca. 50 t/a. It
as various chemotypes, the composition of the has antiseptic properties because of its high phe-
oil may vary widely. For example, each of the nol content and is, therefore, used for perfuming
above-mentioned ketones may occur in a con- after-shave lotions.
centration over 50 % or less than 10 %.
Armoise oil is used in fairly large amounts in Benzoe Siam resinoid is obtained by solvent
fine fragrances (e.g., for chypre notes). extraction of the resin from Styrax tonkinensis
(Pierre) Craib ex Hartwich trees (Styracaceae).
Basil oil is available in several types that dif- The wild growing Styrax tree is widespread in
fer in their major components; the two most im- Thailand, Laos, Cambodia, and Vietnam.
portant are described. Benzoe Siam resinoid is a reddish to light
brown, viscous liquid with a long-lasting,
1) Réunion basil oil is obtained by steam distil-
chocolate-like, sweet, balsamic odor. It is used
lation of the flowering tops or whole plants of
in perfumery for balsamic nuances and as a fix-
Ocimum basilicum L. (Lamiaceae). This oil
ative. (IFRA recommendation)
is produced mainly in Réunion, the Comores,
Madagascar, and the Seychelles. It is a pale
Benzoe Sumatra resinoid is obtained by
yellow to amber-yellow liquid with a fresh,
solvent extraction of the resin from Styrax ben-
green, spicy odor characteristic of estragole.
zoin Dryand, a tree growing predominantly on
d 20
20 0.948 – 0.970; nD
20
1.5100 – 1.5200;
20 ◦ ◦ the island of Sumatra. Benzoe Sumatra resinoid
[α] D − 1 to + 2 ; solubility: 1 vol in 7 vol
is a dark brown viscous liquid with a warm,
of 80 % ethanol [209].
powdery, sweet-balsamic odor. Its main volatile,
The oil typically has a high content of
odor-determining components are derivatives of
methylchavicol (min. 75 %, max. 85 %).
benzoic and cinnamic acids and vanillin [211].
Benzoe Sumatra resinoid is used in per-
fumery, mainly as a fixative with a warm, bal-
samic note. (IFRA recommendation)
R = H3 C, methylchavicol (estragole) [140-67-0]
R = H, chavicol [501-92-8]
Bergamot oil see Citrus Oils, page 94.
Annual production (ca. 200 to 300 t) is used
predominantly for seasoning foods. Bitter almond oil (free from hydrogen
2) European basil oil is produced mainly in cyanide) contains benzaldehyde as its main com-
France, Italy, the Balkan countries, Egypt, ponent. Benzaldehyde does not occur as such
and South Africa. The major components in the plant, but is formed, together with hydro-
of this oil are linalool (35 – 50 %) and gen cyanide, by the hydrolytic cleavage of the
88 Flavors and Fragrances

glycoside amygdalin. Amygdalin is present in acetate derivative [57074-34-7] which are two of
bitter almonds, the seeds of Prunus amygdalus the small number of naturally occurring sulfur-
Batsch var. amara (DC.) Focke, and ripe apri- containing terpenoids known to date [213, 214].
cot kernels, Prunus armeniaca L. (Rosaceae).
The press cake, which remains after removal
of the fatty oils, is macerated with water and
left to stand for several hours, after which the
“essential oil” is separated by steam distilla-
tion. The crude oil contains 2 – 4 % hydrogen
cyanide, which is removed by washing with
alkaline solutions of iron(II) salts. Subsequent
redistillation yields an oil free from hydrogen
cyanide. It is a colorless to slightly yellow liquid
with an intense, almond-like, cherry aroma and Buchu oil is used as a flavor ingredient (e.g.,
a slightly astringent, mild taste. in fruit aromas) and in perfumery in chypre bases
d 25 20 and in certain types of eaux de cologne; only
25 1.040 – 1.050; nD 1.5410 – 1.5460; [α]D
◦ ◦ 
0 to + 0 25 ; acid value: max. 8; aldehyde con- very small amounts are employed because of its
tent (calculated as benzaldehyde): min. 95 %; intensity.
solubility: 1 vol in 2 vol of 70 % ethanol [212].
Bitter almond oil is used almost exclusively Calamus oil is obtained by steam distilla-
in natural aroma compositions. tion of fresh or unpeeled, dried roots of Acorus
calamus L. (Araceae). It is a yellow to medium
Black currant absolute ( Bourgeons de cas- brown, moderately viscous liquid with a pleas-
sis absolute) is obtained by solvent extraction via ant, spicy, aromatic odor. (Limiting IFRA rec-
the concrete obtained from the dormant buds of ommendation)
the black currant bush Ribes nigrum L. (Saxifra- The plant occurs in polyploid varieties and
gaceae). The yield is ca. 3 %. Black currant abso- the corresponding essential oils differ pre-
lute is a dark green paste with the characteristic, dominantly in their content of β-asarone (cis-
powerful, penetrating odor of black currants. isoasarone) [5273-86-9]:
It has been used as a major ingredient in some diploid (American) 0%
fine fragrances. triploid (European) 0 – 10 %
tetraploid (Indian) up to 96 %
Bois de rose oil, see Rosewood Oil, page
115.

Buchu leaf oils are obtained by steam dis-

tillation of Agathosma betulina (Bergius) Pil-
lans (syn. Barosma betulina) and A. crenulata
(L.) Pillans (syn. Barosma crenulata) (Ru- β-Asarone
taceae) leaves. The oils are dark yellow to brown
liquids with a characteristic minty-fruity odor, The following data are typical for European
reminiscent of black currant. and Indian oils, respectively:
d 25 20
25 0.912 – 0.956, nD 1.474 – 1.488; [α]D
d 25
25 0.940 – 0.980 and 1.060 – 1.080; nD
20
◦ ◦
− 36 to − 8 ; acid value: 1 – 5; ester value: 1.5010 – 1.5160 and 1.5500 – 1.5525; [α]D + 5 ◦
20 – 85. to + 35 ◦ and − 2 ◦ to + 6.5 ◦ ; acid value: max.
The bushes grow wild and are cultivated in 4; ester value: 3 – 20; solubility: 1 vol in 5 vol of
South Africa. The major components of the 90 % ethanol; solutions may be turbid [215].
oils are (+)-limonene (ca. 10 %) and other cy- Calamus oil is used in perfumery for spicy-
clic terpenoids that are structurally related to herbaceous notes; small quantities are also em-
menthone. However, the constituents responsi- ployed in the alcoholic beverage industry. How-
ble for the characteristic black currant odor are p- ever, use is legally restricted because of the po-
menthane-8-thiol-3-one [38462-22-5] and its S- tential toxicity of β-asarone.
 Flavors and Fragrances 89

Camphor oil is obtained by steam distilla- Caraway oil is obtained by steam distillation
tion of the wood of the camphor tree Cinnamo- of crushed caraway seeds from Carvum carvi L.
mum camphora Sieb. (Lauraceae) growing in (Apiaceae). It is an almost colorless to amber
China, Taiwan, and Japan. The main constituent liquid with a characteristic caraway odor and a
of the crude oil is camphor (ca. 50 %), which mild-spicy taste.
can be separated by cooling and centrifugation. d 20 20
20 0.905 – 0.920; nD 1.4840 – 1.4890; [α]D
20
◦ ◦
Fractionation of the mother liquor gives two oils: + 67 to + 80 ; ketone content (calculated as
carvone): 50 – 60 %; solubility: 1 vol in 5 vol of
1) White camphor oil is the first distillation frac-
80 % ethanol; acid value: max. 1 [218].
tion (ca. 20 % of the crude camphor oil). It is
The major constituents of common caraway
a colorless or almost colorless liquid with a
oil are (+)-limonene and (+)-carvone, which to-
cineole-like odor.
gether may make up more than 95 % of the oil.
d 25 20
25 0.855 – 0.875; nD 1.4670 – 1.4720; [α]D
◦ ◦ (+)-Carvone is the essential odor component.
+ 16 to + 28 ; solubility: 1 vol in 1 vol
Caraway oil is produced mainly in Poland
of 95 % ethanol; solutions usually become
and Hungary. It is used primarily for flavoring
cloudy on further dilution [216].
foods and alcoholic beverages, but also for the
In addition to monoterpene hydrocarbons,
production of (+)-carvone.
this oil contains up to 35 % cineole.
Camphor oils with a higher cineole content
can be obtained by further fractionation or Cardamom oil is obtained by steam distilla-
by steam distillation of the leaves of other tion of the seeds of Elettaria cardamomum (L.)
varieties of the camphor tree. They are mar- Maton var. minuscula Burkill (Zingiberaceae). It
keted under the trade name eucalyptus oil is a colorless or very pale yellow liquid with an
70 – 80 % by Chinese producers, but are not aromatic, penetrating, slightly camphoraceous
true eucalyptus oils (see Eucalyptus Globu- odor and a persistent, pungent, strongly aromatic
lus Oil, page 100). taste.
2) Brown camphor oil is a fraction with a boil- d 20 20 20
20 0.919 – 0.936; nD 1.4620 – 1.4680; [α]D
◦ ◦
ing point higher than that of camphor (ca. + 22 to + 41 ; solubility: 1 vol in 2 to 5 vol
20 %). It is a pale yellow to brown liquid with of 70 % ethanol, solutions sometimes slightly
the characteristic odor of sassafras oil. opalescent [219].
d 25 20 The major components of cardamom oil are
25 1.064 – 1.075; nD 1.5100 – 1.5500; [α]D
◦ ◦ ◦
0 to +3 ; fp 6 C; solubility: 1 vol in 2 vol 1,8-cineole and α-terpinyl acetate (ca. 30 %
of 90 % ethanol [217]. each). It is produced from cultivated or wild
plants in the mountainous regions of southern
The oil contains more than 80 % safrole and, India, Sri Lanka, Indonesia, Thailand, southern
like Brasilian sassafras oil, is therefore used as China, and Guatemala. Cardamom oil is used
a raw material for the production of piperonal primarily for seasoning foods and occasionally
via isosafrole (see page 69). (IFRA recommen- in perfumery.
dation)
Camphor oils with a high safrole content can Carrot seed oil is obtained by steam distil-
also be obtained by steam distillation of the lation of the crushed seeds of Daucus carota L.
wood of Cinnamomum parthenoxylon Nees. (Apiaceae). It is a light yellow to amber-yellow
The production of natural camphor and cam- liquid with a pleasant, aromatic odor.
phor oils was formerly several thousand of tons d 20 20
20 0.900 – 0.945; nD 1.4800 – 1.4930; [α]D
20
per year. Nowadays it has declined to 500 t/a as − 30 ◦ to − 4 ◦ ; acid value: min. 5.0; ester value:
a result of the production of synthetic camphor. 9 – 58; ester value (after acetylation): 50 – 95;
The same is true for the distillation of linalool- solubility: 1 vol in 2 vol of 80 % ethanol [220].
containing camphor oils (Ho oil, Ho leaf oil), The main constituent of carrot seed oil is
which are derived from other varieties of the carotol [465-28-1], which may be present in over
camphor tree. 50 % concentration and is responsible for the
characteristic odor.
Cananga oil, see Ylang-Ylang and Cananga
Oils, page 120.
90 Flavors and Fragrances

Carotol
(−)-Thujone
Carrot seed oil is used in the alcoholic bev- The oil is produced in the northern states of
erage industry, in food flavors, and in perfume the United States and in Canada. It is used
compositions. in perfumery for dry nuances in citrus and
woody compositions.
Castoreum, see Animal Secretions, page 87. 3) Chinese cedarwood oil is similar in compo-
sition to Texas cedarwood oil (see below).
Cedar Oils. Several different conifer species Chinese cedarwood oil is obtained by steam
are called cedars and the corresponding oils vary distillation of the wood of Chamaecyparis fu-
considerably in composition. Worldwide annual nebris Endl. = Cupressus funebris Endl. (Cu-
production is about 800 t. The following cedar pressaceae), which is a weeping cypress, in-
oils are commercially important: digenous to China [223]. Annual production
1) Atlas cedarwood oil is obtained by steam lies between 850 and 900 t. Chinese cedar-
distillation of wood from Cedrus atlantica wood oil is an almost colorless to light yel-
(Endl.) Manetti ex Carr. (Pinaceae). It is a low oil with a woody, bitter odor. d 2020 0.938 –
yellowish to brownish, slightly viscous liq- 0.960; n20D 1.5000 – 1.5080; [α] 20
D − 35 to
◦
◦
uid with a sweet aromatic odor and a lasting, − 20 ; cedrol content : min. 10 %, max. 16 %
woody undertone. (by GLC); solubility: 1 vol in 5 vol of 95 %
d 25 20 ethanol at 20 ◦ C [224].
25 0.925 – 0.940; nD 1.5060 – 1.5160; [α]D
◦ ◦
+ 50 to + 77 ; ketone content (calculated as 4) Texas cedarwood oil is produced by steam
atlantone): min. 20 %; solubility: 1 vol in at distillation of chopped wood of the Texas
least 5 vol of 95 % ethanol [221]. cedar, Juniperus mexicana Schiede (Cupres-
Atlas cedarwood oil and Himalaya saceae). It is a brown to reddish-brown, vis-
cedarwood oil [from Cedrus deodara cous liquid that may partially solidify at room
(D. Don) G. Don] both contain α-atlantone temperature. It has a characteristic cedar-
[32207-08-2] as their main odoriferous com- wood odor.
ponent. They are used mainly in soap per- d 20
20 0.950 – 0.966; nD
20
1.5020 – 1.5100;
20 ◦ ◦
fumes. [α]D − 52 to − 30 ; total alcohol content
(calculated as cedrol): 35 – 48 %; cedrol con-
tent: min 20 % (by GLC), solubility: 1 vol in
5 vol of 90 % ethanol at 20 ◦ C [225].
For uses, see Virginia cedarwood oil.
5) Virginia cedarwood oil is produced by steam
E-(+)-α-Atlantone distillation of sawdust, finely chipped waste
wood from the manufacture of cedarwood
2) Cedar leaf oil ( Thuja oil) is produced by products, or from stumps and logs of the
steam distillation of fresh leaves and branch red cedar; Juniperus virginiana L. (Cupres-
ends of the tree Thuja occidentalis L. (Cu- saceae). It is an almost colorless to pale
pressaceae). It is a colorless to yellow liquid yellow, viscous liquid with a characteristic
with a powerful, herbaceous odor, character- cedarwood odor. The oil sometimes solidi-
istic of thujone [546-80-5]. fies at room temperature.
d 25 20
25 0.910 – 0.920; nD 1.4560 – 1.4590; [α]D
d 20
20 0.941 – 0.965; nD
20
1.5020 – 1.5100;
20 ◦ ◦
◦ ◦
− 14 to − 10 ; ketone content (calculated [α]D − 36 to − 16 ; solubility: 1 vol in
as thujone): min. 60 %; solubility: 1 vol in 5 vol of 95 % ethanol; sum of cedrol and wid-
3 vol of 70 % ethanol at 25 ◦ C [222]. drol: min. 15 %, max. 30 % (by GLC) [226,
227].
 Flavors and Fragrances 91

While the Texas cedar grows in Mexico and Celery for the production of seed oil is grown
other Central American countries, the Virginia mainly in southern France, India, and California.
cedar grows exclusively in the Southeast of The seed oil is used chiefly for flavoring foods,
the United States. Both cedar oils (production although small quantities are also used in per-
around 1600 t/a) are used mainly for perfuming fumery.
soaps and other products, as well as a starting
material for the isolation of cedrol [77-53-2]. Chamomile oils are available in three types:
Further fragrance substances such as cedryl ac-
etate (see p. page 41) and cedryl methyl ether 1) Blue chamomile oil (German chamomile
(see p. page 34) are produced from cedrol. The oil) is obtained by steam distillation of the
oils contain other sesquiterpenes, particularly α- flowers and stalks of Chamomilla recutita
cedrene and thujopsene, which can be converted (L.) Rauschert (Matricaria recutita. L., M.
to valuable fragrance materials. By acetylation chamomilla L. p.p.-Asteraceae), which is
of the mixture cedryl methyl ketone (see page grown mainly in central and eastern Eu-
39) is produced; for production of ambrocenide rope, Egypt, and Argentina. Annual produc-
pure α-cedrene is used (see page 76). tion is ca. 10 t. Blue chamomile oil is a
deep blue or bluish-green liquid that turns
green and, finally, brown when exposed to
light and air. The oil has a strong, char-
acteristic odor and a bitter-aromatic taste.
Chamazulene [529-05-5] is responsible for
its blue color. Chamazulene and (−)-α-
(+)-Cedrol bisabolol [23089-26-1] contribute to the anti-
inflammatory properties of blue chamomile
oil.
Celery seed oil is obtained by steam distilla-
tion of the crushed, ripe seeds of celery, Apium
graveolens L. (Apiaceae). It is an almost color-
less to brownish-yellow liquid with a character-
istic, pervasive, spicy, very persistent odor.
d 20
20 0.867 – 0.908; nD
20
1.4780 – 1.4880;
[α] 20
D + 65 ◦
to + 78 ◦
; solubility: 1 vol in no Chamazulene (−)-α-Bisabolol
more than 6 vol of 90 % ethanol at 20 ◦ C; acid
value: max. 6; ester value: 20 – 70 [228]. d 25
25 0.910 – 0.950; acid value: 5 – 50; ester
Major mono- and sesquiterpene hydrocar- value: 0 – 40; ester value (after acetylation):
bons in the oil are (+)-limonene (58 to 79 % ac- 65 – 155; solubility: solutions in 95 % etha-
cording to ISO) and β-selinene [17066-67-0]. Its nol usually remain turbid [229].
typical, long-lasting odor is caused primarily by 2) Roman chamomile oil (English chamomile
two lactones, 3-butylphthalide [6066-49-5] and oil) is produced from the dried flowers of
sedanenolide [62006-39-7] which each occur at Chamaemelum nobile (L.) All. (Anthemis
a concentration of ca. 1 %. nobilis L.), Asteraceae, which are cultivated
primarily in Belgium, but also in England,
France, and Hungary. The oil is distilled in
France and England. It is a light blue or light
greenish-blue liquid with a strong aromatic
odor characteristic of the flowers.
(+)-β-Selinene 3-Butylphthalide d 20
20 0.900 – 0.920; nD
20
1.4380 – 1.4460;
20 ◦ ◦
[α]D − 2 to + 3 , acid value: max. 8; ester
value: 250 – 340; solubility: 1 vol in 0.6 vol of
90 % ethanol (solutions may contain a slight
precipitate) [230].
Sedanenolide (3-butyl-4,5-dihydrophthalide)
92 Flavors and Fragrances

The constituents of Roman chamomile oil in- The main component of cinnamon leaf oil is
clude esters of angelic and tiglic acids. eugenol. The oil is used as such or as a source
3) Moroccan chamomile oil (wild chamomile of high-grade eugenol (see page 66).
oil) is produced from Ormenis species 3) Sri Lanka cinnamon bark oil is obtained by
(e.g., O. multicaulis, O. mixta) that grow steam distillation of the dried bark of the cin-
wild in Morocco. It is a light yellow liq- namon tree. It is a yellow liquid with the odor
uid with a sweet, herbaceous, woody bal- and burned-spicy taste of cinnamon.
samic odor. Its main constituents are ir- d 25 20
25 1.010 – 1.030; nD 1.5730 – 1.5910; [α]D
◦ ◦
regular monoterpenes, such as santolina al- − 2 to 0 ; aldehyde content (calculated
cohol [35671-15-9] and artemisia alcohol as cinnamaldehyde): 55 – 78 %; solubility:
[29887-38-5]. 1 vol in at least 3 vol of 70 % ethanol [233].
The oil is used predominantly in flavor com-
positions. (Limiting IFRA recommendation)

Cistus oil, see Labdanum Oil, page 104.

Santolina alcohol Artemisia alcohol
Citronella oil, see Cymbopogon Oils, page
98.
Cinnamon oils
1) Cassia oil (Chinese cinnamon oil) is ob- Citrus oils comprise both essential oils ob-
tained by steam distillation of the leaves, leaf tained from the peels of citrus fruits and essence
stalks, and young twigs, of Cinnamomum oils obtained by concentrating citrus juice (see
aromaticum Nees (C. cassia Bl., Lauraceae). Section 3.2.1). The essential oils and the essence
It is a yellow to reddish-brown liquid with a oils have similar compositions.
sweet-spicy, cinnamon-like odor, annual pro- Oils isolated from other parts of citrus plants
duction around 300 t. (blossoms and leaves) are not classified as citrus
d 20 20
20 1.052 – 1.070; nD 1.6000 – 1.6140; sol- oils because the former show marked differences
ubility: 1 vol in 3 vol of 70 % ethanol at in composition and organoleptic properties, they
20 ◦ C; acid value: max. 15; content of car- are described in other sections (see Neroli Oil,
bonyl compounds (calculated as cinnamalde- page 109 and Petitgrain Oils, page 112).
hyde): min. 80 % [231]. Production of Citrus Peel Oils. Apart from
In contrast to cinnamon bark oil, cassia distilled lime oil, citrus peel oils are produced
oil contains a considerable amount of 2- by pressing. Pressing of the peels for oil is often
methoxycinnamaldehyde (5 to 10 %) in addi- combined with juice production.
tion to its main constituent, cinnamaldehyde. In the first industrial production process, the
Cassia oil is used predominantly in flavor citrus fruit was cut into halves and the juice was
compositions. (Limiting IFRA recommenda- then pressed out. Further pressing of the peel
tion) liberated the desired oil. This mechanical pro-
2) Cinnamon leaf oil is produced by steam dis- cedure, which is still used, is known as cold
tillation of the leaves of the cinnamon tree, pressing. Currently, most citrus peel oils are pro-
Cinnamomum zeylanicum Blume. The main duced by other methods. For instance, the peel
countries in which the oil is produced are of the whole fruit is rasped or punctured before
Sri Lanka, the Seychelles, southern India, juice extraction to release the oil. The oil is then
Madagascar, and the Comoro Islands. It is rinsed off with water and is subsequently sepa-
a reddish-brown to dark brown liquid with rated from the resulting emulsion by centrifuga-
a characteristic spicy odor, reminiscent of tion.
clove buds. Production of Citrus Essence Oils. Distilla-
Specifications of cinnamon leaf oil from Sri tive concentration of citrus juices yields essence
Lanka are d 20 20
20 1.037 – 1.053; nD 1.5270 – oils, which separate from the aqueous phase in
1.5400; [α] 20D − 2.5 ◦
to + 2 ◦
; solubility: the receiver when the distillate condenses. The
1 vol in 2 vol of 70 % aqueous ethanol at composition of essence oils is similar to that of
20 ◦ C; phenol content: 75 – 85 % [232].
 Flavors and Fragrances 93

peel oils, but the essence oils usually contain oil, thus an IFRA recommendation exists.
a larger amount of aliphatic ethyl esters (e.g., Bergamot oil is used in many perfumes and is
ethyl butyrate in orange essence oil). Thus, their an important component of eaux de cologne.
aroma resembles that of a particular juice more 2) Grapefruit oil is obtained by cold pressing
than that of peel oils. of the outer peels of the fruits of Citrus par-
Citrus oils contain up to 95 % monoter- adisi Macfad. (Rutaceae). It is a yellow to
pene hydrocarbons (usually limonene, but oth- reddish orange liquid, with fresh citrus-like
ers as well, e.g., lemon oil also contains α- odor characteristic of grapefruit peel.
terpinene and β-pinene). The important aroma- d 20
20 0.852 – 0.860; nD
20
1.4740 – 1.4790;
20 ◦ ◦
determining components of citrus oils are func- [α]D + 91 to + 96 ; carbonyl value: min.
tionalized terpenes and aliphatic compounds 3.25; evaporation residue: min. 5.0 %, max.
(predominantly carbonyl compounds and es- 10.0 % [235].
ters), present only in very low concentrations. Grapefruit oil is produced mainly in the
Thus, several methods are employed to con- United States and its composition varies
centrate citrus oils on an industrial scale. The with the species. White grapefruit oil ob-
monoterpene hydrocarbon content is decreased tained from the varieties Marsh seedless and
by distillation, liquid–liquid partitioning bet- Duncan that are grown in Florida, contains
ween two immiscible solvents, or absorption on ca. 90 % terpene hydrocarbons (mainly (+)-
a carrier such as silica gel. The deterpenized con- limonene), 0.5 % alcohols (mainly linalool),
centrates are marketed under the name “Citrus 1.8 % aldehydes (mainly octanal and de-
oil x-fold”, depending on the concentration fac- canal), 0.5 % ketones (mainly nootkatone),
tor. 0.3 % esters (mainly octyl and decyl ac-
etate), and 7.5 % nonvolatile components
1) Bergamot oil, Italian is obtained by cold- [236, 237].
pressing peels from the unripe fruits of Cit- The sesquiterpene ketone nootkatone (for
rus aurantium L. subsp. bergamia (Risso et structure, see page 39) is primarily responsi-
Poit.) Wight et Arn. (Rutaceae). It is a green ble for the characteristic aroma of grapefruit
to greenish-yellow liquid, which sometimes oil.
contains a deposit. The oil has a pleasant, Grapefruit oil is used mainly for flavoring
fresh, sweet, fruity odor. fruit beverages. Annual production is 200 to
d 20 20
20 0.876 – 0.883; nD 1.465 – 1.470; [α] D
20
220 t. (Limiting IFRA recommendation)
◦ ◦
+ 15 to + 32 ; evaporation residue 4.5 – 3) Lemon oil is obtained by pressing peel from
6.4 %; solubility: 1 vol in 1 vol of 85 % etha- the fruits of Citrus limon (L.) Burm. f., (Ru-
nol at 20 ◦ C; acid value: max. 2.0; ester value: taceae). It is a pale yellow to pale greenish-
86 – 129, corresponding to an ester content yellow liquid with a characteristic lemon
of 30 – 45 % (calculated as linalyl acetate) peel odor. ISO differentiates between Ameri-
[234]. can, Mediterranean, and Equatorial type. The
Bergamot is still grown almost exclusively American type is subdivided into ‘coastal’
in the Italian province of Calabria, where and ‘desert’ type. In the following the physi-
the soil and climatic conditions are very fa- cal properties of the ‘coastal’ type are given.
vorable for its cultivation. The bergamot is d 20
20 0.852 – 0.858; nD
20
1.4730 – 1.4760;
grafted onto bitter orange plants. The quality [α] 20
D + 57 ◦
to + 65.6 ◦
; evaporation residue:
of the oil is determined by its ester content 1.75 – 3.6 % [238]; acid value: max. 2 %;
and varies with the species. Annual produc- content of carbonyl compounds (calculated
tion is ca. 90 t. as citral): 8.0 – 14.0 %.
Linalyl acetate, linalool (10 %), and citral The composition of lemon oils depends on
(1 %) are important components of bergamot the variety of lemon and the country of ori-
oil. Its terpene content (25 – 50 %) is rela- gin. Their main components are terpenes –
tively low for a citrus oil. (+)-limonene (ca. 65 %), β-pinene, and γ-
Use of the untreated oil in cosmetics is lim- terpinene (8 – 10 % each) being the most im-
ited by the photosensitizing properties of portant. The characteristic odor of lemon oil
bergaptene (a furocoumarin) present in the differs from that of other citrus oils and is
94 Flavors and Fragrances

largely due to neral and geranial. The con- Distilled lime oils are produced by steam dis-
tent of these compounds is in the coastal type tillation of an oil–juice emulsion that is ob-
between 1.6% and 2.9 %, in Italian lemon oil tained by chopping the whole fruit. The acid
between 1.4 and 3.2 % [238]. present in the juice acts on the oil released
Annual worldwide production is about from the peel and changes its characteris-
3.7 × 103 t, most of which originates from tics. The original components are modified
the United States, Italy, and Argentina. to form a series of new compounds.
Lemon oil is used in many food flavors. Be- Distilled lime oil is a colorless to pale yel-
cause of its fresh odor, relatively large quan- low liquid, with a characteristic odor, which
tities are also employed in eaux de cologne differs from that of the fresh fruit and the
and other perfumery products (see IFRA rec- cold-pressed oil.
ommendation). d 20 20
20 0.856 – 0.865; nD 1.474 – 1.478; [α] D
20

4) Lime oil may be either cold-pressed or dis- + 34 ◦ to + 45 ◦ ; evaporation residue: max.

tilled, but the distilled oil is produced on a 2.5 %; content of carbonyl compounds (cal-
much larger scale. culated as citral): max. 1.5 % [243].
Two varieties of limes are of importance in Acid-catalyzed cyclization and dehydra-
the commercial production of lime oils: the tion of citral and linalool give rise to
West Indian (Mexican or Key) lime, Citrus several compounds that occur at com-
aurantiifolia (Christm. et Panz.) Swingle and paratively high concentrations and con-
the Persian (Tahiti) lime, C. latifolia Tanaka tribute to the typical aroma of distilled
(Rutaceae). The former has small fruits with lime oil (e.g., 1,4-cineole [470-67-7],
many seeds, and the latter bears larger, seed- 1,8-cineole [470-82-6], 2,2,6-trimethyl-6-
less fruits. West Indian limes are grown pri- vinyltetrahydropyran [7392-19-0], and 2-
marily in Mexico, the West Indies and Peru; (2-buten-2-yl)-5,5-dimethyltetrahydrofuran
Persian limes are cultivated in Florida and [7416-35-5]).
Brazil. Annual worldwide production of distilled
Persian lime oils contain lower concentra- West Indian lime oil is about 750 t. The oil is
tions of the typical organoleptic components used primarily in soft drinks.
than the West Indian lime oils and are thus 5) Mandarin oil is obtained by cold pressing
comparatively mild and flat [239]. Conse- the peel of mandarin oranges, the fruits of
quently, West Indian lime oils are more pop- Citrus reticulata Blanco (Rutaceae). The oil
ular. is a greenish-yellow to reddish-orange liq-
Pressed lime oilsare obtained by rasping and uid, depending on the degree of ripeness of
puncturing (type B). Other methods are also the fruit, with a pale blue fluorescence and a
employed for West Indian limes: the whole characteristic odor, reminiscent of mandarin
fruits may be chopped and the oil–juice peel.
emulsion subsequently centrifuged (type A) d 20 20
20 0.848 – 0.855; nD 1.474 – 1.478, [α] D
20

[240, 241]. + 64 ◦ to + 75 ◦ ; evaporation residue: 1.6 –

Pressed lime oil (Mexican type, A) is a yel- 4.0 %; content of carbonyl compounds (cal-
lowish green liquid with a strong, charac- culated as decanal): 0.4 – 1.2 %; acid value:
teristic odor, reminiscent of lemon. Limiting max. 2.0 [244].
IFRA recommendation. The main components are limonene (ca.
Type A: d 20 20
20 0.875 – 0.884, nD 1.482 – 70 %) and γ-terpinene (ca. 20 %). The char-
20 ◦ ◦
1.486, [α] D + 35 to + 42 ; carbonyl value: acteristic feature of mandarin oil is its content
min. 16, max. 31, corresponding to 4.5 of α-sinensal, methyl N-methylanthranilate
to 8.5 % of carbonyl compounds expressed (which is responsible for fluorescence), and
as citral; evaporation residue: 10.0 – 14.5 % long-chain unsaturated aliphatic aldehydes.
[242]. Annual production of mandarin oil in Italy is
Cold-pressed lime oils are produced in a ca. 100 t; smaller quantities are produced in
quantity of about 300 t/a. The composition Spain, Brazil, and Argentina.
and uses of pressed lime oil are similar to Mandarin oil is used to enrich the bouquet of
those of pressed lemon oil. flavor compositions containing sweet orange
 Flavors and Fragrances 95

oils as the main component. It is also used in the flavoring of beverages and confectioner-
liqueurs and perfumery. ies and perfuming eaux de cologne, soap, and
6) Orange oil bitter is obtained by pressing household products.
fresh peel from the fruits of Citrus auran-
tium L. subsp. aurantium (Rutaceae). It is
produced mainly in Mediterranean countries
and is a pale yellow to yellowish-brown liq-
uid with a slightly mandarin-like odor and a
somewhat bitter aroma.
d 20 20
20 0.8480 – 0.8600; nD 1.4720 – 1.4760;
20 ◦ ◦ α-Sinensal β-Sinensal
[α]D + 88 to + 98 ; evaporation residue:
2 – 5 %; aldehyde content (calculated as de-
canal): min. 0.5 %, max. 2.9 % [245]. Civet, see Animal Secretions, page 87.
The composition of bitter orange oil differs
from that of sweet orange oil; i.e., its alde- Clary sage oil, see Sage Oils, page 115.
hyde content is lower and its ester content is
higher. Clove oils are produced from the 15 – 20-
Worldwide production of bitter orange oil m high clove tree Syzygium aromaticum (L.).
(ca. 10 t/a) is lower than that of other pressed Merr. et L. M. Perry, syn: Eugenia caryophyl-
peel oils. Bitter orange oil is used in eaux de lus (Spreng.) Bullock ex S. G. Harrison (Myr-
cologne and liqueurs. Limiting IFRA recom- taceae).
mendation.
7) Orange oil sweet is obtained from the peel 1) Clove bud oil is obtained in 15 – 20 % yield
of the fruits of Citrus sinensis (L.) Osbeck. It by steam distillation of the dried flower buds.
is a yellow to reddish-yellow liquid with the Clove bud oil, like the leaf oil, is a yellow to
characteristic odor of orange peel and may brown, sometimes slightly viscous liquid. It
become cloudy when chilled. Sweet orange turns dark purple-brown on contact with iron.
oil is often produced in combination with or- The oil has the spicy odor characteristic of
ange juice (e.g., in the United States, Brazil, eugenol.
Israel, and Italy). Specifications for the oils d 20
20 1.042 – 1.063; nD
20
1.5280 – 1.5380;
depend on the cultivated varieties and the [α] 20
D − 1.5 ◦
to 0 ◦
; solubility: 1 vol in 2 vol
country of origin [246] of 70 % ethanol at 20 ◦ C; phenol content:
The ISO specification of Orange oil sweet is min. 85 %, max. 93 % [247].
as follows: 2) Clove leaf oil is obtained in 2 – 3 % yield by
d 20
20 0.842 – 0.850; nD
20
1.4700 – 1.4760; steam distillation of the leaves of the above-
20 ◦ ◦ mentioned.
[α] D + 94 to + 99 ; evaporation residue:
1.0 – 5.0 %; content of carbonyl compounds d 20 20
20 1.039 – 1.049; nD 1.5280 – 1.5350; sol-
(calculated as decanal): 0.9 – 3.1 %. ubility: 1 vol in 2 vol of 70 % ethanol at
The oils have a high terpene hydrocarbon 20 ◦ C; phenol content: minimum 82 % [248].
content (> 90 %, mainly (+)-limonene), but The main component of all clove oils is
their content of oxygen-containing com- eugenol (draft for a GLC specification for
pounds differs and affects their quality. Im- leaf oils: 80 to 92 %), which is responsible
portant for aroma are aldehydes, mainly for their odor and antiseptic properties. Other
decanal and citral, and aliphatic and ter- major constituents are eugenyl acetate and
penoid esters. The sesquiterpene aldehydes caryophyllene. Clove bud oil has a higher ac-
α-sinensal [17909-77-2] and β-sinensal etate content and a more delicate odor than
[6066-88-8], which contribute particularly to leaf oil, but is much more expensive than the
the special sweet orange aroma, also occur in leaf oil. Leaf oil is produced and used in the
other citrus oils, although in lower concen- largest quantities.
tration. The most important countries that produce
Worldwide production of cold-pressed or- clove oils are Madagascar, Tanzania, and In-
ange oil is over 27 000 t/a. Its main uses are donesia. Smaller quantities are produced in
96 Flavors and Fragrances

other tropical areas (e.g., Malaysia and Sri used extensively in seasoning mixtures and in
Lanka). Worldwide production of clove oils perfume compositions.
is 2000 – 2200 t/a, of which Indonesia pro-
duces about half. Cornmint oil, see Mint Oils, page 107.
The oils are used in many perfume and aroma
compositions, because of their spicy clove Cumin oil is obtained by steam distillation of
odor. A small amount is used as an antiseptic, ripe fruits of Cuminum cyminum L. (Apiaceae).
mainly in dentistry. The leaf oil, in particular, It is a light yellow to brown liquid with a strong,
is also used as a raw material for the produc- somewhat fatty and green odor.
tion of eugenol, which is the starting material d 20 20
20 0.905 – 0.930; nD 1.490 – 1.5060; [α]D
20
for further commercially important fragrance ◦ ◦
+ 1 to + 8 ; solubility: 1 vol in 8 vol of 80 %
compounds, such as isoeugenol and eugenyl ethanol at 20 ◦ C; aldehyde content: 45 – 58 %
esters (see page 65). (calculated as cuminaldehyde) [251].

Copaiba (balsam) oils are obtained by Cymbopogon oils are produced from several
steam distillation of the exudate (balsam) from aromatic grasses that belong to the genus Cym-
the trunk of several species of Copaifera L. bopogon Spreng. (Poaceae). The oils are ob-
(Fabaceae), a genus of trees growing in the Ama- tained by steam distillation of the parts of the
zon basin. They are colorless to light yellow liq- plants that grow above ground. The following
uids with the characteristic odor of the corre- oils are of commercial interest:
sponding balsams and an aromatic, slightly bit-
ter, pungent taste. 1) Citronella oil is available in two types:
d 25 20
25 0.880 – 0.907, nD 1.4930 – 1.5000; [α]D
a) Ceylon or Sri Lanka citronella oil is
− 33 ◦ to − 7 ◦ ; solubility: 1 vol in 5 – 10 vol of produced by steam distillation of fresh
95 % ethanol [249]. or partly dried leaves and stems of the
The oils consist primarily of sesquiter- grass species Cymbopogon nardus (L.)
pene hydrocarbons; their main component is W. Watson–“lenabattu”–cultivated in Sri
caryophyllene (> 50 %, for formula, see Sec- Lanka. It is a pale yellow to brownish liq-
tion 2.3). uid with a fresh, grassy, camphoraceous
Copaiba balsam oils and balsams are used odor.
mainly as fixatives in soap perfumes. d 20
20 0.891 – 0.910; nD
20
1.479 – 1.490;
[α] 20
D − 25 ◦
to − 12 ◦
; solubility: 1 vol
Coriander oil is obtained by steam distil- in 2 vol of 80 % ethanol at 20 ◦ C; ester
lation of ripe fruits of Coriandrum sativum L. value (after acetylation): 157 – 200; car-
(Apiaceae). It is an almost colorless to pale yel- bonyl value: 18 – 55, corresponding to 5 –
low liquid with a characteristic spicy odor, rem- 15 % carbonyl compounds (calculated as
iniscent of linalool. citronellal) [252].
d 20 20
20 0.862 – 0.878; nD 1.4620 – 1.4700; [α]D
20 Ceylon oil is less valuable than Java oil and
+ 7 ◦ to + 13 ◦ ; solubility: 1 vol in 8 vol of 65 % is used almost exclusively for perfuming
ethanol at 20 ◦ C; acid value: max. 3.0; linalool toilet soaps, washing powders, and house-
content by chromatography: min. 68 % [250]. hold products.
The main component of coriander oil is (+)- b) Java citronella oil is obtained by steam
linalool (60 – 80 %). Mono- and polyunsaturated distillation of fresh or partially dried stems
fatty aldehydes, although minor components, and leaves of Cymbopogon winterianus
contribute to the characteristic aroma of the oil Jowitt syn. Cymbopogon nardus W. Wat-
because of their powerful odor. son var. mahapengiri Winter, which is
Coriander is mainly cultivated in the CIS, grown in Southeast Asia, India, and In-
Poland, and Hungary. Worldwide oil production donesia, as well as in Central and South
is 50 – 100 t/a. Coriander oil is no longer im- America. It is a pale yellow to pale yel-
portant as a raw material for the production of lowish brown liquid with a slightly sweet,
linalool and its derivatives. However, it is still flowery, roselike odor with the strong cit-
rus note of citronellal.
 Flavors and Fragrances 97

d 20
20 0.880 – 0.893; nD
20
1.467 – 1.473; Residues remain after vacuum distillation
20 ◦ ◦
[α] D − 5 to 0 ; solubility: 1 vol in of oils stored for longer times due to the
2 vol of 80 % ethanol at 20 ◦ C, opales- high molecular mass products formed by
cence is sometimes observed when ethanol polymerization of myrcene. The oil con-
is continuously added; ester value (after tains up to 20 % myrcene [255].
acetylation): min. 250, corresponding to b) Indian lemongrass oil is obtained from
85 % acetylizable compounds (calculated the so-called Indian variety of lemongrass,
as geraniol, this percentage includes cit- Cymbopogon flexuosus (Nees ex Steud.)
ronellal, since it is converted quantitatively Stapf. The oil is produced mainly in India.
into isopulegyl acetate under the acety- Its physical constants differ slightly from
lation conditions); carbonyl value: min. those of the West Indian type, the main dif-
127, corresponding to 35 % carbonyl com- ference being in the density, which is d 20 20
pounds (calculated as citronellal) [253]. 0.885 – 0.905 [256].
Java citronella oil may contain up to 97 % The two oils were formerly the main
acetylizable compounds and up to 45 % source of natural citral, obtained as a ca.
carbonyl compounds, depending on the 4 : 1 mixture of geranial and neral by dis-
time of harvesting. Is is used extensively tillation (see page 21). However, lemon-
not only in perfumery, but also as one of grass oil has declined in commercial im-
the most important raw materials for the portance due to the competitive synthe-
production of citronellal. In addition, a sis of citral (see page 21) and isolation of
fraction with a high geraniol content is ob- natural citral from Litsea cubeba oil (see
tained from the oil. Both citronellal (see page 106). Nevertheless, between 300 and
page 22) and the geraniol fraction (see 500 t/a are still produced. In addition to be-
page 15) are starting materials for the syn- ing processed into citral, it is used to some
thesis of a large number of other fragrance extent for perfuming soap and household
compounds. The oil produced in Taiwan products.
and in Java contains, in addition to the ma- 3) Palmarosa oil is obtained by steam distilla-
jor components citronellal and geraniol, tion of wild or cultivated Cymbopogon mar-
11 – 15 % citronellol, 3 – 8 % geranyl ac- tinii (Roxb.) W. Watson. var. motia, collected
etate, 2 – 4 % citronellyl acetate, and many when in blossom. It is a pale yellow liq-
other minor components. uid with a characteristic roselike odor and
Annual worldwide production was re- a grassy note.
ported to be > 5000 t in 1971 and is now d 20
20 0.880 – 0.894; nD
20
1.4710 – 1.4780;
20 ◦ ◦
less than 2000 t. Main producers are Tai- [α] D − 1.4 to + 3 ; solubility: 1 vol in 2 vol
wan, China (province of Hainan), and Java of 70 % ethanol at 20 ◦ C; acid value: max.
[254]. 1.0; the following data are valid for oil from
2) Lemongrass oil is available in two types, India, oils of other origin possess slightly dif-
which are produced by steam distillation. ferent data, ester value: min. 7, max. 36; es-
a) West Indian or Guatemala lemongrass oil ter value (after acetylation): 260 – 280, cor-
is obtained from Cymbopogon citratus responding to a total alcohol content of 88 –
(DC.) Stapf in Central and South Amer- 95 %, free alcohol content (calculated as
ica, as well as in a number of African and geraniol): 74 – 94 % [257]. High-grade pal-
East Asian countries. It is a pale yellow marosa oil may contain up to 95 % geraniol
to orange-yellow liquid with a lemon-like and its esters; it is produced in smaller quan-
odor, characteristic of citral. tities than other oils obtained from aromatic
d 20
20 0.872 – 0.900; nD
20
1.483 – 1.489; grasses. Annual worldwide production is ca.
[α] 20
D − 6 ◦
to 0 ◦
; content of carbon- 150 t. Palmarosa oil is the starting material
yl compounds (calculated as citral): min. for geraniol and geranyl esters of high odor
75 %; solubility: freshly distilled oil is sol- quality, but it is also used for perfuming soaps
uble in 70 % ethanol at 20 ◦ C, but solu- and cosmetics.
bility diminishes on storage and the oil
may become insoluble in 90 % ethanol.
98 Flavors and Fragrances

4) Gingergrass oil is produced in India from Commercially available dill oils are mixtures
the sofia variety of Cymbogon martinii and of both types, because the plants are harvested
is less important than palmarosa oil. not according to the criteria for the special
oils, but when the state of ripeness guarantees
Cypress oil is produced by steam distillation a maximum yield. They generally contain α-
of terminal branches of Cupressus sempervirens phellandrene (10 – 20 %), limonene (30 – 40 %),
L. (Cupressaceae). It is a liquid with a woodlike dill ether (3 – 10 %), and carvone (30 – 40 %).
odor that has an ambergris note. The main growing areas are the Balkan states,
d 20 20
20 0.863 – 0.885; nD 1.468 – 1.478; [α]D
20 Hungary, and the United States. Dill oils are used
◦ ◦ primarily for seasonings in the pickling and can-
+ 15 to + 30 ; solubility: 1 vol in 8 vol of 90 %
ethanol. ning industries.
This oil is produced exclusively in southern
France and Algeria (ca. 10 t/a); its major com- Elemi oil, Elemi resinoid are obtained from
ponents are α-pinene and 3-carene. Degradation exuded gum resin of Canarium luzonicum
products of higher terpenoids are responsible for (Miq.) (Burseraceae), a tree growing in the
the typical ambergris note [258, 259]. Phillipines. The resin is extracted with a solvent
to form the resinoid, which is a yellow to orange
Davana oil is obtained by steam distillation mass of high viscosity. The oil is produced by
of the herb Artemisia pallens Wall. (Asteraceae), steam distillation of the gum oleoresin and is a
grown in south India. It is an orange-brown colorless to light yellow liquid.
liquid with a sweet tealike odor reminiscent d 20 20
20 0.850 – 0.910; nD 1.4720 – 1.4900; [α]D
20
◦ ◦
of dried fruits. The composition of the oil is + 44 to + 85 [260].
very complex; its main components are fura- The major components of elemi oil are
noid sesquiterpenes. It is used predominantly for limonene, α-phellandrene, and the sesquiter-
aroma compositions. pene alcohol elemol. Both the resinoid and the
oil have a fresh, citrus-like, peppery odor and
Dill oil is obtained from the dill plant, are used predominantly in soap perfumes.
Anethum graveolens L. (Apiaceae), in two dif-
Estragon oil, see Tarragon Oil, page 117.
ferent forms:
1) Dill weed oil is prepared from flowering Eucalyptus oils are produced from plants
dill by steam distillation. Its main compo- belonging to the genus Eucalyptus (Myrtaceae),
nents are α-phellandrene (up to 60 %) and which includes ca. 500 species in Australia, the
the so-called (+)-dill ether [74410-10-9] (up country of origin, alone. Correct botanical clas-
to 30 %). The latter is responsible for the typ- sification was possible only by determining the
ical organoleptic properties of the dill plant chemical composition of the essential oils ob-
and, thus, of dill weed oil. tained from the leaves. At present, few of these
oils are commercially important.
1) Cineole-rich Eucalyptus oils
a) Australian eucalyptus oil is obtained by
steam distillation of the foliage of certain
Eucalyptus species indigenous to Aus-
tralia, e.g., from Eucalyptus fruticetorum
F.v. Muell. (E. polybractea R. T. Bak.), E.
smithii R. T. Bak., and E. leucoxylon F.v.
2) Dill seed oil is prepared by steam distillation Muell.
of the crushed ripe fruits of the dill plant. Its d 20
20 0.918 – 0.928; nD
20
1.458 – 1.465;
20 ◦ ◦
main components are limonene (up to 40 %) [α] D − 2 to + 2 ; solubility: 1 vol in
and (+)-carvone (up to 60 %). This oil has 3 vol of 70 % ethanol at 20 ◦ C; 1,8-cineole
a typical caraway odor and taste in contrast content: 80 – 85 % [261].
to the weed oil, which contains only a small The minor components of this oil differ
amount of carvone. from those of E. globulus oil.
 Flavors and Fragrances 99

b) Eucalyptus globulus oil is produced by Africa and India). The annual production
steam distillation of the leaves and twigs, worldwide is about 1300 t. Eucalyptus citri-
recently collected of Eucalyptus globulus odora oil is a starting material for the manu-
Labillardière. It is an almost colorless to facture of citronellal and products derived
pale yellow liquid with a fresh odor, char- from it. It is also used in perfumery for the
acteristic of 1,8-cineole. The crude oil con- same purposes as citronellal (see page 22).
tains ca. 65 % cineole and more than 15 % 3) Eucalyptus dives oil is obtained by steam
2)
α-pinene. Commercially available quali- distillation of fresh leaves of Eucalyptus
ties are rectified, and have a cineole con- dives var. Schau, Typus, grown in New South
tent of 70 – 75 % or 80 – 85 %. The respec- Wales.
tive specifications of these two types are as d 15 0.889 – 0.910; n20D 1.477 – 1.481; [α]D
20
◦ ◦
follows: − 75 to − 50 ; content of carbonyl com-
d 20
20 0.904 – 0.920 and 0.906 – 0.920; nD
20
pounds (calculated as piperitone): 40 – 50 %
20 ◦
1.460 – 1.468 and 1.458 – 1.465; [α] D 0 [264].
to + 10 ◦ and + 2 ◦ to + 10 ◦ ; solubility 1 vol In addition to (−)-piperitone (for formula see
in 5 vol of 70 % ethanol and 1 vol in 5 vol page 30), the oil contains 15 – 25 % α- and
of 80 % ethanol at 20 ◦ C [262]. β-phellandrene. The oil was previously used
The oil is produced mainly in Spain and as a starting material in the manufacture of
Portugal, where the wood is used in the cel- (−)-menthol, but has lost much of its signifi-
lulose industry, and in China. Worldwide cance. Annual worldwide production in 2002
production is between 3500 and 4000 t/a. has dropped to 50 t.
Eucalyptus oils with a high cineole con- 4) Eucalyptus staigeriana oil is produced by
tent are used for cineole production (see steam distillation of the leaves of Eucalyptus
page 72). The oils and cineole itself are staigeriana F. v. Muell. It has a fresh, lemon-
used primarily in pharmaceutical prepara- like odor and contains ca. 30 % citral. Further
tions. Fairly large quantities are also used constituents are geraniol and nerol and their
in perfumery, e.g., to imitate the odor of acetates, as well as (−)-limonene. It is used
cineole-containing essential oils. Distilla- mainly in perfumery [265].
tion fractions of camphor oil (see page 90)
are also marketed as eucalyptus oils with Fennel oil is commercially available in sweet
a cineole content of 70 – 80 %. and bitter types that are obtained from two vari-
Eucalyptus citriodora oil is obtained by eties of a subspecies of common fennel, Foenicu-
steam distillation of leaves and twigs of Eu- lum vulgare Mill., subsp. capillaceum Gilib.
calyptus citriodora Hook. It is an almost col- (Apiaceae). The sweet oil is obtained from the
orless, pale yellow, or greenish-yellow liquid dulce variety and the bitter oil from the variety
with a citronellal-like odor. vulgare (Mill.) Thell.
d 20 20
20 0.860 – 0.870; nD 1.450 – 1.456; [α]D
20 The oils are produced both in the Mediter-
− 1 ◦ to + 3 ◦ ; solubility: 1 vol in 2 vol of 80 % ranean countries and in other continents and are
ethanol at 20 ◦ C; carbonyl value (calculated obtained by steam distillation of crushed fennel
as citronellal): min. 70 % [263]. seeds. They are colorless to pale yellow liquids
In addition to the main component, citronel- with a typical fennel odor and a camphoraceous,
lal, the oil contains citronellol and isopulegol initially sweet taste that later becomes bitter.
(5 – 10 % each). d 20 20
20 0.961 – 0.977; nD 1.5280 – 1.5430; [α]D
20
◦ ◦ ◦
Young E. citriodora trees that are grown ex- + 11 to + 24 ; fp 3 – 11.5 C; solubility: 1 vol
clusively for essential oil production are cut in 5 vol of 80 % ethanol.
back to a height of 1 – 1.50 m and develop Both oils are similar in composition; their ma-
into shrubs. The leaves can be harvested jor components are trans-anethole (> 80 % in
throughout the year; more than 200 kg of oil sweet fennel oil) and fenchone (up to ca. 25 %
can be obtained per hectare. in bitter fennel oil). Sweet fennel oil is more im-
The major producer is Brazil with over portant because of its higher anethole content.
500 t/a, but considerable quantities are also While both oils are used in flavors, small quan-
produced in other countries (e.g., South tities are also employed in perfumery.
100 Flavors and Fragrances

Fir needle oils, see Pinaceae Oils, page 113. Galbanum oil is used for creating green top
notes in perfume compositions.
Galbanum oil and galbanum resinoid are Galbanum resinoid is produced by extraction
produced from the gumlike exudate of Ferula of the gum with a nonpolar solvent. It is used for
galbaniflua Boiss. and Buhse (Apiaceae) grow- the same purposes as the oil and has excellent
ing in northern Iran and F. rubricaulis Boiss. fixative properties.
growing in southern Iran.
The gum is collected from a cut in the upper Geranium oil is obtained by steam distilla-
part of the uncovered roots. The annual yield of tion of the flowering herb Pelargonium grave-
gum is ca. 100 t. olens l’Heritier ex Aiton, P. roseum Willde-
The oil is produced by steam distillation and now, and other nondefined hybrids that have
is a colorless to light yellow liquid with a green, developed into different ecotypes in different
slightly spicy odor. geographical regions. The oil is an amber to
d 20 20
20 0.8670 – 0.8900; nD 1.4780 – 1.4850; greenish-yellow liquid with the characteristic
20 ◦ ◦
[α]D + 7 to + 17 ; acid value: max. 2; sol- roselike odor of the plant.
ubility: 1 vol in at least 6 vol of 90 % ethanol The main cultivation areas are Réunion
[266]. and Madagascar (Bourbon type), Morocco and
In addition to 75 % monoterpene hydrocar- Egypt (North African type), and China. The
bons and ca. 10 % sesquiterpene hydrocarbons, Bourbon quality is more valuable and thus more
galbanum oil contains a fairly large number of expensive. Annual worldwide production is ca.
terpene and sesquiterpene alcohols and their ac- 300 t. Specifications of geranium oils [267] are
etates. Minor components, with entirely differ- given in Table 3.
ent structures and low odor threshold values, The composition of the Bourbon oil differs
contribute strongly to the chacteristic odor. Ex- quantitatively as well as qualitatively from that
amples are as follows: of North African oil. However, they both contain
an unusually high percentage of (−)-citronellol,
isomenthone, formates, and tiglates, which are
rarely found in essential oils. The two types of oil
(E,Z)-1,3,5-Undecatriene [51447-08-6]
can be differentiated by two characteristic minor
constituents: the Bourbon type contains (−)-6,9-
guaiadiene [36577-33-0] and the African type
contains 10-epi-γ-eudesmol [15051-81-7] (for
structure see page 86). The Chinese type also
2-Methoxy-3-isobutylpyrazine [24683-00-9]
contains (−)-6,9-guaiadiene, however a smaller
amount of menthone/isomenthone and a higher
amount of (−)-citronellol than the Bourbon
type.
S-sec-Butyl 3-methyl-2-butenethioate
[34322-09-3]

Table 3. Specifications of geranium oils

Parameter Type of geranium oil

Bourbon Egyptian Moroccan Chinese

d 20
20 0.884 – 0.892 0.887 – 0.892 0.883 – 0.900 0.882 – 0.8
n20
D 1.4620 – 1.4680 1.4660 – 1.4700 1.4640 – 1.4720 1.4600 – 1
[α]20
D − 14 ◦ to − 8 ◦ − 12 ◦ to − 8 ◦ − 13 ◦ to − 8 ◦ − 14 ◦ to − 8 ◦
Solubility in 70 % ethanol (20 ◦ C), vol : vol 1:3 1 : 2.2 1:3 1:5
Acid value (max.) 10 6 10 10
Ester value 52 – 78 42 – 58 35 – 80 55 – 75
Ester value (after acetylation) 205 – 230 210 – 222 192 – 230 215 – 232
Content of carbonyl compounds (as isomenthone), % max. 16 max. 16 max. 16 max. 10
Alcohol content (as citronellol), % 42 – 55 40 – 58 35 – 58
 Flavors and Fragrances 101

Main cultivation areas for ginger are India,

Malaysia, Taiwan, and the Fiji Islands. Ginger
concentrates are used in large amounts in bever-
ages (e.g., ginger ale), as well as in baked goods
and confectioneries.
(−)-6,9-Guaiadiene
Grapefruitoil, see Citrus Oils, page 94.
Geranium oil is one of the most important
natural raw materials in the fragrance industry. Green cognac oil, see Lie de Vin Oil, page
It is used for creating rosy notes, especially in 106.
soap.
Guaiac wood oil is obtained by steam distil-
Ginger oil and ginger oleoresin are pro- lation of ground wood and sawdust from the tree
duced from the ginger plant Zingiber officinale Bulnesia sarmienti Lorentz (Zygophyllaceae),
(L.) Rosc. (Zingiberaceae). which is up to 20 m high and grows wild in
Ginger oil is produced by steam distillation the Gran Chaco region of Paraguay and in Ar-
of dried, ground rhizomes. It is a light yellow to gentina. The annual production is ca. 150 t. The
yellow liquid with the aromatic, persistent odor oil is a dark yellowish, viscous liquid with a mild,
of ginger, but lacking the pungency usually as- pleasant odor reminiscent of that of tea roses and
sociated with ginger. The citrus note of ginger faintly of violets. The oil solidifies at room tem-
oil is due to traces of citral. perature to a yellow-white to light amber colored
d 25 20
25 0.871 – 0.882; nD 1.4880 – 1.4940; [α]D mass (mp 40 – 50 ◦ C).
− 45 ◦ to − 28 ◦ ; saponification value: max. 20; d 25 20
25 0.960 – 0.975; nD 1.5020 – 1.5070; [α]D
◦ ◦
soluble in ethanol, solutions are usually turbid − 12 to − 3 ; solubility: 1 vol in at least
[268]. 7 vol of 70 % ethanol; solutions are sometimes
The major components of the oil are β- slightly turbid or opalescent; total alcohol con-
sesquiphellandrene [20307-83-9] (about 15 %) tent (calculated as guaiol): min. 85 % [269].
and zingiberene [495-60-3] (30 to 40 %). The main constituents of the oil are the
sesquiterpene alcohols guaiol [489-86-1] and
bulnesol [22451-73-6]. The oil may be used as
a starting material for the synthesis of guaiazu-
lene, which has anti-inflammatory properties.

β-Sesquiphellandrene Zingiberene

Ginger oleoresin is prepared by extracting

ginger rhizomes with acetone or alcohol. The
product contains the essential oil along with the
substances responsible for the pungency of gin- Guaiol Bulnesol

ger. These compounds are substituted phenols Guaiac wood oil is used extensively in per-
of the following structure: fume compositions for its excellent fixative
properties. Also the acetates of the sesquiterpene
alcohols of this oil are used in perfumery.

Gurjun balsam oil is produced by steam dis-

tillation of balsams obtained from several Dipte-
rocarpus species (Dipterocarpaceae); the trees
grow in South and East Asia. The oil is a yellow,
slightly viscous liquid with a weak, woodlike
odor.
102 Flavors and Fragrances

d 15 0.918 – 0.930; n20

D 1.5010 – 1.5050; [α]D The absolute is one of the most valuable blos-
− 130 ◦ to − 35 ◦ ; solubility: 1 vol in 10 vol of som fragrances used in fine fragrances.
ethanol.
It consists almost entirely of sesquiterpene Juniper berry oil is obtained by steam distil-
hydrocarbons, and its main component (> 60 %) lation of berries of Juniperus communis L. var.
is α-gurjunene [489-40-7]. erecta Pursh. (Cupressaceae). It is a colorless,
pale green or yellowish liquid with a character-
istic, conifer-like odor, and an aromatic-bitter
taste.
d 20 20
20 0.857 – 0.872; nD 1.4710 – 1.4830; [α]D
20

− 15 ◦ to 0 ◦ ; solubility: 1 vol in 10 vol of 95 %

ethanol, solutions usually turbid; acid value:
max. 2; ester value: min. 12 [270].
α-Gurjunene The slightly turpentine-like odor and the
relatively low solubility of the oil are caused
Gurjun balsam oil and gurjun balsams are
by its high content of α-pinene and other
used for their good fixative properties, e.g., in
monoterpene hydrocarbons. The main oxygen-
soap perfumes and serve also as a starting ma-
containing component is 1-terpinen-4-ol.
terial for the production of guaiazulene.
Most juniper berries are obtained from
bushes growing in European countries, such as
Jasmin absolute is obtained by solvent ex-
Italy, Czech Republic, Slovakia, Hungary, and
traction, via the concrete, from the flowers of
former Yugoslavia.
Jasminum grandiflorum L. (Oleaceae), culti-
The oil is used to a limited extent in per-
vated in Egypt, Italy, Morocco, and India, and
fumery for creating fresh, dry effects and as an
of J. sambac (L.) Ait. from China and India.
aroma ingredient in alcoholic beverages of the
The concrete is usually a brown to dark brown
gin type.
waxy mass, with a characteristic jasmin odor.
mp 48 – 51 ◦ C; ester value: 70 – 125. Labdanum absolute and Labdanum oil are
The absolute is generally a reddish-brown liq- obtained from labdanum gum, which is exuded
uid with a delicate jasmin odor; the color deep- when twigs of Cistus ladaniferus L. (Cistaceae)
ens on storage. are boiled in water.
n20
D 1.4780 – 1.4920; acid value: 8 – 14; ester Labdanum absolute is produced by extrac-
value: 120 – 220. tion of the gum with alcohol (e.g., methanol or
One ton of jasmin blossoms yields ca. 2.5 – ethanol). So-called colorless absolutes are ob-
3 kg of concrete when it is extracted two or three tained from absolutes by extraction with, for ex-
times with hexane or benzene. Extraction of the ample, hexane.
concrete with ethanol gives a ca. 60 % yield of Steam distillation of the gum yields lab-
the absolute. danum oil which is a golden yellow, viscous liq-
The main volatile component of jasmin uid that quickly turns dark brown on standing:
oil is benzyl acetate. However, minor compo- d 25 20
25 0.905 – 0.993; nD 1.4920 – 1.5070; [α]D
nents such as indole [120-72-9], cis-jasmone ◦  ◦
+ 0 15 to + 7 , often difficult to determine due
[488-10-8], and methyl jasmonate [1211-29-6] to its dark color; solubility: 1 vol in 0.5 vol of
contribute strongly to the typical jasmin fra- 90 % ethanol, solutions frequently opalescent to
grance. turbid, paraffins may separate upon further di-
lution; acid value: 18 – 86; ester value: 31 – 86
[271].
Other odoriferous materials are derived from
the leaves and young twigs of Cistus ladaniferus.
Cistus oil is obtained by steam distillation; sol-
cis-Jasmone Methyl jasmonate vent extraction yields cistus concrete. Cistus oil,
in contrast to labdanum oil, consists mainly of
monoterpene hydrocarbons.
 Flavors and Fragrances 103

Cistus and labdanum products come from acetate (25 – 45), 1-terpinen-4-ol (2 – 6), and
Mediterranean countries, mainly Spain, where lavandulyl acetate (> 2).
the Cistus shrub grows abundantly. They are Cloned varieties of lavender (e.g., Maillette
used widely in perfumery, giving perfume com- and Matherone) yield more oil per hectare
positions a warm, balsamic tonality with a touch and can be grown at lower altitudes; however,
of ambergris. The resinoids and absolutes are ex- they produce a poorer quality oil. Bulgarian
cellent natural fixatives. lavender oil is similar in composition to that
obtained from French population lavender,
Laurel leaf oil is obtained by steam distil- but is of poorer quality: about 50 to 70 t are
lation of leaves from Laurus nobilis L. (Lau- produced per year.
raceae), an evergreen tree cultivated primarily Lavender oils of a special quality are also
in Mediterranean countries. The oil is a light produced in several other areas throughout
yellow to yellow liquid with an aromatic, spicy the world (e.g., Tasmania).
odor. 2) Spanish spike lavender oil is produced by
d 25 20
25 0.905 – 0.929; nD 1.4650 – 1.4700; [α]D steam distillation of flowering tops of spike,
◦ ◦
− 19 to − 10 ; solubility: 1 vol in at least 1 vol Lavandula latifolia Medik. (Lamiaceae). It
of 80 % ethanol; acid value: max. 3; saponifica- is an almost colorless to light orange liquid
tion value: 15 – 45; saponification value (after with a characteristic, rough odor slightly like
acetylation): 36 – 85 [272]. cineole and camphor.
The main component of the oil is 1,8-cineole d 20
20 0.894 – 0.907; nD
20
1.4610 – 1.4680;
20 ◦ ◦
(30 – 70 %); other important components are [α] D − 7 to + 2 ; solubility: 1 vol in
linalool (ca. 10 %) and eugenol. 3 vol of 70 % ethanol; solutions may become
Laurel leaf oil is used extensively in the food opalescent on dilution; acid value: max. 1.0;
industry, e.g., for seasoning meat products and ester value: 3 – 14; ester value (after acetyla-
soups. tion): 130 – 200 [274].
The main components of Spanish spike
Lavandula products comprise the follow- lavender oil are linalool (34 – 50 %), cineole
ing oils and extracts: (16 – 39 %), and camphor (8 – 16 %).
Spike plants grow wild in the entire Mediter-
1) Lavender oil is produced by steam distilla- ranean area and prefer warmer, lower-lying
tion of freshly cut, flowering tops of Lavan- regions than lavender and lavandin. Oil is
dula angustifolia Mill. (Lamiaceae). It is a primarily produced from plants cultivated in
pale yellow liquid with a fresh, sweet, floral, Spain. At present, annual worldwide produc-
herbaceous odor on a woody balsamic base. tion is ca. 150 – 200 t.
The following physical constants are valid 3) Lavandin oil abrialis is obtained by steam
for spontaneous lavender from France. distillation of freshly cut flowering tops of
d 20 20
20 0.880 – 0.890; nD 1.458 – 1.464; [α] D
20
lavandin, which is a hybrid of lavender and
◦ ◦
− 11.5 to − 7 ; solubility: 1 vol in 2 vol spike (Lavandula angustifolia Mill. x Lavan-
of 75 % ethanol at 20 ◦ C; acid value: max. dula latifolia Medik.). It is a pale yellow liq-
1.0; ester value: 102.5 – 165, corresponding uid with a lavender-like odor and a slightly
to an ester content of 35.8 – 58 % (calculated camphoraceous note.
as linalyl acetate) [273]. Data for lavandin oil abrialis:d 20 20 0.887 –
True French lavender grows in the Haute 0.897; n20D 1.4560 – 1.4660; [α] 20
D −5
◦
to
◦
Provence at an altitude of 600 – 1500 m. − 2 ; solubility: 1 vol in 4 vol of 70 % etha-
The plants are grown from seeds of the nol at 20 ◦ C; acid value: max. 1.0; ester value:
wild lavender (“spontaneous” or “popula- 77 – 108, corresponding to an ester content
tion” lavender). Lavender oil is produced of 27 – 38 % (calculated as linalyl acetate)
in a yield of 10 – 25 kg/ha; total produc- [276].
tion is ca. 100 t/a. It has the following typ- Data for lavandin oil grosso (a specific
ical composition (%): cis-β-ocimene (4 – clone of lavandin, cultivated in the South
10), trans-β-ocimene (1.5 – 6), cineole (< 1), of France: d 20 20
20 0.891 – 0.899; nD 1.4580 –
camphor (< 0.5), linalool (25 – 38), linalyl 1.4620; [α]20 D − 7 ◦
to − 3.5 ◦
; solubility:
104 Flavors and Fragrances

1 vol in 3 vol of 70 % ethanol at 20 ◦ C; acid Lie de vin oil ( green cognac oil or wine lees
value: max. 1; ester value: 100 – 137, cor- oil) is obtained by steam distillation of the yeast
responding to an ester content of 35 – 48 % and other sediments (lees) formed in wine. It is a
(calculated as linalyl acetate) [262]. green to bluish-green liquid with a characteristic
Lavandin plants are sterile and can be prop- cognac aroma.
agated only by using cuttings. The oils from d 25 20
25 0.864 – 0.870; nD 1.4275 – 1.4295; [α]D
◦ ◦
the most important varieties, abrialis and − 1 to + 2 ; acid value: 32 – 70; ester value:
grosso, contain linalool and linalyl acetate as 200 – 245; solubility: 1 vol in at least 2 vol of
major constituents as well as 6 – 11 % cine- 80 % ethanol [277].
ole and 7 – 11 % camphor for abrialis, and 4 – Lie de vin oil consists mainly of the ethyl
7 % cineole and 6 – 8 % camphor for grosso. and isoamyl esters of fatty acids, formed during
A third variety is called super because its oil fermentation. It is used mostly in aroma compo-
contains a high concentration of linalyl ac- sitions; only very small amounts are employed
etate, and, thus, resembles lavender oil most in perfume compositions.
closely.
Although lavender oil is more valuable than Lime oil, see Citrus Oils, page 94.
lavandin oil as a fragrance raw material, la-
vandin plants are more commonly cultivated Litsea cubeba oil is produced by steam dis-
because they give a higher yield of oil (ca. tillation of the fruits of Litsea cubeba C. H. Per-
50 – 100 kg/ha) and are hardier than lavender soon (Lauraceae) growing in East Asia. It is a
plants. pale yellow to dark yellow liquid with a fresh
Cultivation in southern France is no longer odor, reminiscent of citral.
restricted to the traditional lavender regions, d 20 20
20 0.880 – 0.892; nD 1.4800 – 1.4870; [α]D
20
but also now includes the Languedoc. Former + 3 ◦ to + 12 ◦ ; carbonyl content (calculated as
Yugoslavia is another lavandin-producing citral): min. 74 %; solubility: 1 vol in 3 vol of
country. Worldwide annual production is up 70 % ethanol at 20 ◦ C [278].
to 1100 t. The oil is used mainly for the production of
All three oils are used primarily in soap per- citral; smaller quantities are employed for per-
fumes; considerable quantities are also em- fuming household products. The main producer
ployed in eaux de cologne and in bath prod- is China. The worldwide annual production is
ucts. about 1000 t.
4) Lavender and lavandin extracts are also
commercially important and are produced Lovage oils are obtained by steam distilla-
in southern France by solvent extraction of tion of either the leaves (leaf oil) or the fresh
flowering lavender and lavandin herbs. Pro- roots (root oil) of the perennial plant Levisticum
duction of lavandin concrete is higher than officinale Koch (Apiaceae). Both oils are yellow-
that of lavender. Extraction of the pastelike greenish-brown to dark brown liquids with a
concretes with ethanol, followed by evapo- strong, characteristic, aromatic odor reminiscent
ration, yields absolutes. These extracts dif- of celery and angelica.
fer from the essential oils in being more sol- d 25 20
25 0.960 – 0.985 (leaf oil); d 20 1.010 – 1.090
uble and in having a dark green color and (root oil); n20
D 1.5350 – 1.5580; [α]20 ◦
D − 1 to
a longer-lasting odor with a haylike, spicy ◦
+ 5 ; acid value: 2 – 16; ester value: 170 – 260;
note. They are also used in eaux de cologne solubility: 1 vol in 1.5 vol of 85 % ethanol at
and fine fragrances, sometimes after decol- 20 ◦ C [279].
oration (removal of chlorophyll with acti- The main constituent of the leaf oil is α-
vated charcoal). terpinyl acetate, while the main constituent and
odor-determining component of the root oil is
Lemon oil, see Citrus Oils, page 94. ligustilide [4431-01-0]. A few percent ligustilide
are also present in the leaf oil.
Lemongrass oil, see Cymbopogon Oils,
page 98.
 Flavors and Fragrances 105

Mentha citrata oil, see Mint Oils.

Mimosa absolute is obtained from the blos-

soms of the mimosa tree Acacia dealbata Link
Ligustilide (Mimosaceae), which grows in the forests of
southern France and in Morocco.
The oils are very expensive. They are mainly The absolute is a yellowish brown liquid with
used in the alcoholic beverage industry and for a slightly green, flowery odor and extremely
flavoring of tobacco; small amounts are also high tenacity.
used in perfumery. Annual production in France (Grasse) is ca.
3 – 6 t [282]. Mimosa absolute is used mainly in
Mace oil, see Nutmeg Oil, page 109. fine fragrances as a flowery fixative.

Mandarin oil, see Citrus Oils, page 94. Mint oils are listed in order of the quantities
produced.
Marjoram oil (sweet marjoram oil) is ob-
tained by steam distillation of the herb 1) Cornmint oil is produced by steam distilla-
Origanum majorana L. (Majorana hortensis tion of the flowering herb Mentha arvensis
Moench, Lamiaceae). The plants are cultivated L. var. piperascens Malinv. and var. glabrata
in France, Hungary, Egypt, and Tunisia. The oil Holmes (Lamiaceae). The crude oil, con-
is a yellow to greenish-yellow liquid with a char- taining ca. 70 % (−)-menthol, is then par-
acteristic earthy-spicy odor. tially dementholized by freezing and cen-
d 25 20
25 0.890 – 0.906; nD 1.4700 – 1.4750; [α]D
trifuging. The dementholized oil is an almost
+ 14 ◦ to + 24 ◦ ; acid value: max. 2.5; saponifi- colorless to amber-yellow liquid with a char-
cation value: 23 – 40; saponification value (after acteristic minty odor; typical specifications
acetylation): 68 – 86; solubility: 1 vol in 2 vol of for oils of Chinese and Indian origin are as
80 % ethanol [280]. follows:
The main constituent of the oil is 1-terpinen- d 20
20 0.890 – 0.910; nD
20
1.4570 – 1.4650;
20 ◦ ◦
4-ol (> 20 %), which with (+)-cis-sabinene hy- [α]D − 24 to − 13 ; ester content (calcu-
drate [15537-55-0] (3 – 18 %) is responsible for lated as menthyl acetate): 3 – 9 %; total al-
the characteristic flavor and fragrance of marjo- cohol content (calculated as menthol): 40 –
ram oil. 60 %; ketone content (calculated as men-
thone): 25 – 45 %; solubility: 1 vol in 4 vol
of 70 % ethanol [283].
Dementholized oil still contains ca. 45 %
(−)-menthol; (−)-menthone and (−)-
menthyl acetate are other major components.
Dementholized Mentha arvensis oil was for-
(+)-cis-Sabinene hydrate merly produced primarily in Brazil. Cur-
rently, cornmint oil is produced mainly in
Sweet marjoram oil is used mainly for flavor- China; smaller amounts are produced in In-
ing foods, but also in smaller amounts in per- dia and Paraguay. The world production of
fumery for spicy shadings in men’s fragrances. the oil is estimated to be 17 000 to 18 000 t/a.
Spanish marjoram oil is obtained by steam Dementholized cornmint oil tastes more bit-
distillation of the flowering tops of Thymus mas- ter and stringent than peppermint oil. Thus,
tichina L. (Lamiaceae), a wild plant growing in the former is used as a cheaper substitute
Spain. The oil is a slightly yellow liquid with a for the latter and for the production of (−)-
fresh camphoraceous, spicy odor. menthol (see page 30).
d 20 20
20 0.890 – 0.920; nD 1.460 – 1.470; [α] D
20
2) Peppermint oil is produced by steam distilla-
◦
− 4 to + 6 ; 1,8-cineole content: min. 30 %, tion of the aerial plant Mentha x piperita L.
max. 68 %; solubility: 1 vol in 3 vol of 70 % eth- var. piperita. It is an almost colorless to pale
anol [281].
106 Flavors and Fragrances

greenish-yellow liquid with a characteristic The compositions of Scotch and native

peppermint odor. spearmint oils differ as shown in Table 4
d 20
20 0.898 – 0.918; nD
20
1.4590 – 1.4650; [286]. The main producer of spearmint oil
20 ◦ ◦
[α] D − 30 to − 14 ; solubility: 1 vol in is the United States, primarily the state of
5 vol of 70 % ethanol at 20 ◦ C; ester value: Washington. Smaller amounts are also pro-
12 – 30; ester value (after acetylation): 135 – duced in some Midwest states. Total annual
200; carbonyl value: 54 – 115 [284]. production is ca. 1750 t, 55 % being of the
As in cornmint oil, the main component native type and 45 % of the Scotch type.
of peppermint oil is (−)-menthol; it also
contains (−)-menthone (ca. 20 %) and (−)- Table 4. Characteristic components of Scotch and native spearmint
menthyl acetate (up to 8 %). However, pep- oils
permint oil, unlike cornmint oil, has a high Compound Content of compound in
content of (+)-menthofuran [17957-94-7] spearmint oil, %
(1 – 8 %, according to GLC). Scotch Native

Limonene 15 9
3-Octanol 2 1
Menthone 1 < 0.1
Dihydrocarvone 1 2.5
Sabinene hydrate 0.1 1.5
Dihydrocarvyl acetate < 0.1 0.6
cis-Carvyl acetate 0.1 0.6
(+)-Menthofuran

The leading producer of peppermint oil is By far the most spearmint oil is used for fla-
the United States, where annual production voring toothpaste and chewing gum. Smaller
from the variety M. piperita L. var. vulgaris quantities are used in other oral hygiene prod-
Sole (Black Mitcham) is ca. 3600 t. Cultiva- ucts and in pharmaceutical preparations.
tion areas are located in the Midwest states, 4) Mentha citrata oil is distilled from the herb
Idaho, Oregon, and Washington. The oils Mentha citrata Ehrh. It has a lavender-like
differ in quality and are named according odor and contains linalool and linalyl acetate
to their geographic origin (e.g., Midwest, as major components (together ca. 70 %). Re-
Idaho, Madras, Willamette, Yakima). Pro- cently, hybrids of the plant have been devel-
duction of European oil has decreased sig- oped in the United States and other countries
nificantly, despite its high quality. Pepper- that yield oils with a total linalool content of
mint oil is used mainly for flavoring tooth- over 80 % [287]. Currently, the main culti-
paste, other oral hygiene products, and chew- vation area is Eastern Asia. Mentha citrata
ing gum. Smaller quantities are used for fla- oils are used mainly for perfuming soap and
voring confectioneries. Due to its high price, cosmetics.
peppermint oil is not used for the production 5) Pennyroyal oil is obtained by steam distilla-
of menthol. tion of the flowering tops of Mentha pulegium
3) Spearmint oil is obtained by steam distilla- L. It is an almost colorless to amber-yellow
tion of the flowering tops of Mentha spicata liquid with a herbaceous, minty odor.
L. (native spearmint) and Mentha x cardiaca d 20
20 0.930 – 0.944; nD
20
1.4800 – 1.4900;
Ger. (Scotch spearmint). It is an almost col- [α] 20
D + 15 ◦
to + 24 ◦
; solubility: 1 vol in
orless to yellow-green liquid with a fresh, 3 vol of 70 % ethanol; content of carbon-
caraway-minty odor. yl compounds (calculated as pulegone) min.
d 20 20 20 80 % [288].
20 0.920 – 0.937; nD 1.485 – 1.491; [α]D
◦ ◦
− 60 to − 45 ; solubility: 1 vol in 1 vol of The main component of pennyroyal oil is (+)-
80 % ethanol at 20 ◦ C; carbonyl value: min. pulegone [89-82-7] (ca. 80 %). About 50 t of
200, corresponding to a carvone content of the oil are produced per year, mainly in south-
55 % [285]. ern Spain and Tunisia.
 Flavors and Fragrances 107

Citrus aurantium L. subsp. amara var. pumilia,

(Rutaceae), which is grown in France, Italy, and
North Africa. Neroli oil is produced by steam
distillation (about 4 t/a) and is a pale yellow to
amber-colored liquid, with a slight blue fluo-
(+)-Pulegone rescence and a characteristic sweet, spicy-bitter
odor of orange blossom.
An oil of similar composition, also called d 20 20
20 0.864 – 0.876; nD 1.460 – 1.474; [α] D
20
pennyroyal oil, is obtained in North America ◦ ◦
+ 2 to + 11 ; solubility: 1 vol in 3.5 vol of 85 %
from Hedeoma pulegioides L. Pennyroyal oil ethanol at 20 ◦ C; acid value: max. 2.0; ester
has lost its significance as a starting material value: 26 – 60 [292].
for the production of (−)-menthol. However, After separation of neroli oil, the aqueous
it is still used in perfume compositions for layer of the steam distillate, known as orange
soap and oral hygiene products. blossom water, is extracted with suitable sol-
vents (e.g., petroleum ether). Evaporation gives
Musk, see Animal Secretions, page 87. orange flower water absolute (absolue de l’eau
de fleurs d’oranger), which is a dark brown-red
Myrrh oil and myrrh resinoids are pro- liquid. It contains less terpene hydrocarbons and
duced from the air-dried gum of Commiphora correspondingly more polar compounds than
myrrha (Nees) Engl. var. molmol Engl., C. neroli oil.
abyssinica (Berg) Engl. and C. schimperi (Berg) Orange flower absolute is obtained from the
Engl. (Burseraceae), shrubs that grow in North- blossoms by solvent extraction via the concrete.
east Africa and Arabia. It is a dark brown liquid with a warm, spicy-bitter
Myrrh resinoids are obtained in 20 – 45 % odor.
yield by extracting the gum with suitable sol- The main volatile constituent of all three
vents (e.g., benzene, hexane). They are waxlike, products is linalool. Their typical flavor is cre-
brown-yellow to red-brown masses with a bal- ated by a number of nitrogen-containing trace
samic odor and an aromatic bitter taste. constituents, such as indole and derivatives of
Acid value: 20 – 35; ester value: 165 – 200; anthranilic acid.
carbonyl value: 20 – 75 [289]. Neroli oil and the related products are some
Myrrh oil is obtained from the gum by steam of the most expensive natural raw materials and
distillation; it is a light brown or green liquid are produced only in small quantities (a few tons
with the characteristic odor of the gum. per year). They are used in fine fragrances; neroli
d 25 20
25 0.995 – 1.014; nD 1.5190 – 1.5275; [α]D oil, for example, is one of the classical compo-
◦ ◦
− 83 to − 60 ; acid value: 2 – 13; saponifica- nents of eaux de cologne.
tion value: 9 – 35; solubility: 1 vol in 7 – 10 vol of
90 % ethanol; solutions are occasionally opales- Nutmeg (mace) oil is obtained by steam dis-
cent or turbid [290]. tillation of the dried and crushed nuts and/or the
Typical aroma-determining compounds of coverings (mace) of nutmeg, which are the fruits
the myrrh plant are furanosesquiterpenoids such of Myristica fragrans Houtt. (Myristicaceae).
as lindestrene [2221-88-7] [291]. The tree grows in Indonesia and in the West In-
dies and becomes 15 – 20 m high. Nutmeg oil is
a colorless to pale yellow liquid with a pleas-
ant spicy odor. Its physical constants and odor
vary with the place of origin. Specifications of
Indonesian and (in parentheses) West Indian nut-
Lindestrene meg oil are as follows:
d 20
20 0.885 – 0.907 (0.862 – 0.882); n20 D
1.4750 – 1.4850 (1.4720 – 1.4760); [α]20 D +6
◦
Neroli oil and orange flower absolute are ◦ ◦ ◦
to + 18 (+ 25 to + 40 ); solubility (both oils):
obtained from the blossoms of the bitter orange 1 vol in 5 vol of 90 % ethanol at 20 ◦ C (solutions
tree, Citrus aurantium L. subsp. aurantium, syn.
108 Flavors and Fragrances

sometimes opalescent), for freshly distilled oils, Large quantities of oakmoss (mousse de
1 vol in 3 – 4 vol [293]. chêne) and tree moss (mousse d’arbre) are col-
Indonesian oils contain a higher percentage lected annually in former Yugoslavia, France,
of higher boiling components than do West In- and Morocco [294]. In 1997 1900 t of Pseude-
dian oils (produced mainly in Grenada). vernia furfuracea and 700 t of Evernia prunastri
The oils contain ca. 90 % terpene hy- were processed, mainly in Grasse [295].
drocarbons, mainly sabinene and α- and β- The extracts and absolutes are used in per-
pinene. Major oxygen-containing constituents fumery for nuances and as a fixative to give com-
are 1-terpinen-4-ol and phenol ether derivatives positions a dry, sweet base note, e.g, in fougère
(mainly myristicin). and chypre perfumes. (IFRA recommendation).
Nutmeg oil is used mainly in food flavorings
and to a lesser extent in perfumery. Worldwide Olibanum oil and olibanum resinoid are
annual production is 400 to 450 t, more than obtained from frankincense, which is a gum
120 t/a is produced in Indonesia alone. resin collected from the bark of the tree
Boswellia carteri Birdw. (syn. B. sacra Flueck.)
Oakmoss absolute and tree moss absolute or B. frereana Birdw. (Burseraceae) growing in
are obtained from tree lichens. Oakmoss abso- Yemen and Somalia. The resinoid is produced by
lute is derived from Evernia prunastri (L.) Arch. solvent extraction, and steam distillation gives
(Usneaceae), a lichen growing on oak trees. The the oil, which is a pale yellow, slightly viscous
lichen is first extracted with nonpolar solvents to liquid with a balsamic odor and a faint lemon
give a concrete. The waxes are then removed by note.
precipitation with ethanol, leaving an absolute. d 25 20
25 0.862 – 0.889; nD 1.4650 – 1.4820; [α]D
◦ ◦
The concretes are green to brown waxy − 15 to + 35 ; solubility: 1 vol in 6 vol of 90 %
pastes; the absolutes are more or less viscous ethanol, solutions occasionally opalescent; acid
liquids with an earthy, mossy, woody odor and value: max. 4.0; ester value: 4 – 40 [296].
a slight phenolic, leather note. Various qualities are commercially available.
Resorcinol derivatives, e.g., orci- Their compositions may vary considerably be-
nol [504-15-4], β-orcinol [488-87-9], cause they are prepared from the resins of dif-
their monomethyl ethers, and methyl 3- ferent Boswellia species [297].
methylorsellinate [4707-47-5] are mainly re- Olibanum oil and resinoid are used in orien-
sponsible for the characteristic earthy-moss-like tal type perfumes for their odor and their good
odor of the oakmoss products. fixative properties.
Tree moss concretes and absolutes are pre-
pared from Pseudevernia furfuracea, a lichen Opopanax oil and opopanax resinoid (also:
growing on conifer bark. Their odors are dif- Opoponax) are obtained from the resin of Com-
ferent from those of the corresponding oakmoss miphora erythraea Engl. var. glabrescens Engl.,
products. a tree growing in Somalia (Burseraceae). The
resinoid is prepared by solvent extraction, and
steam distillation of the resin gives the essential
oil, which is a yellow to greenish-yellow liquid
with a warm, sweet, balsamic odor.
d 25 20
25 0.865 – 0.932; nD 1.488 – 1.504; [α]D
◦ ◦
− 32 to − 9 ; acid value: max. 4; saponifica-
Orcinol β-Orcinol tion value: 4 – 20; solubility: 1 vol in 10 vol of
90 % ethanol; solutions are occasionally turbid
[298].
Opopanax oil and resinoid are used in per-
fume compositions with oriental characteristics.
(IFRA recommendation).
Methyl 3-methylorsellinate
Orange flower absolute, see Neroli Oil,
page 109.
 Flavors and Fragrances 109

Orange oils, see Citrus Oils, page 94. The main constituents of the oil are (−)-
cis-γ-irone [89888-04-0] and (−)-cis-α-irone
Origanum oils are produced from several [89888-03-9], which are responsible for its odor
species of the flowering herb Origanum (Lami- [302].
aceae). Spanish origanum oil is derived from
Coridothymus capitatus Rchb. and is often
called white thyme oil. The oils differ mainly
in their content of carvacrol and thymol, which
are major constituents. Oil with a high carvacrol (−)-cis-γ-Irone (−)-cis-α-Irone
content [499-75-2] (for formula, see page 116)
is a yellowish-red to dark brown liquid with a The oil, respectively the butter, is very ex-
spicy, herbaceous odor, reminiscent of thyme. pensive and is used in perfumery and in flavor
The color quickly turns to black when in contact compositions.
with iron.
d 25 20
25 0.935 – 0.960; nD 1.5020 – 1.5080; [α]D Palmarosa oil, see Cymbopogon Oils, page
− 2 ◦ to + 3 ◦ ; phenol content: 60 – 75 %; solu- 98.
bility: 1 vol in 2 vol of 70 % ethanol; solutions
may become turbid when further diluted [299]. Parsley oils are produced from the plant Pet-
According to ISO the Spanish origanum oil roselinum crispum (Mill.) Nyman. ex A.W. Hill
is derived from Thymbra capitata (L.) Cav. It (P. sativum Hoffm.), (Apiaceae):
is a yellowish to dark brown, almost black oil
with an aromatic, phenolic, and spicy odor; d 20 20 1) Parsley leaf oil is produced by steam distilla-
0.930 – 0.955; n20 20
D 1.5000 – 1.5130; [α]D − 5
◦ tion of the aerial parts of the plant, including
◦ the immature seeds. It is a yellow to light-
to + 2 ; solubility: 1 vol in 4 vol of 70 % ethanol
at 20 ◦ C; carvacrol content by GLC: 60 to 75 % brown liquid with the typical odor of the herb.
[300]. (Both botanical names – Coridothymus d 25 20
25 0.908 – 0.940; nD 1.5030 – 1.5300; [α]D
◦ ◦
and Thymbra – are not mentioned in the Zander − 9 to + 1 ; acid value: max. 2; soluble in
dictionary [196].) 95 % ethanol; solutions may be opalescent
Origanum oils are used in perfume composi- [303].
tions and in seasoning mixtures. The oil consists mainly of monoterpene hy-
drocarbons. Its main constituent is 1,3,8-
Orris root oil is obtained by steam distilla- menthatriene [18368-95-1], which – to-
tion of the rhizomes of the two species of iris, Iris gether with two pyrazines and (Z)-dec-6-
pallida Lam. or Iris germancia L. (Iridaceae). enal – is important for the aroma of parsley
Prior to distillation the rhizomes are stored for leaves [304].
about two years in order to develop the aroma 2) Parsley seed oil is obtained by steam distil-
and are then ground. The steam distillate is a lation of ripe fruits of parsley. It is an almost
light yellow to brown-yellow solid mass with a colorless to amber-yellow liquid whose dry
violet-like odor. The solid liquefies to a yellow odor is characteristic of the crushed fruit, but
to yellow-brown liquid at 38 – 50 ◦ C. different from that of the green parts of the
Acid value: 175 – 235, corresponding to an plant.
acid content of 71 – 95 % (calculated as myristic d 20
20 1.043 – 1.083; nD
20
1.5130 – 1.5220;
20 ◦ ◦
acid); ester value: 4 – 35; ketone content (calcu- [α]D − 10 to − 4 ; acid value: max. 6; es-
lated as irone): 9 – 20 %; soluble with ethanol in ter value: min. 1, max. 10; solubility: 1 vol
all proportions at 50 ◦ C [301]. in 6 vol of 85 % ethanol, solutions are some-
Because of its high content of myristic and times slightly turbid [306].
other fatty acids, the steam distillate is a waxy Characteristic components of parsley seed oil
mass that resembles a concrete and is sold un- are myristicin [607-91-0], apiol [523-80-8],
der this name or as Beurre d’Iris ( Orris butter). and 2,3,4,5-tetramethoxyallylbenzene
In addition, a neutral product, obtained after re- [15361-99-6] [305].
moval of the acids with alkali, is marketed under
the name orris oil absolute or as orris oil 10-fold.
110 Flavors and Fragrances

oil is an almost colorless to bluish-green liquid

with a characteristic odor, reminiscent of pepper,
but without the pungency of the spice.
d 20 20
20 0.870 – 0.890; nD 1.480 – 1.492; [α]D
20
◦ ◦
Myristicin Apiol
− 16 to + 4 ; solubility: 1 vol in 3 vol of 95 %
ethanol; ester value: max. 11 [309].
The oil contains mainly monoterpene hydro-
carbons (ca. 80 %), its main constituent being
sabinene [3387-41-5] (20 – 25 %).
2,3,4,5-Tetramethoxyallylbenzene

Parsley oils are used in the food industry in

seasonings, for example, for meat and sauces.

Patchouli oil is produced by steam distilla-

tion of the dried leaves of Pogostemon cablin Sabinene
(Blanco) Benth. (Lamiaceae). It is a yellow to
reddish-brown, more or less viscous liquid with Pepper oleoresin is produced by solvent ex-
a characteristic, slightly camphoraceous, woody traction and, unlike the oil, contains the principal
balsamic odor. pungent compound, piperine [94-62-2], along
d 20 20
20 0.952 – 0.975; nD 1.5050 – 1.5150; [α]D
20 with some essential oil.
◦ ◦ ◦
− 60 to − 40 (in exceptional cases to − 32 );
solubility: 1 vol in 10 vol of 90 % ethanol at
20 ◦ C; acid value: max. 4.0; ester value: max.
10 [307].
The patchouli shrub is cultivated primarily in
Piperine
Indonesia. It grows to 1 m, but during harvest-
ing is cut back to 10 – 15 cm. The oil yield from Pepper products are used for flavoring foods;
preferably sun-dried leaves is ca. 2 %. pepper oil is also employed to a small extent in
Although the sesquiterpene alcohol (−)- perfume compositions.
patchoulol [5986-55-0] is the main component
of patchouli oil (27 – 35 %), this compound con- Peppermint oil, see Mint Oils, page 107.
tributes less to the characteristic odor of the oil
than norpatchoulenol [41429-52-1] present only
Peru balsam oil is obtained by distillation
at a concentration of 0.2 – 1 % [308].
of the balsam of Myroxylon pereirae (Royle)
Klotzsch (Fabaceae). It is a yellow to pale brown,
slightly viscous liquid, which may form crystals
with a rather sweet, balsamic odor.
d 25 20
25 1.095 – 1.110; nD 1.5670 – 1.5790; [α]D
◦ ◦
Patchoulol Norpatchoulenol
− 1 to + 2 ; acid value: 30 – 60; ester value:
200 – 225; solubility: 1 vol in at least 0.5 vol of
Worldwide production lies between 900 and 90 % ethanol [310].
1000 t/a. Patchouli oil is very tenacious and is Peru balsam is produced almost exclusively
used in perfumery for oriental and fougère notes. in El Salvador. The oil yield from the balsam is
ca. 50 %. Major components are benzyl benzoate
Pennyroyal oil, see Mint Oils, page 107. and benzyl cinnamate. Nerolidol and vanillin
contribute to the odor.
Pepper oil and pepper oleoresin are ob- The oil is used for its excellent fixative prop-
tained from the black pepper Piper nigrum L. erties in perfumes for soap and cosmetics. Use
(Piperaceae). Pepper oil is produced by steam of Peru balsam itself is now banned because it
distillation of whole or broken unripe fruits. The is allergenic. (IFRA recommendation)
 Flavors and Fragrances 111

Petitgrain oils are obtained by steam distil- (80 – 90 %). Annual production of leaf oil is ca.
lation of the leaves of citrus trees (Rutaceae 50 t, which exceeds that of the berry oil.
family). The oils derived from the bitter orange Pimento oils, like the spice itself, are used
tree are the most important. Other petitgrain oils mainly in the food industry, as well as in per-
(mandarinier, citronnier, and bergamotier) are fume compositions for creating spicy, clovelike
less important. Petitgrain oil mandarinier is a notes.
source of natural methyl N-methylanthranilate,
which is present at a concentration of more than Pinaceae needle oils from Pinaceae species
50 %. Petitgrain oils are essential constituents of contain (−)-bornyl acetate as their main odor-
eaux de cologne. iferous component. Other main constituents are
Petitgrain oil Paraguay is obtained from an monoterpene hydrocarbons such as α- and β-
acclimatized variety of the bitter orange tree, pinene, limonene, 3-carene, and α- and β-
Citrus aurantium L. subsp. aurantium, which is phellandrene. The oils are used in perfumes for
grown in Paraguay. Leaves and twigs are steam soap, bath products, and air fresheners and in
distilled. Petitgrain oil Paraguay is a colorless to pharmaceutical preparations.
pale yellow liquid with a characteristic, strong,
pleasant odor, reminiscent of linalool and linalyl 1) European silver fir oil is produced in cen-
acetate. tral Europe by steam distillation of needle-
d 20 20
20 0.882 – 0.893; nD 1.455 – 1.463; [α]D
20 bearing twigs of Abies alba Mill. It is a col-
◦ ◦
− 6 to − 1 ; solubility: 1 vol in 4 vol of 70 % orless to pale yellow liquid with a pleasant
ethanol at 20 ◦ C; acid value: max. 1; ester value: odor of freshly cut fir needles.
127 – 184, corresponding to an ester content of d 25 20
25 0.867 – 0.878; nD 1.4700 – 1.4750; [α]D
◦ ◦
45 – 65 % (calculated as linalyl acetate) [311]. − 67 to − 34 ; solubility: 1 vol in 7 vol
Annual production is ca. 250 – 280 t. of 90 % ethanol; ester content (calculated as
Petitgrain oil bigarade is obtained by steam bornyl acetate): 4 – 10 % [314].
distillation of the leaves, twigs, and small green Silver fir cone oil (templin oil) obtained from
fruits of the bitter orange tree Citrus aurantium the cones of Abies alba Mill. has similar
L. subsp. aurantium, grown in France, Italy, and properties.
North Africa. It is a pale yellow to amber yellow 2) Siberian fir needle oil is obtained by steam
liquid, with a slight blue fluorescence and with distillation of needles and twigs of Abies
a characteristic ethereal and pleasant odor. sibirica Ledeb., the Siberian silver fir. It is an
d 20 20
20 0.886 – 0.898; nD 1.4560 – 1.4720; [α]D
20 almost colorless or pale yellow liquid with a
− 6 ◦ to + 1 ◦ ; solubility: 1 vol in 5 vol of 70 % characteristic fir odor.
ethanol at 20 ◦ C; acid value: max. 2; ester value: d 25 0.898 – 0.912; n20
D 1.4685 – 1.4730; [α]D
140 – 217, corresponding to an ester content of − 45 ◦ to − 33 ◦ ; solubility: 1 vol in 1 vol of
50 – 77 % (calculated as linalyl acetate) [312]. 90 % ethanol, solutions may become hazy
Annual production is ca. 3 to 5 t. when further diluted; ester content (calcu-
lated as bornyl acetate): 32 – 44 % [315].
Pimento oils ( allspice oil) are derived from 3) Canadian fir needle oil ( balsam fir oil) is
pimento fruits and leaves. Pimento berry oil is produced in Canada and in several northern
obtained by steam distillation of the dried, fully states of the United States from needles and
grown, unripe, berry-like fruits of the pimento twigs of Abies balsamea (L.) Mill. It is an
shrub, Pimenta dioica (L.) Merrill. (Myrtaceae), almost colorless to pale yellow liquid with a
growing in Jamaica. It is a pale yellow to brown pleasant balsamic odor.
liquid with a spicy odor, reminiscent of eugenol. d 25 20
25 0.872 – 0.878; nD 1.4730 – 1.4760; [α]D
◦ ◦
d 20 20
20 1.027 – 1.048; nD 1.5250 – 1.5400; [α]D
20 − 24 to − 19 ; solubility: 1 vol in 4 vol
◦ ◦
− 5 to 0 ; solubility: 1 vol in 2 vol of 70 % eth- of 90 % ethanol (turbidity may occur), es-
anol at 20 ◦ C; phenol content: min. 65 % [313]. ter content (calculated as bornyl acetate): 8 –
The major components of pimento berry 16 % [316].
oil are eugenol (up to 75 %), 1,8-cineole, and 4) Pine needle oil is produced primarily in Aus-
caryophyllene. Distillation of the leaves gives tria (Tyrol), former Yugoslavia, and the CIS
an oil that has an even higher content of eugenol by steam distillation of the needles of the
112 Flavors and Fragrances

Norwegian or Scotch pine, Pinus sylvestris d 20

20 0.848 – 0.880; nD
25
1.4520 – 1.4700;
20 ◦ ◦
L. It is a colorless or yellowish liquid with [α]D − 5 to − 1.8 ; fp between 16 and
an aromatic, turpentine-like odor. 23.5 ◦ C; ester value: min. 7, max. 24. Due
d 25 20
25 0.857 – 0.885; nD 1.4730 – 1.4785; [α]D to the presence of paraffin hydrocarbons
◦ ◦
− 4 to + 10 ; solubility: 1 vol in 6 vol of (stearoptenes) the determination of the phys-
90 % ethanol, sometimes slightly opalescent; ical constants at 20 ◦ C can be difficult or
ester content (calculated as bornyl acetate): impossible because of a low freezing-point
1.5 – 5 % [317]. [319].
5) Dwarf pine needle oil is obtained in Aus- The major constituents of rose oil are (−)-
tria (Tyrol) and other mountainous areas of citronellol, geraniol, and nerol. In contrast to
central and southeast Europe by steam distil- the absolute (see below), the oil contains only
lation of fresh needles and twig tips of Pinus a minor amount of phenethyl alcohol, which
mugo Turra subsp. mugo Zenari and subsp. is extremely soluble in water.
pumilio (Haenke) Franco. It is a colorless liq- In addition to the major components men-
uid with a pleasant, balsamic odor. tioned above, Bulgarian rose oil also contains
d 25 20
25 0.853 – 0.871; nD 1.475 – 1.480; [α]D
25
a number of components which, although
◦ ◦
− 16 to − 3 ; solubility: 1 vol in 10 vol of present in low concentrations, contribute to
90 % ethanol; bornyl acetate content is sim- the characteristic fragrance. Among these are
ilar to that of pine needle oil. β-damascenone (see page 39) and rose oxide
6) Spruce and hemlock oils are produced in (see page 72) [320].
Canada and the Northeast of the United Since ca. 3 t of blossoms are required to pre-
States by steam distillation of needles and pare ca. 1 kg of oil, rose oil is one of the
twigs from Picea mariana (Mill.) B.S.P. most expensive essential oils. Production is
(black spruce), Picea glauca (Moench) limited and is only about 30 t per year.
Voss (white spruce), Tsuga canadensis (L.) 2) Rose absolute is prepared from the concrete
Carrière (Eastern Hemlock), and related extracted from Rosa x damascena in the
species. They are very pale to light yellow countries mentioned above, as well as from
liquids with a pleasant odor reminiscent of Rosa centifolia L. (rose de mai) in Morocco
pine needles. and the south of France.
d 25 20
25 0.900 – 0.915; nD 1.4670 – 1.4720; [α]D The absolute is a reddish liquid with a typical
◦ ◦
− 25 to − 10 ; solubility: 1 vol in at least rose odor. The phenethyl alcohol content of
1 vol of 90 % ethanol; solutions may become its volatile fraction is 60 – 75 % [321].
hazy when > 2 vol of 90 % ethanol are added;
ester content (calculated as bornyl acetate): Rosemary oil is obtained by steam distilla-
37 – 45 % [318]. tion of the twigs and flowering tops of Ros-
marinus officinalis L. (Lamiaceae). It is an al-
most colorless to pale yellow or yellow-greenish
Rose oil and rose absolute are used mainly liquid with a characteristic, refreshing, pleasant
in fine fragrances. Rose oil is also used in small odor.
amounts for flavoring purposes. For oils type Spain: d 2020 0.892 – 0.910; nD
20
20 ◦ ◦
1.4640 – 1.4760; [α]D − 5 to + 8 ; ester con-
1) Rose oil is obtained by steam distilla- tent (calculated as bornyl acetate): 2 – 5 %; acid
tion of blossoms of Rosa x damascena value: 1.0; solubility: 1 vol in 3 vol of 90 % eth-
Mill. (Rosaceae) that is mainly cultivated in anol.
Turkey, Bulgaria (Kazanlik rose), and Mo- For oils type Tunisia and Morocco: d 20 20
rocco. Since a reasonable amount of rose oil 0.907 – 0.920; n20 20 ◦
D 1.4640 – 1.470; [α]D − 2
is still dissolved in the aqueous phase after ◦
to + 5 ; ester content (calculated as bornyl ac-
steam distillation, the distillation water (rose etate): 2 – 5 %; acid value: 1.0; solubility: 1 vol
water) is redistilled or extracted. in 2 vol of 80 % ethanol [322]
Rose oil is a yellow to greenish-yellow liquid Major components are 1,8-cineole, α-pinene,
with the characteristic odor of rose blossoms and camphor, which comprise up to 55 %, 30 %
and distinct tea and honey notes. and 22 %, respectively of commercial oils. The
 Flavors and Fragrances 113

composition of the oil varies with its origin. exists, which is obtained by steam distilla-
North African oils (e.g., from Tunisia) are com- tion after drying of the tops and foliage on
paratively high in cineole. Spanish oils have a the field. Both qualities are pale yellow to
lower cineole content, but a higher camphor (up yellow liquids with a herbaceous odor and a
to 22 %) and monoterpene hydrocarbon content winelike bouquet.
(30 – 40 %). Verbenone [18309-32-5] is also im- Physical constants for the quality Broyée en
portant for the odor; it may occur in traces or as a vert: d 20 20
20 0.890 – 0.902; nD 1.4560 – 1.4660;
major component; its content in the Spanish oils [α]20
D − 20 ◦
to − 10 ◦
; solubility: 1 vol in
is higher than in the North African ones [323]. 3 vol of 80 % ethanol; solutions become
opalescent on dilution; acid value: max. 1;
ester content (calculated as linalyl acetate):
63 – 75 % [325].
In addition to linalyl acetate, the oil contains
linalool and other terpene alcohols, as well as
Verbone their acetates. When the volatile components
are evaporated, a distinct ambergris note de-
The main producers of rosemary oil are in velops that is attributed to oxidative degrada-
Tunisia and Spain. About 100 to 150 t are pro- tion products of sclareol [515-03-7]. Sclareol
duced annually. Rosemary is used widely in per- is the main component in the concrete, ob-
fumery and in large amounts for perfuming bath tained by solvent extraction of S. sclarea L.
foams, shampoos, and hair tonics. leaves.
Rosewood oil, Brazilian (Bois de rose
oil) is obtained by steam distillation of wood
from Aniba rosaeodora Ducke var. amazon-
ica Ducke and/or A. parviflora (Meissner) Mez
(Lauraceae). It is an almost colorless to pale yel-
low liquid with a characteristic, sweet odor, rem-
iniscent of linalool.
d 20 20
20 0.870 – 0.887; nD 1.4620 – 1.4690; [α]D
20
Sclareol
− 2 ◦ 50 to + 4 ◦ ; solubility: 1 vol in 9 vol of 60 %
ethanol at 20 ◦ C; acid value: max. 1; ester value: Sclareol is used as a starting material for a
max. 5; ester value (after acetylation): 247 – 280, number of ambergris fragrances. Major cul-
corresponding to an alcohol content of 82 – 96 % tivation areas for S. sclarea L. are the CIS,
(calculated as linalool) [324]. the Mediterranean and Balkan countries, and
Brazilian rosewood oil is no longer compet- more recently the United States. The annual
itive as a raw material for linalool. Increasing production is between 50 and 150 t.
production costs, as well as the development of Clary sage oil is used extensively in fine fra-
large-scale processes for fully synthetic linalool grances.
(for production of vitamin A), have led to a 2) Dalmatian sage oil is obtained by steam dis-
sharp decline in production (annual production tillation of the partially dried leaves of Salvia
ca. 20 – 30 t). Currently, rosewood oil is only officinalis L. (Lamiaceae). It is a colorless to
used in small amounts in perfumes, e.g., for yellow liquid with a warm camphoraceous,
soaps. thujone-like odor and sharp and bitter taste.
d 20 20
20 0.910 – 0.930; nD 1.4580 – 1.4740; [α]D
Sage oils are of three main types: + 2 ◦ to + 30 ◦ ; saponification value: 6 – 20;
ketone content (calculated as thujone): 28 –
1) Clary sage oil is obtained by steam distil- 78 %; solubility: 1 vol in 2 vol of 80 % etha-
lation of flowering tops and foliage of cul- nol at 20 ◦ C [326].
tivated Salvia sclarea L. (Lamiaceae). The The major components of S. officinalis oil
quality Broyée en vert is obtained after cut- are camphor and α-thujone [546-80-5]. β-
ting the fresh material and immediate distil-
lation. Another quality named Traditionelle
114 Flavors and Fragrances

thujone [471-15-8] is present in ca. 5 % con- The trees cultivated for oil production must be
centration. at least 30 years old to make oil production prof-
itable. The oil yield, calculated on the amount of
wood used for steam distillation, is 4 – 6.5 %. In-
dian production is ca. 60 t/a. Smaller quantities
are produced in neighboring countries.
East Indian sandalwood oils are used exten-
sively in perfumery as very valuable, stable fix-
α-Thujone [(−)-thujone] β-Thujone [(+)-isothujone]
atives.
The oil is used in pharmaceutical prepara-
tions and in perfumery to create dry, spicy- Sassafras oil, Brazilian is obtained by steam
herbaceous notes. distillation of the roots, trunks, and branches of
3) Spanish sage oil is produced by steam dis- Ocotea pretiosa (Nees) Mez (Lauraceae). The
tillation of leaves and twigs of Salvia lavan- oil was formerly called Ocotea cymbarum oil
dulifolia Vahl (Lamiaceae) growing in Spain due to incorrect botanical naming. It is a yellow
in the provinces Granada, Murcia, Almeria, to brownish liquid with the characteristic odor
and Jaén. The oil is an almost colorless to pale of safrole.
yellow liquid with the characteristic cam- d 20
20 1.082 – 1.094; nD
20
1.5330 – 1.5370;
20 ◦ ◦
phoraceous odor of the leaves. [α] D − 0.5 to + 3.0 ; solubility: 1 vol in 2 vol
d 20 20 20 of 90 % ethanol; fp + 7.5 to + 9.5 ◦ C [329].
20 0.907 – 0.930; nD 1.465 – 1.472; [α]D
◦ ◦
− 12 to + 17 ; solubility: 1 vol in 2 vol of The main component of the oil is safrole,
80 % ethanol at 20 ◦ C; acid value: max. 2.0; which may make up more than 90 % of the oil
ester value: min. 15, max. 55 [327]. and determines its freezing point. (IFRA recom-
Unlike Dalmatian sage oil, Spanish sage oil mendation)
contains no or only traces of α- or β-thujone; Production from trees that grow wild in
camphor and 1,8-cineole are the major com- Brazil, Paraguay, and Columbia exceeds that of
ponents and are responsible for the odor of North American sassafras oil, which is similar
the oil, which is used primarily in pharma- in composition. The main use of the oil is for the
ceutical preparations. production of safrole and products derived from
Altogether about 50 t of Spanish and Dalma- it (e.g., isosafrole and piperonal, see page 69).
tian oils are produced annually. Chinese sassafras oils (annual production
about 950 t) are fractions, rich in safrole, that
Sandalwood oil, East Indian is obtained by are obtained from oils of different species of the
steam distillation of the heartwood of Santalum camphor tree (see Camphor Oils, page 90).
album L. (Santalaceae). It is a slightly viscous,
almost colorless to golden yellow liquid with a Savory oil is obtained by steam distillation
characteristic, sweet, woody, long-lasting odor. of the whole dried herb Satureja hortensis L.
d 20 20 20 (Summer savory) or S. montana L. (Lamiaceae)
20 0.968 – 0.983; nD 1.5030 – 1.5080; [α]D
◦ ◦
− 21 to − 12 ; solubility: 1 vol in 5 vol of 70 % (Winter savory). It is a light yellow to dark brown
ethanol at 20 ◦ C; ester value: min. 10; free alco- liquid with a spicy odor, reminiscent of thyme
hol content (calculated as santalol): min. 90 %. or origanum.
East Indian sandalwood oil consists almost d 25 20
25 0.875 – 0.954; nD 1.4860 – 1.5050; [α]D
◦ ◦
exclusively of closely related sesquiterpenoids; − 5 to + 4 ; phenol content: 20 – 59 %; saponi-
the alcohols cis-α-santalol [115-71-9] (45 – fication value: max. 6; solubility: 1 vol in 2 vol
55 %) and cis-β-santalol [77-42-9] (18 – 24 %) of 80 % ethanol at 25 ◦ C; solutions in 10 vol of
are mainly responsible for its odor [328]. ethanol may be slightly hazy [330].
Several qualities of savory oil exist, depend-
ing on the Saturejaspecies used. The main cul-
tivation areas are France, Spain, some of the
Balkan countries, and some midwestern states
of the United States. Characteristic of savory oil
α-Santalol β-Santalol is its high content of carvacrol [499-75-2].
 Flavors and Fragrances 115

Tagetes oil (Marigold oil) is produced by

steam distillation of the flowering plants Tagetes
minuta L. (T. glandulifera Schrank., Aster-
aceae). The main producers are in France, South
Africa, and India. The oil is a yellow to dark
orange liquid with a strong, aromatic-fruity
Carvacrol odor. Its main components are cis-ocimene, di-
hydrotagetone, tagetone, and cis- and trans-
Savory oil is used mainly in the food industry,
ocimenone.
e.g., for flavoring sauces and soups.
It is used in accentuated flowery fragrances
and in aroma compositions to achieve fruity ef-
Spearmint oil, see Mint Oils, page 107. fects. (IFRA recommendation)
Spike oil, see Lavandula Products, page 105 Tarragon oil ( estragon oil) is produced by
steam distillation of leaves, stems, and flowers
Star anise oil is obtained by steam distilla- of Artemisia dracunculus L. (Asteraceae). It is a
tion of the star-shaped fruits of Illicium verum colorless to pale yellow liquid with a character-
Hook. f. (Illiciaceae), an evergreen tree growing istic, spicy, delicate estragon odor reminiscent
in Vietnam and China. It is a colorless to pale of liquorice and sweet basil.
yellow liquid, which solidifies on cooling. d 20 20 20
20 0.918 – 0.943; nD 1.5080 – 1.5180; [α]D
d 20 20
20 0.979 – 0.985; nD 1.5530 – 1.5560; [α]D
20
◦ ◦
+ 2 to + 6 ; acid value: max. 1; ester value:
◦ ◦
− 2 to + 2 ; solubility: 1 vol in 3 vol of 90 % max. 18; solubility: 1 vol in 4 vol of 90 % etha-
ethanol; fp min. 15 ◦ C [331]. nol [332].
The main component of star anise oil, as The main component of tarragon oil is es-
in anise oil, is trans-anethole (86 – 93 %, deter- tragole (methylchavicol, see page 89), which
mined by GLC). Pure anethole can be obtained may make up > 60 % of the oil.
by rectification (see page 64). Star anise oil has Worldwide production of tarragon oil only
replaced true anise oil derived from Pimpinella amounts to a few tons per year. It is used mainly
anisum in the production of natural anethole. in aroma compositions, smaller quantities are
Star anise oil and its product, anethole, are employed in perfumery.
used primarily in the alcoholic beverage indus-
try (anise liquors), but also for flavoring food Tea tree oil is obtained by steam distillation
and toothpaste. of leaves and twig tips of Melaleuca alternifo-
lia Cheel, M. linariifolia Sm. and M. dissitiflora
Styrax oil and styrax resinoid are obtained F. Mueller, and other Melaleuca species, which
from styrax balsam, which is collected from the are trees growing in Australia (Myrtaceae). It is
artificially injured trees, Liquidamber orientalis a colorless to pale yellow liquid with an earthy,
Mill. (Asia Minor) and L. styraciflua L. (Central spicy odor.
America) (Hamamelidaceae). d 20 20 20
20 0.888 – 0.906; nD 1.4750 – 1.4800; [α]D
Styrax resinoid is a light grey to dark grey- + 5 ◦ to + 15 ◦ ; cineole content: max. 15 % (by
brown viscous liquid that is prepared by sol- GLC); terpinen-4-ol content: min. 30 % (by
vent extraction. It has a sweet balsamic, slightly GLC); solubility: 1 vol in 2 vol of 85 % ethanol
grasslike odor and is used in perfumery as a fix- [333].
ative. Tea tree oil is used in perfumery for creating
Steam distillation of the balsam gives styrax certain nuances and for earthy notes. In addition
oil, a light yellow liquid that contains a rel- there is an increasing interest for using this oil in
atively large amount of cinnamic acid, which aroma therapy. Annual production is ca. 150 t.
partially crystallizes. Styrax oil has a sweet-
balsamic odor with a styrene-like top note. It Thuja oil, see Cedar Leaf Oil, page 92.
is used in perfumery in flowery compositions.
(IFRA recommendation).
116 Flavors and Fragrances

Thyme oil is obtained by steam distillation Tuberose absolute is obtained by solvent ex-
of flowering plants of Thymus zygis L. var. gra- traction, via the concrete, from the blossoms of
cilis Boissier (Lamiaceae). Thyme oil is not to Polianthes tuberosa L. (Agavaceae). The plants
be confused with white thyme oil; see under Ori- are cultivated in Morocco, Egypt, and India.
ganum Oil. Thyme oil is a red or reddish liquid Tuberose absolute was formerly produced in
with a strong, characteristic, spicy-phenolic odor southern France by enfleurage. It is an orange
and a sharp, lasting taste. to brown liquid with a sweet-narcotic blossom
d 20 20
20 0.910 – 0.937; nD 1.4940 – 1.5040; [α]D
20
odor and is used in modern, flowery perfume
◦ ◦
− 6 to − 1 ; total phenol content: min. 38 %, compositions.
max. 56 %; solubility: 1 vol in 3 vol of 80 % eth-
anol [334]. Turpentine oils (→ Turpentines) are used in
The main constituents of thyme oil are thymol large quantities by the fragrance industry as
and carvacrol (up to 60 %); for structures of these starting materials for the manufacture of sin-
compounds, see p. page 63, page 116. Other gle fragrance and flavor compounds. Turpentine
chemotypes of T. vulgaris are limited to specific oils are obtained either from balsams or from
areas and yield, e.g., oils that contain geraniol, the wood of various Pinaceae species. They are
linalool, α-terpineol, and cineole; these oils are less valuable as odor materials than the oils ob-
of minor importance. tained from needles, young twigs, and cones (see
Thyme shrubs grow in France, Spain, Alge- Pinaceae Needle Oils, page 113). Nevertheless,
ria, and Morocco. Spain is the main producer of they are used either as such or indirectly as fra-
the oil. Thyme oil is used mainly for flavoring grant solvents for perfuming household prod-
foods and oral hygiene products, but is also used ucts. IFRA recommends that these oils should
in perfumery to create spicy, leathery notes. Be- only be used when the level of peroxides is kept
cause of its high phenol content, thyme oil has to the lowest practical level.
germicidal and antiseptic properties. Balsam turpentine oil is obtained from the
resins of living trees of suitable Pinus species
Tolu balsam resinoid is produced by extrac- by distillation at atmospheric pressure and tem-
tion of the balsam of Myroxylon balsamum (L.) peratures up to 180 ◦ C, or by other fractionation
Harms (Fabaceae). It is a dark orange brown methods, which do not change the terpene com-
mass with a sweet, resinous, long-lasting odor, position of the resins. Wood turpentine oils, on
reminiscent of hyacinth. An essential oil is also the other hand, are generally obtained by steam
distilled from the balsam. distillation of chopped tree trunks, dead wood,
Tolu balsam resinoid contains a fairly large or of resin extracted from this wood. Sulfate tur-
amount of benzyl and cinnamyl esters of benzoic pentine oil is produced as waste in the manu-
and cinnamic acid. facture of cellulose by the sulfate process and is
Both the resinoid and the balsam are used in also a wood turpentine. Pine oil is another wood
perfumery, mainly for their fixative properties. turpentine oil that is obtained by dry distillation
of suitable pine and fir trees, followed by frac-
Tonka bean absolute is prepared by solvent tionation.
extraction either directly from so-called Tonka Balsam and wood turpentine oils are color-
beans or via the concrete. Tonka beans are the less liquids with a mild, characteristic odor. Oils
seeds of fruits from Dipteryx odorata (Aubl.) obtained by dry distillation often also have a phe-
Willd. (Fabaceae). nolic note. The specifications of turpentine oils
Tonka bean absolute is a solid or crystalline are listed in Table 5 [335].
mass with a sweet, caramel-like odor, reminis- Worldwide production of turpentine oils is ca.
cent of coumarin. In perfumery tonka bean ab- 300 000 t/a, of which approximately one third is
solute is used as a fixative and produces a dry produced in the United States and Canada as sul-
sweetness in men’s fragrances. fate turpentine oil. Other major producers are the
CIS, Scandinavia, and China.
Tree moss absolute, see Oakmoss Absolute, The main components of all turpentine oils
page 110. are terpene hydrocarbons. The balsam and sul-
fate turpentine oils produced in the South-
 Flavors and Fragrances 117
Table 5. Specifications of turpentine oils

Parameter Type of turpentine oil

Balsam Wood, steam distilled Sulfate Wood, dry distilled

d 20
4 0.855 – 0.870 0.855 – 0.870 0.860 – 0.870 0.850 – 0.865
n20
D 1.465 – 1.478 1.465 – 1.478 1.465 – 1.478 1.463 – 1.483
◦
Distillate up to bp 170 C, % 90 90 90 60
Evaporation residue, % 2.5 2.5 2.5 2.5
Acid value 1 1 1 1

east of the United States contain mainly α- tifolia Miq., cultivated in Japan, give a much
and β-pinene (60 – 70 % and 20 – 25 %, respec- larger yield of oil.
tively); Pinus palustris Mill. (long leaf pine) Valerian oil is produced in limited quantities
gives the (+)-enantiomers and Pinus caribaea and is used in flavor and fragrance compositions
Morelet (slash pine) gives the (−)-enantiomers. and, to a small extent, in pharmaceutical prepa-
The remaining constituents are p-menthadienes, rations.
oxygen-containing terpenoids, and anethole. In
contrast with the Scandinavian and Russian tur- Vanilla extract (an oleoresin) is produced
pentine oils, the American oils contain very lit- by extraction of the pods of Vanilla planifolia
tle 3-carene or camphene. Large amounts of the Andrews or V. tahitensis J. W. Moore (Orchi-
American oils are separated by fractional dis- daceae) with a polar solvent (e.g., methanol, eth-
tillation into their components, which are used anol, or acetone, which may also contain water).
as starting materials in the manufacture of fra- The composition of the extract depends on the
grance and flavor compounds. European turpen- type and amount of solvent used. Generally, the
tine oils originate mainly from Portugal, where percentage of vanillin in the extract (yield 25 –
distillation of Pinus pinaster Aiton resin or 30 %) is 3 – 4 times higher than that in the pods.
wood gives a turpentine oil that consists of 70 – Vanillin and phenol derivatives are primarily
85 % (−)-α-pinene and 10 – 20 % (−)-β-pinene responsible for its aroma. The main producers of
[336]. V. planifolia pods are Madagascar, the Comoro
Islands, and Réunion (Bourbon); V. tahitensis
Valerian oil is obtained by steam distillation pods are grown mainly in Tahiti.
of well-dried ground roots of Valeriana offici- Vanilla extracts are used extensively in
nalis L. (Valerianaceae). It is a yellow-green to chocolate and baked products, but even more so
yellow-brown liquid with an extremely strong, in ice cream.
characteristic, penetrating odor. The oil becomes
dark and viscous on aging or on exposure to air. Verbena oil is produced by steam distilla-
d 25 20
25 0.942 – 0.984; nD 1.4860 – 1.5025; [α]D tion of the leaves of Aloysia triphylla (L’Hér.)
− 28 ◦ to − 2 ◦ ; acid value: 5 – 50; saponification Britton [Lippia citriodora(Lam) Humb., Bonpl.
value: 30 – 107; solubility: 1 vol in 0.5 – 2.5 vol et Kunth, L. triphylla (L’Hér.) Kuntze, (Verbe-
of 90 % ethanol at 25 ◦ C, solutions are clear to naceae)]. It is a light yellow liquid with a delicate
opalescent when up to 10 vol of ethanol is added lemon odor.
[337]. d 20 20
20 0.890 – 0.920; nD 1.4820 – 1.4880; [α]D
The main component of the oil is (−)-bornyl − 18 ◦ to − 10 ◦ ; content of carbonyl compounds
acetate, but it also contains other bornyl esters (calculated as citral): 32 – 38 %; solubility: 1 vol
(e.g., bornyl isovalerate), terpene and sesquiter- in 1 vol of 90 % ethanol.
pene hydrocarbons, as well as free isovaleric The major components of “true” verbena oil
acid, which contributes strongly to the odor of are citral (ca. 40 %), geraniol, and nerol (ca. 5 %
the oil. each).
Valerian is cultivated in Belgium, northern The verbena plant, originates in South Amer-
France, east Germany, Poland, Hungary, and ica, but is cultivated mainly in southern France.
southern Russia. The so-called Kesso roots ob- The oil is used in fine fragrances. IFRA recom-
tained from Valeriana officinalis L. var. angus- mendation.
118 Flavors and Fragrances

Vetiver oil is produced by steam distillation The absolute is a dark green to brown liq-
of the roots of the grass Vetiveria zizanioides (L.) uid with a strong, green odor. The main con-
Nash (Poaceae), which grows wild or is culti- stituent of the volatile fraction is 2-trans-6-cis-
vated in many tropical and subtropical countries. nonadienal [557-48-2] (violet leaf aldehyde).
The oil is a brown to reddish-brown, viscous Violet leaf absolute is used frequently in per-
liquid with a characteristic precious-wood- and fume compositions, but only in very low con-
rootlike, long-lasting odor. The following spec- centration because of its intense odor.
ifications are for oil produced in Haiti:
d 20
20 0.980 – 1.001; nD
20
1.5160 – 1.5270; Ylang-ylang and cananga oils are essential
20 ◦ ◦
[α] D + 22 to + 46 ; acid value: min. 1, max. oils that are obtained from two subspecies of the
14; ester value: 5 – 35; carbonyl value: 23 – 59; cananga tree.
solubility: 1 vol in 2 vol of 80 % ethanol at 20 ◦ C.
The tenacity of the highly complex vetiver oil 1) Ylang-ylang oils are obtained by steam distil-
is attributed to its high sesquiterpene content. lation of freshly picked blossoms of Cananga
The ketones α-vetivone [15764-04-2] and β- odorata (Lam.) Hook. f. et Thomson (An-
vetivone [18444-79-6], which form up to 10 % nonaceae). These cananga trees normally
of the oil, as well as khusimol [16223-63-5] (up grow to a height of 20 m but are pruned to a
to 15 %) and its derivatives, contribute signifi- height of 2.10 – 3.00 m and flower through-
cantly to its odor [338]. out the year. The oil is produced mainly
in Madagascar and the Comoro Islands.
Four fractions are collected at progressively
longer distillation times and are known as
“Extra”, “I”, “II”, and “III”. They are all
pale to dark yellow liquids with a charac-
teristic floral, spicy, balsamic odor. The first
α-Vetivone β-Vetivone fractions are the most valuable; they have a
higher density and a higher saponification
value. Specifications of fractions obtained
from Comoro Island oils are given in Table 6
[339, 340].
Khusimol
The compositions of the various oil frac-
tions depend on the duration of distilla-
The oil contains a considerable number of tion. The first fraction, ylang-ylang oil Ex-
bi- and tricyclic primary, secondary, and ter- tra, has the highest content of strongly odor-
tiary sesquiterpene alcohols, called vetiverols or iferous constituents such as p-cresyl methyl
vetivenols. These alcohols, as well as their ac- ether (about 8 %), methyl benzoate (about
etates, are valuable fragrance materials. Since 5 %), (−)-linalool (about 11 %), benzyl ac-
several varieties of vetiver grass exist and since etate (about 30 %), and geranyl acetate (about
fresh as well as air-dried roots are distilled under 4 %). The other fractions contain increas-
conditions that vary with the producer, the qual- ing amounts of sesquiterpene hydrocarbons
ity of the commercial oils differs considerably. (mainly caryophyllene and germacrene D),
Oil yields are up to 3 %. The main producers are which can reach 70 % in ylang-ylang III.
Indonesia, China, and Haiti (ca. 300 t/a). Components such as p-cresol, eugenol, and
Vetiver oil is used in fine fragrances for long- isoeugenol are important for the odor, al-
lasting precious-wood notes. It is also used as though they are present only in low concen-
starting material for vetiveryl acetate (see page tration.
41). Ylang-ylang Extra and I are used mostly in
fine fragrances; ylang-ylang II and III are em-
Violet leaf absolute is obtained by solvent ployed in soap perfumes.
extraction, via the concrete, from the leaves of 2) Cananga oil is produced by steam distil-
Viola odorata L. (Violaceae), which is grown lation of the flowers of Cananga odorata
predominantly in southern France. (DC) Hook. f. et Thomson subsp. macro-
 Flavors and Fragrances 119
Table 6. Specification of ylang-ylang oils from the Comoro Islands

Parameter Ylang-ylang fractions

Extra I II III

d 20
20 0.955 – 0.976 0.938 – 0.960 0.925 – 0.945 0.906 – 0.925
n20
D 1.498 – 1.506 1.501 – 1.509 1.502 – 1.511 1.503 – 1.513
[α]20
D − 40 ◦ to − 20 ◦ − 46 ◦ to − 25 ◦ − 60 ◦ to − 35 ◦ − 72 ◦ to − 45 ◦
Acid value <2 <2 <2 <2
Ester value 140 – 185 100 – 160 75 – 115 45 – 75

phylla (Annonaceae). The yield, based on the of these parameters are their speed of measure-
weight of the flowers, is ca. 1 %: The oil is a ment and the possibility of comparison with
light to dark yellow liquid with a character- other laboratories; therefore, they will continue
istic, floral, slightly woody odor. to be indispensable. In addition, these measure-
d 20
20 0.906 – 0.923; nD
20
1.4950 – 1.5030; ments can be done more and more by robots
20 ◦ ◦
[α] D − 30 to − 15 ; solubility: 1 vol in controlled by computers.
1 vol of 95 % ethanol at 20 ◦ C (solution may Determinations of content by chemical pa-
be turbid); acid value: max. 2; ester value: rameters, such as ester and carbonyl values, are
13 – 35 [341]. being increasingly supplemented by chromato-
The qualitative composition of cananga oil graphic procedures such as GC and HPLC and
resembles that of ylang-ylang III oil, but by spectroscopic techniques (UV, IR, NIR, and
is distinguished by its higher caryophyllene NMR).
content (30 – 40 %). Standardization of specifications for complex
Cananga oil originates almost exclusively fragrance and flavor materials, such as essen-
in Java, where the flowers are collected tial oils and animal secretions, is far more dif-
throughout the year; annual production is ficult than for single compounds. In addition to
30 – 50 t. The oil is used mainly in soap per- organoleptic and physical properties, the con-
fumes. tent of certain typical components is determined.
Problems concerning the natural, botanical, and
geographical origins of these products are solved
4. Quality Control by using modern chromatographic and spectro-
scopic analytical techniques (and combinations
Quality control of fragrance and flavor sub- such as GC – MS). Furthermore the determina-
stances, as well as the products derived from tion of chiral properties of the molecules by
them, comprises the comparison of sensory, enantioselective capillary GC has become a rou-
analytical, and if necessary, microbiological tine method. Isotope ratio mass spectrometry
data with standards and specifications. To a (IRMS) reveals the stable isotope ratios of the
large extent these have been established in offi- bioelements C, H, O, N, and S and the posi-
cial specification collections (Pharmacopoeias, tional isotope analysis can be performed by Site-
ISO, Association Française de Normalisation specific Natural Isotope Fractionation – NMR
(AFNOR), Essential Oil Association, Merck In- (SNIF – NMR) [343]. These methods have be-
dex). come very effective tools for authenticity con-
In the past few decades, a precise analyti- trol.
cal methodology has been developed for sensory The analysis of trace components (halogens,
evaluation and has proved to give reliable results heavy metals, and pesticides) in flavors and fra-
[342]. Analytical determination of identity and grances that are used in foods and cosmetics
purity aids greatly in establishing the acceptabil- is becoming increasingly important. Radioactiv-
ity of fragrance and flavor materials. ity values in materials of natural origin are also
Single fragrance and flavor compounds are monitored.
characterized by generally accepted physical
constants, such as density, refractive index, opti-
cal rotation, and melting point. The advantages
120 Flavors and Fragrances

5. Economic Aspects Already in 1966 in the USA the Research

Institute for Fragrance Materials, Inc. (RIFM,
The flavor and fragrance industry has grown Two University Plaza, Suite 406, Hackensack,
from an artisanal development into an industrial N.J. 07601) was established for the sole pur-
business. The total market for these product cat- pose of fragrance safety. As an independent non-
egories is estimated to about $ 16 × 109 , Europe profit organization, RIFM has a continuing pro-
and North America being the leading markets gram, testing fragrance materials of good com-
with shares of about $ 5.4 and 4.1 × 109 , respec- mercial quality. All judgements in matters per-
tively. Total annual growth rates till 2005 are taining to the evaluation of safety are made ex-
forecasted to reach about 4.5 %, growth in Eu- clusively, and independently by an international
rope and North America will be below 3 %. In expert panel of toxicologists, pharmacologists,
general it is predicted that sales of flavors will and dermatologists drawn from the academic
grow by about 5.5 % and fragrances on a whole world. Those results are published as ’RIFM
by about 3 %. monographs’ in the journal ’Food and Chem-
The flavor and fragrance industry has un- ical Toxicology’ [344] and in the Internet un-
dergone a great degree of consolidation since der www.rifm.org/data/start.cfm. These mono-
the mid-1990s. The top ten flavor and fragrance graphs contain specifications and data on bio-
producers have combined sales in excess of logical activity (e.g., acute, short-term, and long-
$ 9 × 109 , corresponding to about 55 % of the term toxicity, toxicokinetics, and metabolism).
total value. The remaining 45 % of the market In 1973 national associations of fragrance
are shared by more than 1000 other companies, manufacturers have formed the International
many of them serving only one to three cus- Fragrance Association (IFRA, 8, Rue Charles
tomers. Out of the top ten companies, four have Humbert, CH-1205 Genève, Switzerland), an
annual sales in excess of $ 1 × 109 , namely Gi- international organization with scientific aims
vaudan and Firmenich of Switzerland, IFF of concerned with all aspects of safety evalua-
the USA and Quest, which is affiliated with ICI. tion and regulation of the fragrance industry.
Takasago of Japan also reports sales in excess IFRA represents over 100 fragrance manufac-
of $ 1 × 109 , however its sales in the flavors and turers in 15 countries and edits guidelines ad-
fragrances field are less than that. The remaining vising against the use of fragrance materials un-
top ten companies, in addition to the aforemen- der conditions that might provoke irritation and
tioned, are Dragoco and Haarmann and Reimer, sensitization reactions or phototoxic effects (see
both in Germany, Universal Flavors in the USA, Section 1.5.2). The activities of RIFM and IFRA
and Hasegawa in Japan. The last one of this are harmonized by a Joint Advisory Committee.
group, BBA of the USA, has recently been taken Similarly to IFRA, the International Organiza-
over by IFF. In conclusion, it can be foreseen tion of the Flavor Industry (IOFI, same adress
that further consolidation will increase the mar- as IFRA) publishes lists of naturally occurring
ket shares of these top ten companies over the and nature-identical flavor components, which
next five years. may be used up to given concentrations, and of
artificial flavor substances that are considered to
be nontoxic.
6. Toxicology and Environmental For more than 40 years the Flavor and Ex-
tract Manufacturers’ Association’s (FEMA) Ex-
Aspects pert Panel Food Additives conducts a compre-
hensive program of safety evaluation of fla-
The addition of flavor and fragrance compounds
voring substances under the authority of Sec-
to foods, cosmetics and toiletries, and other con-
tion 201(s) of the Federal Food, Drug, and Cos-
sumer products is intended to improve the qual-
metic Act. FEMA publishes compendiums with
ity of those products. So these chemicals must
flavor components commonly known as GRAS.
not have adverse effects on health or well-being.
In the 1980s and especially in the 1990s a
To avoid any problems caused by perfumed con-
growing awareness developed that flavor and
sumer products, the fragrance industry decided
fragrance chemicals can also affect the environ-
to build up a self-regulatory system.
ment. So the Material Safety Data Sheets of fla-
 Flavors and Fragrances 121

vors and fragrances (MSDS, see EEC Directive 2. W. Pickenhagen in W. Pickenhagen, C.-T. Ho,
91/155/EEC) now contain in addition to the tox- A. M. Spanier (eds.): The Contribution of Low-
icological information also ecological informa- and Nonvolatile Materials to the Flavor of
tion, mainly: biodegradability and aquatic tox- Foods, Allured Publishing Corporation, Carol
icity. In most countries, the use of flavor and Stream, Ill. 1996, p. 3.
fragrance materials in consumer products is ex- 3. E. Wick, Food Technol. 19 (1965) 145.
tensively regulated. 4. G. Ohloff: Scent and Fragrances, Springer
Verlag, Berlin – Heidelberg – New York 1994.
Recent Discussions. In 2002 nitromusks 5. F. Wöhler, Ann. Phys. Chem. 12 (1828) 253.
were identified in surface water, fish, and hu- 6. A T. James. A. I. P. Martin, Analyst 77 (1952)
man fat and milk samples. Due to their low 915.
biodegradability these substances – having been 7. E. I. Golay, Gas Chromatog. Proc.
Symposium, Amsterdam 1958, 36 – 38.
used for 100 years – accumulate in the environ-
8. L. M. Nijssen et al. (eds.): Volatile Compounds
ment. In addition a relatively high log (partition
in Food: Qualitative and Quantitative Data,
coefficient octanol – water) (log Pow > 5) shows
TNO Nutrition and Food Research, Zeist
that these substances are lipophilic and therefore 1963 – 1999.
accumulate also in fat tissue. RIFM has initi- 9. R. Harper, E. C. Bate Smith, D. G. Land:
ated the execution of various studies: acute and Odour Description and Odour Classification,
subchronic toxicity, irritation, sensitization and J.+A. Churchill Ltd., London 1968.
photosensitization potential, genotoxicity, car- 10. D. Kastner, Parfümerie Kosmetik 54 (1973)
cinogenicity bioassay; studies on dermal absorp- 97.
tion and pharmacokinetic. 11. J. S. Jellinek, Ann. NY Acad. Sci. 116 (1963)
Reports of polycyclic musks in the environ- 725.
ment have also prompted a review of the safety of 12. L. J. van Great, A. H. Nettenbretter:
these important fragrance ingredients and sim- “Compilation of odour threshold values in air
ilar studies as for nitromusks were conducted. and water”, published by The National
For both groups the following summary is valid: Institute for Water Supply, Voorburg and the
Margins of safety based on the no-adverse-effect Netherlands Central Institute for Nutrition and
levels from subchronic studies are sufficient to Food Research, TNO, Zeist 1977.
conclude that direct exposure from use of these 13. F. Drawert, N. Christoph: “Significance of the
materials in fragrances or indirect exposure from sniffing-technique for the determination of
their presence in the environment pose no sig- odour thresholds and detection of aroma
impacts on trace volatiles”, in P. Schreier (ed.):
nificant risks to human health. Their environ-
Analysis of Volatiles, Proceedings
mental risk assessment is the subject of separate
International Workshop Würzburg, Sept. 1983,
reviews.
Walter de Gruyter, Berlin 1984.
The discussions on the nitro and polycy- 14. D. G. Guadagni, R. G. Buttery, J. Food Sci. 43
clic musks have given increased evidence of (1978) 1346.
the importance of knowing as much as possi- 15. Manual on Sensory Testing Methods, ASTM
ble about properties of fragrance materials such Spec. Tech. Publ. 434, American Society for
as biodegradability and partition coefficient oc- Testing Materials, Philadelphia 1968.
tanol – water. 16. M. Rothe, B. Thomas, Z. Lebensm. Unters.
Forsch. 119 (1963) 302.
17. CFR Ch. I,4-1-00 Edition, § 101.22 a, (1).
7. References 18. CFR Ch. I, 4-1-00 Edition, § 101.22 a, (3).
19. Firmenich SA, CH 581 446, 1973 (F. Naef, G.
The authors would like to thank B. M.
Ohloff, A. Eschenmoser).
Lawrence and K. D. Protzen for providing
20. International Flavors & Fragrances Inc., FR
information about production quantities of
1 508 854, 1968 (H. J. Blumenthal).
essential oils.
21. Ruhrchemie AG, EP 7 609, 1978 (H.
The abbreviation EOA refers to the Essential
Bahrmann, B. Cornils, G. Diekhaus, W.
Oil Association of the United States.
1. E. von Skramlik, Z. Psychol. Physiol. Kascha et al.).
Sinnesorg. 53 (1922) 36.
122 Flavors and Fragrances

22. Union Carbide, US 2 628 257, 1953 (R. I. 51. K. Kogami, J. Kumanotani, Bull. Chem. Soc.
Hoaglin, D. H. Hirsh). Japan 41 (1968) 2508 – 2514; Chem. Abstr.
23. Naarden International N.V., NL 76 08 333, 70 (1969) 20230y.
1976 (P. C. Traas, H. Boelens, H. J. Wille). 52. Rhône-Poulenc, DE-AS 1 811 517, 1968 (P.
24. Monsanto Chemical Corp., US 2 455 631, Charbardes).
1945 (O. J. Weinkauff). 53. Hoffmann-La Roche, DE 2 353 145, 1973 (N.
25. Firmenich SA, CH 544 803, 1970 (F. Naef). Hindley, D. A. Andrews).
26. IG Farbenindustrie AG, DE 705 651, 1941 (W. 54. Kuraray Co., JA 51 048 608, 1974 (T. Hosogai,
Flemming, H. Buchholz). T. Nishida, K. Itoi); Chem. Abstr. 85 (1976)
27. Union Camp Corp., EP-A 132 544, 1984 (P. W. 142638t.
Mitchell, L. T. McElligott, D. E. Sasser). 55. BASF, DE-AS 1 901 709, 1969 (H. Overwien,
28. The Glidden Company, US 3 031 442, 1958 H. Müller).
(R. L. Webb). 56. BASF, DE-AS 2 715 209, 1977 (C. Dudeck, H.
29. Kuraray Co., JP 75 58 004, 1973 (O. Yoshiaki, Diem, F. Brunnmüller, B. Meissner et al.).
Y. Ninagawa, Y. Jujita, T. Hosogai et al.). 57. BASF, DE-AS 2 715 208, 1977 (B. Meissner,
30. SCM Corp., US 4 254 291, 1978 (B. J. Kane). W. Fliege, O. Woerz, C. Dudeck et al.).
31. G. Ohloff, E. Klein, Tetrahedron 18 (1962) 58. BASF, DE-AS 2 625 074, 1976 (A. Nissen, G.
37 – 42. Kaibel).
32. Rhône-Poulenc Ind., SA, DE-AS 2 025 727, 59. BASF, EP 21 074, 1980 (A. Nissen, W.
1970 (P. S. Gradeff, B. Finer). Rebafka, W. Aquila).
33. SCM Corp., US 4 018 842, 1976 (L. A. 60. V. N. Kraseva, A. A. Bag, L. L. Malkina, O. M.
Canova). Khol’mer et al., SU 118 498, 1958; Chem.
34. Studiengesellschaft Kohle, US 3 240 821, 1966 Abstr. 53 (1959) 22067h.
(G. Ohloff, E. Klein, G. Schade). 61. Glidden, US 3 028 431, 1962 (R. L. Webb).
35. Glidden Co., US 3 076 839, 1958 (R. L. Webb). 62. Rhodia Inc., US 3 971 830, 1976 (P. S.
36. Hoffmann-La Roche, CH 342 947, 1959 (W. Gradeff).
Kimel, W. N. Sax). 63. D.-J. Wang, K’o Hsueh Fa Chan Yuch K’an 7
37. BASF, GB 848 931, 1960 (H. Pasedach, M. (1979) no. 10, 1036 – 1048; Chem. Abstr. 92
Seefelder). (1980) 124929d.
38. Hoffmann-La Roche, BE 634 738, 1964 (R. 64. L’Air liquide, DE-AS 2 045 888, 1970 (M.
Marbet, G. Saucy). Vilkas, G. Senechal).
39. Kuraray, DE 2 356 866, 1974 (Y. Tamai, T. 65. T. Kumano, JP 70 03 366, 1965; Chem. Abstr.
Nishida, F. Mori, Y. Omura et al.). 72 (1970) 111650t.
40. BASF, DE 1 267 682, 1967 (H. Müller, 66. Givaudan, DE-AS 2 211 421, 1972 (L. M.
H. Köhl, H. Pommer). Polinski, B. Venugopal, E. Eschinasi, J.
41. BASF, DE-AS 1 618 098, 1967 (H. Müller, H. Dorsky).
Overwien, H. Pommer). 67. Takasago Perfumery, DE 3 044 760, 1980 (S.
42. BASF, DE-AS 1 286 020, 1967 (H. Pommer, Akutagawa, T. Taketomi).
H. Müller, H. Overwien). 68. Soda Aromatic Co., JP 73 22 411, 1971 (T.
43. BASF, DE-AS 1 643 710, 1967 (H. Pasedach, Yasukawa, A. Abe, R. Eto, M. Ishitani et al.);
W. Hoffmann, W. Himmele). Chem. Abstr. 79 (1973) 18085x.
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2(2) 75 – 79; Chem. Abstr. 103 (1985) Nayler).
119978k. 70. BASF, DE 1 768 980, 1968 (H. Pasedach).
45. Takasago Perfumery, EP-A 112 727, 1984 (S. 71. Hoffmann-La Roche, GB 774 621, 1957 (J. A.
Mitsuhashi, H. Kumobayashi, S. Akutagawa). Birbiglia, G. O. Chase, J. Galender).
46. Universal Oil Products, US 3 275 696, 1961 72. Haarmann & Reimer GmbH, BE 615 962,
(E. Goldstein). 1962 (K. Bauer, J. Pelz).
47. BASF, DE-OS 2 934 250, 1979 (M. Horner, M. 73. SCM Corp., US 4 000 207, 1976 (G. L.
Irrgang, A. Nissen). Kaiser).
48. K. Ziegler, DE-AS 1 118 775, 1960. 74. R. Emberger, R. Hopp in R. G. Berger, S. Nitz,
49. Hercules Powder, US 2 388 084, 1945 (A. L. P. Schreier (ed.): Topics in Flavour Research,
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75. Takasago Perfumery, EP 68 506, 1982 (S. 102. International Flavors & Fragrances, US
Otsuka, K. Tani, T. Yamagata, S. Akutagawa, 4 014 944, 1976 (J. B. Hall, W. J. Wiegers).
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76. Bush Boake Allen, FR 1 374 732, 1964 (G. K. Lange, K. Bauer).
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77. Glidden, US 3 031 442, 1958 (R. L. Webb). 4 007 137, 1975 (J. M. Sanders, W. L.
78. Sukh Dev: “New Industrial Processes Based Schreiber, J. B. Hall).
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Marekov, I. Ognyanov, A. Arahovates ed.). Steinbach).
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Fleischer, K. Bauer, R. Hopp). H. Kuhlmann).
80. Takasago Perfumery, DE-AS 1 815 845, 1968 107. International Flavors & Fragrances, US
(T. Moroe, S. Hattori, A. Komatsu, Y. 4 045 489, 1976 (W. J. Wiegers, J. B. Hall).
Yamaguchi). 108. Firmenich, DE 2 502 767, 1975
81. Hoechst AG, DE 955 499, 1956 (H. Hoyer, G. (K.-H. Schulte-Elte).
Keicher, H. Schubert). 109. IFF, DE 2 036 936, 1971 (J. B. Hall,
82. Dragoco, DE 1 235 306, 1965 (E. Klein). E. T. Theimer).
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84. Dow Chemical Co., US 3 124 614, 1958 (L. J. 111. Firmenich, US 4 302 607, 1981 (G. H. Büchi,
Dankert, D. A. Pernoda). H. Wüest).
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B. J. Kane, D. G. Young). 113. Toray Industries, DE 2 141 309, 1971 (A.
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88. Haarmann & Reimer, DE 2 455 761, 1974 (G. Kroning).
Blume, R. Hopp, W. Sturm). 116. Van Ameringen-Haebler, US 2 927 127, 1960
89. BASF, DE-AS 1 286 019, 1967 (H. Pommer, (W. T. Somerville, E. T. Theimer).
W. Reit, W. Pasedach, W. Hoffmann). 117. Firmenich, GB 907 431, 1961 (A. Firmenich,
90. BASF, DE-AS 1 286 018, 1967 (H. Pommer, R. Firmenich, G. Firmenich, R. E. Firmenich).
W. Reif, H. Pasedach, W. Hoffmann). 118. Roure Bertrand Dupont S.A., DE 2 732 107,
91. Hoffmann-La Roche, DE 1 109 677, 1959 (R. 1977 (P. J. Teisseire, M. Plattier, E. Giraudi).
Marbet, G. Saucy). 119. Nippon Zeon, EP 0 399 788 A2, 1990 (T.
92. Polak & Schwarz, GB 812 727, 1959 (M. G. J. Yamada, H. Fujisawa, H. Tanaka).
Beets, H. van Essen). 120. Firmenich, WO 96/00 206, 1996, (V.
93. Hoffmann-La Roche, GB 865 478, 1961. Rautenstrauch, J.-J. Riedhauser).
94. Studiengesellschaft Kohle, FR 1 355 944, 1962 121. Polak’s Frutal Works, NL 71 15 065, 1972
(G. Ohloff, G. Schade). (A. M. Cohen).
95. Firmenich, CH 563 951, 1972 (K. H. 122. Toyo Soda, JP 78 31 635, 1976 (K. Kondo, K.
Schulte-Elte). Komiya, H. Iwamoto); Chem. Abstr. 89 (1978)
96. J. Kulesza, J. Podlejski, A. Falkowski, PL 75313a.
57 707, 1966; Chem. Abstr. 72 (1970) 12914a. 123. Ruhrchemie, FR 2 015 475, 1970.
97. Japan Terpene Chemical Co., JP 68 27 107, 124. Engelhard Minerals and Chemicals Corp., US
1966 (Y. Matsubara, K. Takei); Chem. Abstr. 3 655 777, 1968 (P. N. Rylander, D. R. Steele).
70 (1969) 58071k. 125. H. I. Schlesinger, H. C. Brown, US 2 683 721,
98. W. Klose, K. Bochow, DD 69 586, 1967. 1954.
99. Firmenich, DE 2 008 254, 1970 (E. Sundt, G. 126. Ajinomoto, JP 72 42 278, 1971 (Y. Matsuzawa,
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100. E. Demole, P. Enggist, G. Ohloff, Helv. Chim. (1973) 135878y.
Acta 65 (1982) no. 6, 1785 – 1794. 127. Mitsubishi Petrochemical Co., JP 74 25 654,
101. Givaudan, CH 629 461, 1977 (W. M. Easter, 1970 (T. Hashimoto, M. Tanaka); Chem. Abstr.
R. E. Naipawer). 82 (1975) 170375m.
124 Flavors and Fragrances

128. Lee et al., Gas Chromatography, Academic 151. J. Imamura, Yuko Gosei Kagaku Kyokaishi 37
Press, New York 1962, p. 475. (1979) 667 – 677; Chem. Abstr. 92 (1980)
129. Universal Oil Products, US 3 520 934, 1968 6158d.
(W. Dunkel, D. J. Eckardt, A. Stern). 152. BASF, DE 2 848 397, 1978 (D. Degner, M.
130. Rhône-Poulenc, DE-AS 1 145 161, 1958 (I. Barl, H. Siegel).
Scriabine). 153. U. Krings, D. Ganßer, R. G. Berger,
131. BASF, EP 32 576, 1980 (N. Goetz, W. Lebensmittelchem. 52 (1998) 123.
Hoffmann). 154. D. W. Goheen in K. V. Sarkanen (ed.): Lignins,
132. United States Rubber Co., US 2 529 186, 1950 Interscience, New York 1971, pp. 797 – 831.
(H. R. Richmond). 155. Ube Industries, JP 76 128 934, 1975 (S. Nagai,
133. Polak’s Frutal Works, FR 1 392 804, 1963 (J. T. Enomiya, T. Nakamura); Chem. Abstr. 86
Stofberg, B. van der Wal, K. N. Nieuwland). (1977) 189514k.
134. Givaudan, US 3 078 319, 1960 (T. F. Wood).
156. Ube Industries, DE 2 804 063, 1978 (S.
135. Naarden Int. N.V., NL-A 78 02 038, 1977.
Umemura, N. Takamitsu, T. Enomiya, H.
136. Polak’s Frutal Works, DE-AS 1 045 399, 1954
Shiraishi et al.).
(E. H. Polak).
137. Givaudan, US 3 856 875, 1973 (T. F. Wood, E. 157. Brichima, DE-OS 2 703 640, 1977 (P.
Heilweil). Maggioni).
138. Recherche et Industrie Therapeutiques, GB 158. Haarmann & Reimer, DE-OS 2 754 490, 1977
1 032 879, 1965 (P. Crooy). (K. Bauer, R. Mölleken).
139. Warszawa Fabryka Syntetykow Zapachowych, 159. Dragoco Gerberding & Co., GB 876 684, 1958
PL 50 349, 1963 (T. Zardecki); Chem. Abstr. (F. Porsch).
66 (1967) 55210m. 160. BASF, DE-AS 2 145 308, 1971 (R. Fischer, W.
140. Haarmann & Reimer, DE-AS 2 256 483, 1972 Körnig).
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141. Council of Scientific and Industrial Research, Cosmet., Aromes 52 (1983) 45 – 49.
IN 146 359, 1977 (Y. R. Ramachandra, S. N. 162. PFW Beheer, DE 2 359 233, 1974 (A. M.
Mahapatra); Chem. Abstr. 92 (1980) 22281u. Cohen).
142. All-Union Scientific Research Institute of 163. Takasago Perfumery Co., JP 77 122 336, 1976
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1970 (G. E. Svadkowskaya, L. A. Kheifits, Abstr. 88 (1978) 136324h.
A. I. Platova, K. Denisenkova); Chem. Abstr. 164. Studiengesellschaft Kohle, DE 1 137 730,
73 (1970) 14450r. 1961 (G. O. Schenck, G. Ohloff, E. Klein).
143. Haarmann & Reimer, DE-AS 2 418 974, 1974 165. Firmenich, CH 474 500, 1967 (L. Re, G.
(K. Bauer, R. Mölleken). Ohloff).
144. Rhône-Poulenc, DE-AS 1 936 727, 1969 (P. 166. Polak’s Frutal Works, DE-OS 2 812 713, 1978
Gandilhon). (A. M. Cohen).
145. Givaudan, DE-OS 2 508 347, 1975 (A. J. 167. International Flavors & Fragrances, US
Chalk). 3 910 964, 1975 (J. M. Sanders, L. H. Michael).
146. S. G. Polyakova, L. L. Malkina, O. M. 168. Haarmann & Reimer, EP-A 120 257, 1984 (H.
Khol’mer, I. M. Lebedev et al., SU 114 197, Finkelmeier, R. Hopp).
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147. O. M. Khol’mer, S. G. Polyakova, SU 126 879, 714 645, 1954.
1960; Chem. Abstr. 54 (1960) 19596c. 170. DRAGOCO, EP 0 543 470 B1, 1992 (E. J.
148. All-Union Scientific Research Institute of
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Synthetic and Natural Perfumes, SU 407 872,
171. May & Baker, FR 1 577 817, 1967.
1973 (G. E. Svadkovskaya, S. G. Polyakova,
172. DRAGOCO, DE 197 044 84 A1, 1997
N. A. Daev, N. N. Zelenetskii et al.); Chem.
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173. Ube Industries, JP 76 95 058, 1975 (T.
149. Collins Chemical Co., US 3 104 265, 1963 (A.
Yamasaki, M. Nakai, Y. Kuroki, M. Oda, Y.
Fiecchi).
Kawaguchi, M. Kobayashi); Chem. Abstr. 85
150. All-Union Scientific Research Institute of
(1976) 192191n.
Synthetic and Natural Perfumes, DE-OS
174. Haarmann & Reimer, DE 2 136 496, 1971 (R.
2 221 116, 1972 (L. K. Andreeva, I. A.
Hopp, K. Bauer).
Kheifits, T. P. Cherkasova, E. A. Berger et al.);
Chem. Abstr. 78 (1973) 58046w.
 Flavors and Fragrances 125

175. Firmenich, DE 2 026 056, 1970 (J. J. Becker). 193. B. Meyer-Warnod, Perfum. Flavor. 9 (1984)
176. Soda Koryo, DE 2 818 126, 1978 (K. Suzuki, no. 04/05, 93.
T. Eto, T. Otsuka, S. Abe). 194. K. Formazek, K. H. Kubeczka, Essential Oil
177. Haarmann & Reimer, DE 2 731 543, 1977 (K. Analysis by Capillary Chromatography and
Bauer, A. Körber). Carbon-13 NMR Spectroscopy, J. Wiley &
178. Firmenich, EP 0 424 787 A2, 1989 (P. Sons, New York 1982.
Fankhauser, P. Fantini). 195. a) B. Lawrence, Progress in Essential Oils,
179. Haarmann & Reimer, EP 0 512 348, 1992(R. bimonthly column in Perfum. and Flavor. b)
Hopp et al.). Miltitzer Berichte, collection of brief reports
180. Chemische Werke Hüls, DE 2 547 267, 1975 on essential oils, flavors, and fragrances,
(J. Ritter, K. Burzin, K. H. Magosch, R. published annually, VEB Chemisches Werk
Feinauer). Miltitz, Miltitz (German Democratic
181. K. D. Carlson, V. E. Sohns, R. B. Perkins, E. L. Republic).
Huffmann, Ind. Eng. Chem., Prod. Res. Dev. 196. D. Zander in Erhard, Götz, Bödecker, Seybold
16 (1977) no. 1, 95 – 101. (eds.): Handwörterbuch der Pflanzennamen,
182. Dow Chemical, US 4 036 854, 1975 (K. Y. 16th ed., Verlag E. Ulmer, Stuttgart 2000.
Chang). 197. EOA No. 180.
183. Stamicarbon, NL 72 02 539, 1972 (J. A. 198. EOA No. 183.
Thoma, J. M. Deumens, E. J. Verheijen). 199. EOA No. 147.
184. Stamicarbon, DE 2 309 536, 1973 (S. 200. ISO 3525- 1979.
201. T. A.van Beek, R. Kleis, M. A. Posthumus, A.
Schaafsma, J. Deumens).
van Veldhuizen, Phytochemistry 28 (1989)
185. Union Carbide, GB 863 446, 1961 (B. Phillips,
no. 7, 1909 – 1911.
P. Staacher, D. L. Mac’Peek).
202. EOA No. 96.
186. M. Ishihara, K. Yonetani, T. Shibai, Y. Tanaka,
203. EOA No. 97.
7th International Congress of Essential Oils, 204. B. D. Mookherjee, R. R. Patel, VIIth
Kyoto 1977, pp. 266 – 269; Chem. Abstr. 92 International Congress of Essential Oils,
(1980) 75722v. Kyoto 1977, pp. 479 – 482; Chem. Abstr. 92
187. H. Maarse, E. A. Visscher, Volatile compounds (1980) 203412h.
in Foods, Qualitative Data, TNO-Division for 205. EOA No. 194.
nutrition and food research TNO-CIVO Food 206. EOA No. 195.
Analysis Institute, Zeist (Netherlands) 207. B. D. Mookherjee, R. W. Trenkle in Fedarom,
1983 – 1987. Technical Data of the VIIIth Intern. Congress
188. R. Tressl, T. Kossa, M. Holzer in F. Drawert of Essential Oils, Cannes 1980, published
(ed.): Geruch- und Geschmackstoffe, , 1982 (Grasse), p. 580.
,Bildung flüchtiger Aromastoffe durch 208. ISO/CD 3475- 2000.
Maillard-Reaktionen,“ Verlag Hans Carl, 209. ISO/DIS 11043– 1996.
Nürnberg1975, pp. 33 – 47. 210. ISO/WD 3045- 2000.
189. G. Vernin, “Mechanism of Formation of 211. H. M. Boelens et al., Perfum. Flavor. 6
Heterocyclic Compounds in Maillard and (1981/1982) no. 6, 15.
Pyrolysis Reactions”, Chem. Heterocycl. 212. EOA No. 215.
Compd. Flavours Aromas 1982, 151 – 207. 213. R. Kaiser, D. Lamparsky, P. Schudel, J. Agric.
190. G. Ohloff, I. Flament, “The Role of Food Chem. 23 (1975) no. 5, 943 – 950.
Heteroaromatic Substances in the Aroma 214. B. M. Lawrence, Perfum. Flavor 23 (1998)
Compounds of Foodstuffs” in Progress in the no. 4, 47 – 50.
Chemistry of Organic Natural Products, 215. EOA No. 101.
vol. 36, Springer Verlag, Wien 1979, 216. EOA No. 98.
pp. 231 – 283. 217. EOA No. 69.
191. G. Ohloff, I. Flament, W. Pickenhagen, 218. ISO/DIS 8896– 1985.
“Flavor Chemistry”, Food Reviews 219. ISO 4733- 1981.
220. AFNOR NF T 75-352 1989.
International 1 (1985) no. 1, 99 – 148.
221. EOA No. 229.
192. K. D. Protzen, in R. Carle (ed.): Ätherische Öle
222. EOA No. 86.
- Anspruch und Wirklichkeit, 223. O. Motl, S. K. Paknikar, Collect. Czech. Chem.
Wissenschaftliche Verlagsgesellschaft mbH, Commun. 33 (1968) 1939 – 1942; Chem.
Stuttgart 1993, p. 23. Abstr. 69 (1968) 25059p.
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224. ISO/DIS 9843– 2000. 267. ISO 4731- 1978.

225. ISO/CD 4725- 2000. 268. EOA No. 13.
226. EOA No. 36 B. 269. EOA No. 63.
227. ISO/WD 4724- 1997. 270. ISO 8897- 1991.
228. ISO/DIS 3760- 2000. 271. EOA No. 181.
229. EOA No. 156. 272. EOA No. 119.
230. AFNOR T 75-253 1992. 273. ISO/DIS 3515- 2000.
231. ISO/DIS 3216- 1994. 274. ISO/FDIS 4719- 1999.
232. ISO/DIS 3524- 2000. 275. ISO/DIS 3054- 2000.
233. EOA No. 87 276. ISO/FDIS 8902- 1999.
234. ISO/FDIS 3520- 1998. 277. EOA No. 157.
235. ISO/WD 3053- 1975. 278. ISO/DIS 3214- 1998.
236. R. J. Braddock, J. W. Kesterson, J. Food Sci. 279. ISO/FDIS 11019- 1997.
41 (1976) no. 5, 1007 – 1010. 280. EOA No. 76.
237. M. G. Moshonas, E. Shaw, J. Agric. Food 281. ISO/CD 4728- 1999.
Chem. 22 (1974) 282 – 284. 282. C. Ehret, Neue Inhaltsstoffe aus dem
238. ISO/CD 855- 2001. Mimosablütenöl, lecture given at the meeting
239. L. Haro, W. E. Faas, Perfum. Flavor. 10 of the Vereinigung von Seifen-, Parfümerie-
(1985) no. 5, 67. und Waschmittelfachleuten, Bad
240. L. Haro-Guzman in Fedarom, Technical Data Dürkheim,Oct. 1986.
of the VIIIth International Congress of 283. ISO/FDIS 9776- 1998.
Essential Oils Cannes 1980, published 1982 284. ISO/CD 856- 2000.
(Grasse), p. 181. 285. ISO/DIS 3033- 1986.
241. D. McHale in Fedarom, Technical Data of the 286. B. M. Lawrence, Perfum. Flavor. 5 (1980)
VIIIth International Congress of Essential Oils no. 4, 6 – 17.
Cannes 1980, published 1982 (Grasse), p. 177. 287. W. A. Todd, M. J. Murray, Perfum. Essent. Oil
242. ISO/WD 3809- 1997. Rec. 59 (1968) 97 – 102.
243. ISO/DIS 3519- 1994. 288. ISO 3714- 1980.
244. ISO/DIS 3528- 1994. 289. EOA No. 212.
245. ISO 9844- 1991. 290. EOA No. 141.
246. ISO/DIS 3140- 1989. 291. R. A. Wilson, B. D. Mookherjee, IXth Intern.
247. ISO/DIS 3142- 1994. Congress of Essential Oils, Singapore 1983,
248. ISO/DIS 3141- 1994. Technical Paper, vol. 4, p. 1.
249. EOA No. 10. 292. ISO/DIS 3517- 2000.
250. ISO/DIS 3516- 1994. 293. ISO/FDIS 3215- 1998.
251. ISO/DIS 9301- 2000. 294. T. H. Moxham in E. Brunke (ed.): Progress in
252. ISO/CD 3849- 2000. Essential Oil Research, De Gruyter, Berlin
253. ISO/DIS 3848- 2000. 1986, p. 491.
254. O. P. Virmani, S. C. Datta, Flavour Ind. 2 295. S. Huneck in W. Herz et al (ed.): Progress in
(1971) no. 10, 595 – 602. the Chemistry of Organic Natural Products
255. ISO/WD 3217- 2000. vol. 81, Springer-Verlag, New York 2001,
256. ISO/CD 4718- 2000. p. 230.
257. ISO 4727- 1982. 296. EOA No. 68.
258. J. Garnero, P. Buil, D. Joulain, R. Tabacchi, 297. B. M. Lawrence, Perfum. Flavor. 17 (1992)
Parfums, Cosmet. Aromes 20 (1978) 33 – 36. no. 3, 61 – 64.
259. AFNOR NF T 75-254 1992. 298. EOA No. 67.
260. ISO/FDIS 10624- 1997. 299. EOA No. 142.
261. ISO 3065- 1974. 300. ISO/FDIS 14717- 1999.
262. ISO/CD 7704- 1997. 301. EOA No. 116.
263. ISO/DIS 3044- 1994. 302. B. M. Lawrence, Perfum. Flavor. 20 (1995)
264. E. Guenther, Perfum. Essent. Oil Rec. 59 no. 6, 35 – 42.
(1968) 634 – 641. 303. EOA No. 293.
265. F. Porsch, H. Farnow, H. Winkler, Dragoco 304. C. Masanetz, W. Grosch, Flavor Frag. J. 13
Report 1965, 47 – 49. (1998) 115 – 124.
266. ISO/FDIS 14716- 1998. 305. ISO/DIS 3527- 1998.
 Flavors and Fragrances 127

306. ISO 3527- 1975. 326. ISO/DIS 9909- 1991.

307. ISO/CD 3757- 1999. 327. ISO 3526- 1991.
308. P. Teisseire, VIIth International Congress of 328. ISO/DIS 3518- 2000.
Essential Oils, Kyoto 1977, pp. 315 – 319; 329. ISO 590- 1981.
Chem. Abstr. 92 (1980) 129084j. 330. EOA No. 197.
309. ISO 3061- 1979. 331. ISO/FDIS 11016- 1999.
310. EOA No. 65. 332. ISO/DIS 10115- 1989.
311. ISO/DIS 3064- 1998. 333. ISO/DIS 4730- 1992.
312. ISO/CD 8901- 1999. 334. ISO/FDIS 14715- 1999.
313. ISO 3043- 1975. 335. ISO/R 412- 1965.
314. EOA No. 126. 336. ISO/FDIS 11020- 1997.
315. EOA No. 50. 337. EOA No. 165.
316. EOA No. 112. 338. ISO/DIS 4716- 2000.
317. EOA No. 133. 339. ISO/CD 3063- 2000.
318. EOA No 32. 340. E. M. Gaydou, R. P. Randriamiharisoa,
319. ISO/CD 9842- 1999. J.-P-Bianchini, J.-R. Llinas, J. Agric. Food
320. G. Ohloff, E. Demole, J. Chromatogr. 406 Chem. 36 (1988) 574 – 579.
(1987) 181. 341. ISO/DIS 3523- 2000.
321. N. Nicolov, P. Dragostinov, L. Luba, A.
342. G. Jellinek, Sensory Evaluation of Food, VCH
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Stuttgart 1993, p. 103 – 133.
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325. AFNOR NF T 75-255 1992.
 Flocculants 1

Flocculants
Hans Burkert, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
Jürgen Hartmann, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . 1 3.2. Specific Ion Adsorption . . . . . . . . 5

2. Classification of Flocculants . . . . . 2 3.3. Polymer Charge Patch . . . . . . . . . 5
2.1. Inorganic Flocculants . . . . . . . . . 2 3.4. Polymer Bridging . . . . . . . . . . . . 6
2.2. Natural Organic Flocculants . . . . . 2 4. Uses . . . . . . . . . . . . . . . . . . . . . 6
2.3. Synthetic Organic Flocculants . . . 2
5. Choice of Optimum Flocculant . . . 6
2.3.1. Chemical Structure . . . . . . . . . . . . 2
2.3.2. Production Requirements . . . . . . . . 3 6. Legal Aspects . . . . . . . . . . . . . . . 8
3. Flocculation Mechanisms . . . . . . . 5 7. Economic Aspects . . . . . . . . . . . . 9
3.1. Double Layer Compression . . . . . 5 8. References . . . . . . . . . . . . . . . . . 9

1. Introduction discovered at the beginning of the 1950s at

BASF, and at about the same time, Cyanamid
Flocculants are used to optimize the separation filed a patent application for polymeric floccu-
of the solid phase from the liquid phase in aque- lants in Canada [5]. Flocculants produced by
ous suspensions. These suspensions usually con- BASF were first used successfully in 1955 for
sist of organic or inorganic particles, which are the clarification of washing water in German
of finely divided to colloidal consistency and collieries [6]. Shortly afterwards, Dow Chem-
are distributed in water as a dispersion medium. ical introduced their flocculants into the United
With smaller particles, the suspension is more States market. Since then, organic flocculants
stable, i.e., the lower is the tendency for the par- have steadily gained in importance and are now
ticles to agglomerate and sediment. However, used worldwide in many branches of industry
addition of a flocculant drastically increases the and in water-treatment plants.
rate of particle sedimentation so that a clear, su-
pernatant liquid is obtained. The settled sludge
can then be filtered rapidly or centrifuged, re-
sulting in a more efficient separation.
2. Classification of Flocculants
In this article, a distinction is made between
organic and inorganic flocculants in accordance 2.1. Inorganic Flocculants
with the international convention.
Inorganic flocculants are mostly aluminum The most important inorganic flocculants are the
or iron salts that form insoluble hydroxide pre- trivalent salts of aluminum and iron, as well as
cipitates in water. Impurities in the water are ad- activated silica, and are listed in Table 1.
sorbed onto the sedimenting precipitate flocs and
are thus removed from the water. A combination
of inorganic and organic flocculants is frequently 2.2. Natural Organic Flocculants
employed in the treatment of water.
Organic flocculants are natural or synthetic The group of natural organic flocculants in-
water-soluble polymers. They may also be called cludes water-soluble starch [9005-25-8] [7],
sedimentation, clarification, filtration, or cen- guar gum, alginates [9005-38-3], and products
trifugation aids, according to their final use. based on chitin [8], glue, and gelatin [9]. Owing
The ability of synthetic polymers to increase the to their low relative molecular masses (10 000 –
sedimentation rate of suspensions was first ob- 100 000), these flocculants are only moderately
served in 1939 [4]. The flocculation effect ex- efficient. Despite the very low cost of some of
erted by synthetic water-soluble polymers was these natural products, the cost-to-performance

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11 251
2 Flocculants
Table 1. Inorganic flocculants

Type Formula CAS registry Comments

number

Alum Al2 (SO4 )3 · 14 H2 O [7784-31-8] used as a powder (17 wt % Al2 O3 ) or 50 wt % solution

(8.5 wt % Al2 O3 )
Poly(aluminum chloride) Al(OH)1.5 (SO4 )0.125 Cl1.25 [7446-70-0] obtained by partially hydrolyzing AlCl3 [7446-70-0], used
as a solution (10 wt % Al2 O3 )
Sodium aluminate NaAlO2 [1302-42-7] used as a powder and solution
Iron(III) chloride FeCl3 [7705-08-0] used as a powder (100 wt % FeCl3 ) or solution
(35 – 45 wt %)
Iron(III) sulfate Fe2 (SO4 )3 [10028-22-5] used as a granulate
Iron(III) sulfate chloride FeClSO4 [12410-14-9] obtained by oxidation of FeSO4 with chlorine in solution,
used as a solution (30 – 40 wt %)
Iron(II) sulfate FeSO4 · 7 H2 O [7782-63-0] used as a crystalline powder
Sodium silicate (activated silica) Na2 SiO3 [1344-09-8] used as a solution

ratio of synthetic flocculants is considerably poly(ethylene oxide) [25322-68-3] is obtained

more favorable due to their very high rela- by polymerizing ethylene oxide over special
tive molecular masses. Consequently, natural or- catalysts, e.g., alkaline-earth carbonates or alu-
ganic flocculants have steadily declined in im- minum alcoholates (C1 – C4 ) [13], [14]. Non-
portance. Only soluble starch was able to main- ionic homopolymers are, however, of little com-
tain its market position in certain fields for any mercial importance as flocculants.
length of time, e.g., in the preparation of bauxite
(red mud flocculation [10], → Aluminum Ox- Ionic Polymers. The most important ionic
ide, Chap. 3.1.4.) and the purification of water polymeric flocculants are copolymers de-
(→ Water). Starch was chosen for the latter ap- rived from acrylamide [79-06-1] and a
plication because, unlike synthetic organic floc- charged comonomer [→ Polyacrylamides and
culants, its use did not require legal permission. Poly(Acrylic Acids)].
Flocculants based on natural organic polymers Anionic Polymers. Almost all anionic poly-
are now of little importance and are not, there- meric flocculants are synthesized as ho-
fore, further discussed. mopolymers or acrylamide copolymers of the
alkali-metal or ammonium salts of acrylic
acid [79-10-7]. Methacrylic acid [79-41-4],
2.3. Synthetic Organic Flocculants maleic acid [6915-18-0], ethylenesulfonic acid
[1184-84-4], 4-styrenesulfonic acid [98-70-4],
2.3.1. Chemical Structure and 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-
propanesulfonic acid [15214-89-8] are also used
The chemical structure of synthetic organic floc- as comonomers in acrylamide copolymers, but
culants determines their flocculating properties. are of little practical importance.
They are water-soluble polymers which can be Cationic Polymers. Other water-soluble
classified into nonionic polymers [11], and ionic comonomers are used for the production of
polymers (polyelectrolytes); the latter can be cationic polymers in addition to those listed in
further subdivided into anionic, cationic, and Table 2, the most important being the follow-
amphoteric types [12]. Examples of flocculants ing: substituted acrylamide and methacrylamide
from each of these groups are given in Table 2. salts [16–19]; N-vinylformamide [13162-05-5]
and N-vinylacetamide [5202-78-8], which
Nonionic Polymers. Other nonionic ho- are polymerized and hydrolyzed in alkaline
mopolymers not cited in Table 2 can be pro- or acidic media to “vinylamine” copolymers
duced from 1-vinyl-2-pyrrolidone [88-12-0], [593-67-9] [20–23]; and salts of N-vinylimida-
N-vinylformamide [13162-05-5], methoxy- zole [1072-63-5],
ethylene [107-25-5], etc. Poly(vinyl alcohol) 2-vinylpyridine [100-69-6] or 4-vinylpyri-
[9002-89-5] is synthesized by hydrolysis of dine [100-43-6].
poly(vinyl acetate). Very high molecular mass
 Flocculants 3
Table 2. Synthetic organic flocculants

Water-insoluble or sparingly water-soluble purity of the starting materials, especially the

comonomers can also be incorporated, provided monomers. Contamination by inhibitors or by
the resulting copolymers are still soluble in wa- chain-transfer or cross-linking agents must be
ter. avoided. Water is the preferred solvent because
Cationic homopolymers and copoly- other solvents either yield polymers of lower
mers of dialkyldiallylammonium chlorides, molecular mass due to transfer reactions or pose
e.g., diallyldimethylammonium chloride an ecological risk.
[7398-69-8], can be produced by free-radical A second important prerequisite for obtain-
polymerization; these polymers are composed ing a high molecular mass is a polymerization
of chains bearing cyclic structures [24–28]. temperature that is as low as possible. The poly-
The polyamines are another important class merization temperature depends largely on the
of cationic flocculants and are obtained by poly- choice of initiator. Conventional free-radical ini-
condensation. The starting materials are alky- tiators, such as alkali-metal persulfates and per-
lene dichlorides or epichlorohydrin and ammo- oxides, are being superseded by azo initiators,
nia, low molecular mass alkylene polyamines, which decompose at lower temperatures, e.g.,
or polyaminoamides [29–33]. Polycondensation 2,2 -azobis(2-amidinopropane)hydrochloride,
of ethyleneimine [151-56-4] yields polyethylen- 2,2 -azobis(2,4-dimethylvaleronitrile). Alterna-
imines. tive initiators are redox catalysts (e.g., ascorbic
Amphoteric polymers that bear both anionic acid) and UV and γ-radiation [34–39]. Attempts
and cationic charges are of little practical impor- are also being made to achieve homogeneous
tance as flocculants. temperature distribution by removing the heat
produced during polymerization as efficiently
as possible from the reaction vessel, e.g., by us-
2.3.2. Production Requirements ing evaporative cooling, special monomer feed
techniques in thin layers [36], [40], [41], or two-
The raw materials used to synthesize organic phase systems. A method for trapping the heat
flocculants are described in Section 2.3.1. of polymerization with endothermic reactions
High molecular mass polymers are required has also been described [42], [43].
for efficient flocculation (cf. Section 3.4). Thus,
very strict requirements are imposed on the
4 Flocculants

Synthetic organic flocculants are marketed of the polymers with low molecular mass alco-
as liquids (either solutions or emulsions) and hols or acetone in a heavy-duty mixer, drying on
solids. rollers, spray-drying, azeotropic distillation with
inert organic solvents, and irradiation with mi-
Solutions. Polycondensation in an aqueous crowaves. Water-in-oil emulsions are not often
solution is an important technique for produc- dried because of the relatively high initial cost of
ing polyamine flocculant solutions. A polymer the raw materials. Solid flocculants are usually
content of ca. 50 wt % can be attained. obtained from aqueous polymer solutions. High
When acrylamide is copolymerized in so- polymer concentrations are used to reduce dry-
lution, the high molecular masses that are de- ing costs. The solutions form firm gels, which
sired result in highly viscous, gel-like solutions, are cut into small pieces and dried. The particle
which are difficult to handle when the polymer size of the final powder is adjusted by milling
content exceeds 10 wt %. Special metering and and sieving.
solubilizing equipment is required [44]. These An industrially important alternative for ob-
solutions are important starting materials for the taining solid flocculants is based on poly-
manufacture of solid flocculants. merization of a water-in-oil suspension [58–
61] (for details of suspension polymerization,
Emulsions. Emulsion flocculants are more → Polymerization Processes). The concentrated
important than solution flocculants and are made aqueous monomer solution is emulsified in the
by the polymerization of water-in-oil emulsions presence of special protective colloids in a hy-
[45–50] (for details of emulsion polymerization, drophobic phase. The hydrophobic phase may
→ Polymerization Processes). A concentrated be a low-boiling aliphatic compound, an aro-
aqueous monomer solution is emulsified with matic hydrocarbon, or a halogen derivative of
emulsifiers in a dispersion phase that usually the latter. Polymerization is started with water-
consists of a high-boiling mixture of aliphatic soluble initiators and proceeds by evaporative
hydrocarbons. The particle size of the emulsions cooling to produce polymer beads that contain
is 0.1 – 10 µm and their viscosity is low, usually water and have a particle size of 0.1 – 0.5 mm.
less than 1500 mPa · s. Polymerization is then The water is then removed by azeotropic dis-
started by adding oil- or water-soluble initiators; tillation, the hydrophobic phase serving as an
azo initiators are preferred, but the use of UV ir- entraining agent. The solid product is obtained
radiation has also been described [51]. Wetting after separation of the organic solvent, drying,
agents are added to the polymerized water-in-oil and sieving.
emulsions prior to use; the emulsions are then Solid flocculants with high molecular masses
inverted in water [52]. Variations on this simple can also be prepared by precipitation polymer-
batch method dissipate the heat of polymeriza- ization in, for example, tert-butanol or its mix-
tion more efficiently either by evaporative cool- tures with water [62], [63], but this method is
ing [53], [54] or by special monomer feed tech- less important.
niques [55], [56]. These methods yield emul- The advantages of solid products are their
sions with a polymer content of 25 – 45 wt %. high flocculant concentration, which results in
An even higher polymer content can be obtained lower marketing costs and increased stability.
by azeotropic distillation of the internal aque- Their disadvantages are the necessity for a dry-
ous phase and some of the hydrocarbon mixtures ing stage, with the associated risk of product
[57]. damage, and their slow rate of dissolution. The
Water-in-oil emulsions are easy to handle de- latter problem has been largely solved by the
spite their high polymer content and require no development of modern dosing devices.
drying with the attendant risk of product dam-
age. However, the starting materials are more
expensive and the stability of the emulsions is 3. Flocculation Mechanisms
limited.
The stability of a suspension depends on
Solids. Liquid products can be dried to give the number, size, density, and surface prop-
powders. Drying methods include precipitation erties of the solid particles (internal or dis-
 Flocculants 5

persed phase) and on the density of the ex- 3.2. Specific Ion Adsorption
ternal phase or dispersion medium. The sta-
bility and destabilization of colloids, suspen- The mechanism of specific ion adsorption al-
sions, and emulsions are discussed in detail ways applies when cations are bound chemically
elsewhere ( → Colloids, Chap. 5.,→ Colloids, to the particle surface, e.g., by forming com-
Chap. 6.,→ Colloids, Chap. 7.; → Disperse Sys- plexes with the surface atoms. Thus, the particle
tems and Dispersants, Chap. 3., → Disperse Sys- charge may be partially or completely neutral-
tems and Dispersants, Chap. 4.; → Emulsions). ized [68], [69]. In the latter case, the particles no
In aqueous suspensions, the particle sur- longer repel each other and the conditions for
face has an electrical (usually negative) charge, agglomeration are optimal.
which, for example, in mineral solids originates Trivalent aluminum and iron salts are exam-
from the dissociation of protons from surface hy- ples of flocculants that function in this way. In
droxyl groups belonging to silicate groups [64]. water they are partially or totally hydrolyzed
If counterions (e.g., Ca2+ or Mg2+ ) are present to form positively charged dibasic, tribasic, or
in the surrounding water, they accumulate on polymeric hydroxides that adsorb onto the par-
the surface of the suspended particles, forming ticle surface and neutralize its charge according
an ionic double layer [65]. The excess nega- to their degree of hydrolysis.
tive charge at the shear surface of the double
layer (the zeta potential) can be measured with
a zeta meter. As the zeta potential increases, the 3.3. Polymer Charge Patch
coulombic repulsion between the particles be-
comes stronger and the suspension is more sta- When cationic polymers are added to a suspen-
ble. sion, they are adsorbed to the surfaces of parti-
Many authors distinguish between “coagu- cles with negative charge as described in Sec-
lation” and “flocculation” [66]. Flocculation is tion 3.2. They neutralize the negative charge,
usually taken to mean the process in which parti- but their charge density is higher than that of
cles are interlinked by molecular chains with no the particle surfaces. Thus, positively charged
change in the zeta potential (anionic and non- polymer centers (polymer charge patches) are
ionic organic flocculants). Coagulation, how- formed on the particle surfaces and, in turn,
ever, is taken to mean the electrical neutraliza- come into contact with the negatively charged
tion of suspended particles, as brought about by surfaces of other particles and also destabilize
iron and aluminum hydroxide. the suspension [70], [71]. Flocculation involving
Four models are used to explain how floccu- relatively low molecular mass cationic polymers
lants aid particle agglomeration. However, more (e.g., polyethylenimine) is thought to proceed by
than one of these mechanisms probably act si- this mechanism.
multaneously.

3.4. Polymer Bridging

3.1. Double Layer Compression
In polymer bridging, high molecular mass poly-
As the cation concentration in the water in- mer chains are adsorbed onto the particle sur-
creases, the thickness of the ionic double layer face and form bridges between adjacent parti-
decreases (i.e., the double layer is compressed), cles [72–75]. Adsorption occurs by electrostatic
thereby reducing the number of collisions bet- forces, van der Waals forces, hydrogen bond-
ween the particles and rendering the suspension ing, and chemical bonding. This model is used
unstable [67]. This mechanism accounts to some to account for the flocculation produced by high
extent for the destabilization of suspensions by molecular mass organic flocculants. The bridg-
inorganic salts, especially by monovalent ions. ing mechanisms of anionic, cationic, and non-
ionic organic flocculants are different.
Mineral (anionic) suspensions are generally
flocculated with anionic polyelectrolytes for
6 Flocculants

economic reasons (e.g., in the coal mining in- maximum recovery of a solid matter and/or the
dustry). This is only possible beause the an- separation of a clear aqueous phase. Combina-
ionic particles are not suspended in deionized tions of organic and inorganic flocculants can,
water, but in hard water. Water hardness varies to some extent, remove dyes and oily impurities
and is primarily caused by divalent calcium and from effluents.
magnesium ions. These positively charged ions If the density of the flocs is similar to that of
are adsorbed onto the negatively charged parti- the aqueous phase, they may float and not settle.
cle surface to form an ionic double layer. The Thus, flocculants may promote flotation, but this
positively charged ions face outward and allow may be troublesome if solids of different compo-
the anionic flocculant to approach the particle sition are to be separated (coal and ore flotation)
closely enough to be adsorbed to its surface [77].
[72]. In this case, bridging is the result of a gen- The most important uses of flocculants are
uine chemical bond in which the divalent cations summarized in Table 3.
link the solid particles with the active groups on
the polymer chain. However, hydrogen bonding
may also play a role. Obviously, mineral sus- 5. Choice of Optimum Flocculant
pensions cannot be flocculated in very soft water
due to the absence of divalent ions. Therefore, Flocculant manufacturers now offer comprehen-
the suspensions must be hardened with anhy- sive ranges of anionic, cationic, and nonionic
drous lime prior to the addition of the polymer. flocculants that differ from one another in the
Alternatively, cationic flocculants can be used. chemistry of their monomeric building blocks,
Obviously, the probability that a polymer can the nature and size of their ionic charge, and
be adsorbed simultaneously onto different parti- their molecular mass [137]. It is not always easy
cles and act as a bridge between them increases to predict which flocculant is most suitable to
with an increase in its molecular mass. Accord- obtain the desired sedimentation rate for a spe-
ingly, the most effective anionic flocculants have cific application. Broadly speaking, anionic and
molecular masses of ca. (10 – 20)×106 . Thus, nonionic organic flocculants are best for neutral
sedimentation is quicker and filtration is eas- suspensions that consist primarily of inorganic
ier when large stable agglomerates or flocs are solids, whereas cationic flocculants are best for
formed [76]. neutral suspensions containing predominantly
Since cationic flocculants are positively organic solids.
charged, they partially or completely neutral-
ize negative charge on particle surfaces, and the
polymer chains cross-link adjacent particles.
The only bridging mechanism that is avail-
able to nonionic synthetic flocculants, e.g., poly-
acrylamide and poly(ethylene oxide), is hydro-
gen bonding.

4. Uses
The fact that suspended solid particles can be
made to agglomerate to form large, rapidly set-
tling, easily filterable flocs is exploited to clarify
suspensions and dewater the resulting sludges.
Flocculants are added to accelerate settling in
basins and to dewater sludge in vacuum filters, Figure 1. Relationship between the sedimentation rate of a
suspension and the quantity of flocculant added
sand filters, belt filters, filter presses, and cen- a) Weakly anionic flocculant; b) Strongly anionic flocculant
trifuges. However, water purification is not the
sole application of flocculants. Each branch of Inorganic flocculants are used mainly to clar-
industry has its own priorities, which may be ify suspensions containing a low concentration
 Flocculants 7
Table 3. Uses of Flocculants

Field of application Use Flocculant type∗ Reference

Mining industries
Coal clarification of washwater and flotation tailings, a-PAA [78], [79]
filtration of concentrates, a-PAA [80], [81]
dewatering of tailings a-PAA, PEI, c-PAA [82], [83]
Ores clarification of flotation tailings, a-PAA [84–87]
thickening and filtration of concentrates PAA, a-PAA
Potash clarification of potash solutions a-PAA [88], [89]
(hot solution and flotation processes),
dewatering of tailings PAA, PEO
Fluorite and barytes clarification of flotation tailings a-PAA [90], [91]
Kaolin thickening of kaolin slurries a-PAA [92], [93]
Salt works clarification of raw brine, sludge dewatering PAS, a-PAA [94]
Phosphate water recovery in mines, PAA, a-PAA
filtration of gypsum, a-PAA [95–97]
clarification of phosphoric acid PAA
Uranium processing filtration of acidic or alkaline solutions PAA, PEO [98], [99]
Foundries and clarification of water for scrubbing gas from
metalworking blast furnaces, clarification of effluents from
sintering and pickling plants, a-PAA [100–102]
purification of electrolytic solutions, PAA, a-PAA [103–105]
clarification of electroplating effluents a-PAA [101]
Bauxite benification thickening of red muds (Bayer process) PAS Aluminum Oxide, [106]
TiO2 production clarification of black liquor, c-PAA, CCP [107]
filtration of TiO2 PAA
Paper industry retention of kaolin and PEI, c-PAA, PA [108–114]
dewatering of slurries on paper machines, PEI, c-PAA, PA
pulp recovery PEI, c-PAA, PA
effluent clarification and dewatering a-PAA, c-PAA
Communal and effluent purification, IF, a-PAA [115–117]
industrial water thickening of activated sewage sludge, c-PAA [118]
treatment plants flotation of activated sewage sludge, c-PAA [119]
mechanical dewatering of sewage sludge, c-PAA [120–124]
phosphate precipitation IF, a-PAA [125]
Clarification of flocculation of surface water, IF, a-PAA [126–128]
potable and clarification of wash water used to flush filters, a-PAA
non-potable water filter conditioning a-PAA, PEI, PA [129], [130]
Sugar processing clarification of sugar juice, dewatering of sludge a-PAA [131–133]
Biotechnology dewatering of biological sludges PEI, PA, c-PAA [134–136]

∗ CCP = cationic carbamoyl polymers; IF = inorganic flocculants; PA = poly(alkylene polyamines); PAA = polyacrylamide;
a-PAA = copolymers of acrylamide and sodium acrylate; c-PAA = copolymers of acrylamide and cationic substituted (meth)acrylates,
neutralized and quaternized; PAS = poly(sodium acrylate); PEO = poly(ethylene oxide); PEI = polyethylenimine.

of particulate material, e.g., in the purification are often preferred to cationic flocculants for
of surface water to potable water. The volumi- economic reasons.
nous hydroxide flocs adsorb both solid and dis-
solved contaminants. If the flocs sediment too Flocculant Addition. At a given flocculant
slowly, the sedimentation rate can be acceler- addition rate, the suspension settles more slowly
ated by adding an organic flocculant. if its solid content increases or if its average
particle diameter decreases [6]. However, the
pH Value. The pH is important in selection amount of flocculant that is required also de-
of a flocculant because it determines the degree pends on the strength of its ionic charge. Figure 1
of dissociation of anionic and cationic polyelec- illustrates the difference in behavior between a
trolytes. Complete dissociation of the floccu- strong and a weak anionic flocculant in a neutral
lant is desired, and anionic and cationic floc- suspension.
culants are, therefore, preferred for alkaline and Powder flocculants tend to clump when they
acidic suspensions, respectively. Nonionic poly- are simply added to water, and a great deal of
mers are affected very little by the pH. In the case energy is needed to incorporate emulsions into
of highly acidic suspensions, nonionic polymers water. Manufacturers supply instructions with
their products and also offer simple devices for
8 Flocculants

overcoming the above-mentioned difficulties as terial for which organic flocculants are gen-
well as problems encountered in continuous pro- erally unsuitable.
cesses. Integrated semiautomatic and automatic 8) Dynamic flocculation measurement with the
equipment is commercially available. Polymeric aid of a laser beam [147]. This method is also
flocculants are generally used as 0.05 – 0.1 wt % used for optimizing the flocculant metering
solutions. Inorganic flocculants are supplied in rate in continuously operating systems.
crystalline form or as aqueous solutions and are
used as 10 wt % solutions.
Normally 0.1 – 0.5 g of flocculant is added
per cubic meter of suspension in the thickener 6. Legal Aspects
or settling basin. When sludge is dewatered with
the aid of filters and centrifuges, 2 – 8 kg of floc- The high molecular mass polymeric flocculants
culant per ton of dry sludge is necessary. are not toxic in themselves. Certain precau-
tions should be taken, however, because they
Laboratory Tests. When a flocculant is cho- all contain small proportions of residual toxic
sen, it is always helpful to carry out laboratory monomers [148], especially acrylamide. Legal
trials with a series of different flocculants [138]. controls apply when the flocculants are used in
Fresh suspensions must be used. Representative the manufacture of food, in the purification of
samples should be taken if the composition of potable water, or for the clarification of sugar
the suspension varies considerably. The manu- juice.
facturer’s literature should be consulted for fur- A list of the flocculants that are approved by
ther details. The following tests can be used, de- the EPA for water purification is printed annually
pending on the intended application: in the United States [149]. Many other countries
have their own regulations, but these regulations
1) Sedimentation tests in a shaker provide in- differ very little from each other. Generally, the
formation about the sedimentation rate and residual monomeric acrylamide content must be
clarity of the supernatant [139]. Laboratory less than 0.05 wt % of the polymer content; the
results can be helpful in calculating floccu- amount of flocculant added to untreated water
lant doses required in continuously operating should not exceed 1 g/m3 [150].
thickeners, thus eliminating long trial periods The United States regulations on the clari-
in the initial period of use [140]. fication of sugar juice [151] are generally ob-
2) Filter plate tests (vacuum filtration). served worldwide; they stipulate that the resid-
3) Büchner funnel tests (filtration with and ual acrylamide monomer content must account
without vacuum) [141], [142]. for less than 0.05 wt % of the polymer content,
4) Pressure filter tests [143]. and the quantity of added flocculant must not ex-
5) Determination of filtration rate (capillary ceed 5 g/m3 . Methods for determining the resid-
suction time) [144], [145].Tests 2 – 5 provide ual monomeric acrylamide content of polymers
information about the dewatering of sludges, and the residual flocculant content of treated wa-
especially with regard to the thickness and ter have been described [150], [152].
moisture content of the filter cake and the
filtration efficiency.
6) Determination of floc stability [143]; this test 7. Economic Aspects
provides information about the dewatering of
sludges in centrifuges. In 1984, the use of synthetic organic flocculants
7) Jar test [146]: In this test the flocculant is (calculated as dry mass) in Western Europe was
added to a suspension in a jar (beaker). Slow ca. 15 000 t and in the United States ca. 40 000 t,
stirring induces the formation of voluminous half of this being accounted for by polyacry-
hydroxide flocs that surround the slurry. The lamides. Large markets also exist in Canada,
sedimentation and clarity of the test sam- South America, Africa, Australia, and Japan.
ples are compared after the stirrer has been Of the inorganic flocculants, alum
switched off. This test is performed on slur- (Al2 (SO4 )3 · 18 H2 O) enjoys the largest market
ries containing very little sedimentable ma- share. In 1978, ca. 400 000 t was used in the
 Flocculants 9

United States and ca. 150 000 t in Western Eu- 8. References

rope, in both cases almost exclusively for water
treatment. General References
1. H. G. Flock, E. G. Rausch in N. M. Bikales
Representative worldwide producers of inor-
(ed.): Encyclopedia of Polymer Sci. and
ganic and synthetic organic flocculants are given
Techn., “Water-Soluble Polymers,” vol. 2,
in Tables 4 and 5. Plenum Press, New York 1973, pp. 21 – 73.
Table 4. Representative worldwide producers of inorganic 2. J. Gregory in C. A. Finch (ed.): Chemistry and
flocculants Technology of Water-Soluble Polymers,
Flocculant Producers Plenum Press, New York 1983, pp. 307 – 320.
3. Philip Molyneux: Water-Soluble Synthetic
Alum Allied (USA) Polymers, “Properties and Behavior,” vol. 2,
Amer. Cyanamid (USA)
Boliden (Sweden) CRC Press, Boca Raton 1984, pp 190 – 217.
Giulini Chemie (FRG)
Stauffer (USA)
Nikkei Kako (Japan)
Specific References
Scintoma Aluminium 4. O. Schweitzer, Kautschuk 15 (1939) 169.
Smelting (Japan) 5. Amer. Cyanamid, CA 734 540, 1952 (R. B.
Poly(aluminum chloride) Giulini Chemie (FRG) Booth, J. M. Dobson).
Sachtleben Chemie (FRG)
Sodium aluminate Giulini Chemie (FRG) 6. F. Drexler, Glückauf 92 (1956) 1023; B.
Nalco Chemical (USA) Franke, Glückauf 92 (1956) 1028.
Sachtleben Chemie (FRG) 7. W. Petersen, Glückauf 70 (1934) 125.
Iron(III) chloride BASF (FRG)
Dow Chemical (USA)
8. R. A. A. Muzzarelli: Chitin, Pergamon Press,
Pennwalt (USA) New York 1977.
Solvay (Switzerland) 9. W. Petersen, F. Gregor, Glückauf 68 (1932)
Iron(III) sulfate Giulini Chemie (FRG) 621.
Iron(III) sulfate chloride Kronos Titan (FRG)
Iron(II) sulfate Kronos Titan (FRG) 10. Corn Products Co., BE 626 712, 1963 (E. F.
Pfizer (USA) Paschall, D. D. Wolfe).
Société des Fabriques de 11. P. Molyneux, Water-Soluble Synthetic
Produits Chimiques de
Thann et Mulhouse
Polymers, “Properties and Behavior,” vol. I,
(France) CRC Press, Boca Raton 1984.
Sodium silicate Allied (USA) 12. R. W. Armstrong, U. P. Strauss in N. M.
Solvay (Belgium)
Wöllner-Werke (FRG)
Bikales (ed.): Encyclopedia of Polymer
Science and Technology, vol. 10, Interscience,
New York 1969, pp. 781 – 861 M. F. Hoover, J.
Macromol. Sci. Chem. A4 (1970) no. 6,
Table 5. Primary worldwide producers of synthetic organic 1327 – 1418 P. Molyneux, Water-Soluble
flocculants
Synthetic Polymers, “Properties and
Producer Flocculant trade name Behavior,” vol. II, CRC Press, Boca Raton
1984, pp. 1 – 62.
Allied Colloids (UK) Magnafloc, Percol,
Zetag 13. Union Carbide, US 2 987 489, 1961 (F. E.
Amer. Cyanamid (USA) Superfloc, Accurac Bailey, F. N. Hill).
BASF (FRG) Sedipur, Polymin 14. Union Carbide, US 3 271 328, 1966 (F. N.
Betz Laboratories (USA) Polyfloc, Betz
Calgon (USA) Calgon, Hydraid
Hill).
Chemische Fabrik Stockhausen (FRG) Praestol 15. A. M. Schiller, T. J. Suen, Ind. Eng. Chem. 48
Dow Chemical (USA) Separan, Purifloc (1956) 2132 – 2137.
Hercules (USA) Hercofloc, Reten 16. Amer. Cyanamid, US 2 595 907, 1952 (W. M.
Kurita Kogyo (Japan) Kurifloc
Mitsubishi Chemical (Japan) Diaclear Thomas, J. A. Price).
Nalco Chemical (USA) Nalco 17. Union Carbide, US 3 014 896, 1961 (C. E.
Röhm (FRG) Rohafloc Colwell, R. C. Miller).
Sankyo Chemical (Japan) Sanpoly
Sanyo Chemical (Japan) Sanfloc
18. Lubrizol Corp., US 3 666 810, 1972 (D. I.
Société Nationale de Floculant (France) Floerger Hoke).
19. Jefferson Chemical Comp., US 3 878 247,
1975 (P. H. Moss, R. M. Gipson).
20. M. Nagata, O. Yoshikawa, M. Sakai, Y.
Sakakibara et al., Nippon Kagaku, Kaishi 50
(1975) 1819 – 1822.
10 Flocculants

21. D. J. Dawson, R. D. Gless, R. E. Wingard, J. 45. Dow Chemical, US 3 284 393, 1966 (J. W.
Am. Chem. Soc. 98 (1976) 5996 – 6000. Vanderhoff, R. M. Wiley).
22. Dynapol, US 4 217 214, 1980 (P. L. Dubin). 46. Nalco Chemical Comp., US 3 826 771, 1971
23. BASF, EP-A 71 050, 1983 (M. Kroener, R. (D. R. Anderson, A. J. Frisque).
Schneider, H. Burkert, F. Linhart et al.). 47. J. W. Vanderhoff, E. B. Bradford, H. L.
24. Amer. Cyanamid, US 3 147 218, 1964 (R. B. Tarkowski, J. B. Shaffer et al.: “Polymerisation
Booth, W. F. Linke). and Polycondensation Processes,” Adv. Chem.
25. Calgon Corp., US 3 412 019, 1968 (M. F. Ser. 34 (1962) 32 – 51.
Hoover, B. Park, R. J. Schaper, J. E. Boothe). 48. W. Baade, K. H. Reichert, Eur. Polym. J. 20
26. J. E. Boothe, H. G. Flock, M. F. Hoover, J. (1984) 505 – 512.
Macromol. Sci. Chem. A4 (1970) no. 6, 49. J. W. Vanderhoff, F. V. DiStefano, M. S.
1419 – 1430. El-Aasser, R. O’Leary, J. Dispersion Sci.
27. J. E. Lancaster, L. Baccei, H. P. Panzer, J. Technol. 5 (1984) 323 – 363.
Polym. Sci. Polym. Lett. Ed. 14 (1976) 50. C. Pichot, C. Graillat, V. Glukhikh, Makromol.
549 – 554. Chem. Suppl. 10/11 (1985) 199 – 214.
28. C. Wandrey, W. Jaeger, Acta Polym. 36 (1985) 51. Bayer, DE-AS 2 354 006, 1973 (W. Keller, F.
100 – 102. Müller).
29. Nalco Chem. Comp., US 3 174 928, 1965 52. Nalco Chemical Comp., US 3 624 019, 1970
(G. T. Kekish). (D. R. Anderson, A. J. Frisque).
30. Dow Chemical, US 3 275 588, 1966 (D. C. 53. Hercules Inc., US 3 095 404, 1959 (D. C.
Garms). Lincoln, W. P. Shyluk).
31. Calgon Corp., US 3 391 090, 1968 (D. L. 54. Petrolite Corp., US 4 312 969, 1982 (H. L.
Schiegg, M. Run). Becker, R. S. Buriks, J. G. Dolan).
32. A. T. Coscia in N. M. Bikales (ed.): 55. Allied Colloids, GB 1 482 515, 1973 (D. B.
Encyclopedia of Polymer Science and Anderson, J. Forder, I. M. Johnson).
Technology, vol. 10, Interscience, New York 56. Röhm GmbH, DE-OS 2 840 894, 1978 (J.
1969, pp. 616 – 622. Masanek, H. Pennewiß, H. Trabitzsch).
33. Amer. Cyanamid, US 3 567 659, 1971 (D. E. 57. C. S. Scanley, US 4 052 353, US 4 090 992,
Nagy). 1972.
34. R. Schulz, G. Renner, A. Henglein, W. Kern, 58. Dow Chemical, US 2 982 749, 1961 (R. E.
Makromol. Chem. 12 (1954) 20 – 34. Friedrich, R. M. Wiley, W. L. Garrett).
35. Progil, FR 2 064 729, 1969 (J. P. Communal, J. 59. Röhm GmbH, DE 2 009 218, 1970 (H.
Fritz, B. Papillon). Pennewiß, H. Knoll, J. Masanek).
36. Rhone-Poulenc, FR 2 348 227, 1976 (J. 60. BASF, DE 2 710 372, 1977 (R. Hoene, D.
Boutin, J. Neel). Jung, H. U. Schenck, H. Spoor).
37. Nautschno-Issledowatelskij 61. Mitsubishi Chem. Ind., Kyoritsu Yuki, DE-OS
Fisikochimitschesky institut imeni S. J. 2 800 520, 1978 (O. Kamada, K. Watanabe, K.
Karpowa, DE-AS 1 645 065, 1966 (A. Abkin, Sagamikara, S. Sawayama).
A. P. Scheinker, P. M. Chomikowsky, M. K. 62. Cassella Farbwerke Mainkur AG, DE-AS
Yakowlewa et al.). 1 301 532, 1966 (H. v. Brachel, F. Engelhardt).
38. Hercules Inc., US 3 926 756, 1975 (A. J. 63. Hercules Inc., US 3 336 269, 1967 (D. J.
Restaino). Monagle, W. P. Shyluk).
39. Japan Atomic Energy Research Inst., US 64. T. W. Healy, J. Macromol. Sci. Chem. A8
4 066 522, 1978 (S. Machi, T. Wada, H. (1974) 603.
Sekiya). 65. R. Aveyard, D. A. Haydon: An Introduction to
40. BASF, DE-AS 1 032 922, 1956 (H. the Principles of Surface Chemistry,
Fikentscher, H. Burkert, H.-J. Krause). Cambridge University Press, New York 1973.
41. Sanyo Chem. Ind. Ltd., JP 5 4155-296, 1978 66. D. H. Everett, Pure Appl. Chem. 31 (1972)
(K. Takada, M. Suzuki). 579.
42. Dow Chemical, FR 1 253 602, 1960 (A. C. 67. P. Sennett, J. P. Olivier, Ind. Eng. Chem. 57
Proffitt). (1965) no. 8, 32.
43. Allied Colloids Ltd., EP-A 123 486, 1983 (P. 68. R. O. James, G. R. Wiese, T. W. Healy, J.
Flesher, D. Farrar, I. M. Johnson). Colloid Interface Sci. 59 (1977) 381.
44. Hercules Inc., US 4 113 688, 1978 (S. C. 69. E. Matijevic, J. Colloid Interface Sci. 43
Pearson). (1973) 217.
 Flocculants 11

70. J. Gregory, J. Colloid Interface Sci. 42 (1973) 98. R. Bodu, L. Clappier et al., Ind. Miner. Tech.
448. 1981, 417.
71. A. Rembaum in T. F. Yen (ed.): Recycling and 99. P. Young, R. Gatzweiler, W. Flöter, Erzmetall
Disposal of Solid Wastes, “Flocculation of 35 (1982) 489.
Model Waste Particles by Means of Ionene 100. J. M. Reuter, Umwelt 1981, no. 1, 27.
Polymers,” Ann Arbor Science, Ann Arbor, 101. R. Weiner: Die Abwässer in der
Mich., 1974. Metallindustrie, 3. ed., Eugen G. Lenze
72. A. S. Michaels, Ind. Eng. Chem. 46 (1954) Verlag, Saulgau 1965, pp. 279 – 289.
1485 – 1490. 102. H. Schramek, WLB Wasser, Luft, Betr. 21
73. J. A. Kitchener, Br. Polym. J. 4 (1972) 217. (1977) 450.
74. F. M. Fowkes, M. A. Mostafa, Ind. Eng. Chem. 103. A. v. Röpenack, U. Kleinert, Erzmetall 24
Prod. Res. Dev. 17 (1978) no. 1, 3. (1971) 421.
75. Y. A. I. Attia, J. A. Kitchener: Proc. Eleventh 104. R. R. Knobler, T. I. Moore, R. L. Capps,
Internat. Mineral Proc. Congress, Cagliari, Erzmetall 32 (1979) 109.
Italy, Apr. 1975, pp. 1233 – 1248. 105. P. Mouchet, Ind. Miner. Mineralurgie 1977,
76. H. E. Ries, B. L. Meyers, J. Appl. Polym. Sci. 148 – 159.
15 (1971) 2023 – 2034. 106. Amer. Cyanamid, DE 3 245 806, 1983 (N. J.
77. W. Hey, K.-H. Kubitza, D. Leininger, Brownrigg).
Glückauf-Forschungshefte 44 (1983) 226. 107. Allied Colloids Ltd., BE 848 271, 1977 (D. A.
78. D. A. Dahlstrom, R. P. Klepper: VIII. Intern.
Frost, D. Farrar).
Coal Preparation Congress Donezk D3, 1979.
108. Ullmann, 4th ed., 17, 577 – 635.
79. H. A. Hamza, CIM Bull. 72 (1979) 116.
80. W. Blankmeister, Aufbereit. Tech. 21 (1980) 109. R. Nicke, Zellst. Pap. (Leipzig) 31 (1982)
171. no. 1, 19.
81. K. Legner, J. Schwerdtfeger, Glückauf 119 110. W. Auhorn, Rev. A T I P 37 (1983) 1.
(1983) 237. 111. U. Beck, F. Müller, Wochenbl. Papierfabr. 107
82. H. Hennig, S. Ehlert, E. Beekere, Aufbereit. (1979) 411.
Tech. 25 (1984) 681. 112. F. Müller, U. Beck, Papier (Darmstadt) 33
83. D. Leininger, P. Wilczynski et al., Glückauf (1979) 89 – 95.
115 (1979) 467. 113. D. Horn, Zellst. Pap. (Leipzig) 28 (1979) no. 3,
84. J. Lange, Erzmetall 35 (1982) 117. 129.
85. J. Bialas, J. Ampulski, Aufbereit. Tech. 26 114. H. Heel, Umweltmagazin, 1980, no. 1, 44.
(1985) 240. 115. H. Engelhardt, M. Neuwirth, W. Weisbrodt,
86. M. J. Pearse, J. Barnett: Second World Korresp. Abwasser 32 (1985) 940.
Filtration Congress, London 1979, 116. J. C. Ginocchio, H. Bischofsberger, A.
pp. 333 – 354. Gmünder, Chem. Ing. Tech. 56 (1984) 310.
87. F. N. Kemmer, J. A. Beardsley, Eng. Min. J. 117. H. Predel, Erdöl und Kohle-Erdgas-Petrochem.
172 (1971) 92. 37 (1984) 502.
88. W. Schubert, H. Schubert, Neue Bergbautech. 118. A. Bauer, W. Böwe, Korresp. Abwasser 31
7 (1977) no. 1, 64 – 71. (1984) 39.
89. V. A. Arsentiev, I. Leja, CIM Bull. 70 (1977) 119. R. Schrieber: Berichte der
154. ATV/Jahreshauptversammlung Neumünster
90. R. Rüffer, H. Teichmann, Gas- und Wasserfach 1982, p. 351.
102 (1961) 603. 120. B. Sander, 311. Dechema-Kolloquium,
91. B. Heide, Aufbereit. Tech. 24 (1983) 15. Frankfurt (10. 1. 1985).
92. E. Gmey, Montan. Rundsch. 1958, 333. 121. R. Römer, H. Lauer, Chem. Ing. Tech. 55
93. Calgon Corp., EP 47 118, 1982 (J. A. Aufman). (1983) 568.
94. Mitsubishi Chemical, J 49 012 048, 1974 122. H. Perchthaler, Abwassertech. Abfalltech. 36
(Miyaji Kazuo, Ueda Hideo). (1985) 32.
95. I. Dombalov, Khim. Ind. (Sofia), 51 (1979)
123. D. Reimann: 3. Europäisches Abwasser- und
117.
Abfallsymposium, München, EA 75 (1975).
96. D. W. Leyshon, R. T. Schneider, Phosphorus
124. G. D. Abraham, Umwelt 5 (1984) 419.
Potassium 104 (1979) 32.
125. R. Klute, V. Mertsch, H. H. Hahn, Korresp.
97. E. Jemaa, AFCFP-Quarterly J. Arab.
Abwasser 31 (1984) 809.
Federation of Chemical Fertilizer Producers
(1979) 44.
12 Flocculants

126. R. Rehwoldt, Environ. Sci. Technol. 16 (1982) 140. J. Sievers, Mitteilung für den Bergbau aus der
616 A. Anwendungstechn. Abt. der BASF AG, 1965,
127. H. Bernhardt, GWF Gas Wasserfach: Wasser p. 345 d.
Abwasser 125 (1984) 312. 141. B. Sander, Chem. Ing. Tech. 51 (1979)
128. J. C. Ginocchio, Tech. Rundsch. Sulzer 65 684 – 685.
(1983) no. 3, 12. 142. B. A. Heide, R. Kampf, H2 O 11 (1978) 339.
129. V. Mayer, GWF Gas Wasserfach: Wasser 143. B. Sander, Chem. Ing. Techn. 52 (1980)
Abwasser 125 (1984) 373. 282 – 283.
130. M. Jekel, R. Böckle, Vom Wasser 59 (1982) 144. R. C. Baskerville, R. S. Gale, J. Water Poll.
195. Control. Federation 67 (1968) 233.
131. A. G. Noble: Proc. Queensl. Soc. Sugar
145. U. Loll, Korresp. Abwasser 24 (1977) 295.
Technol., 33th Conf., 1971, p. 251.
146. A. P. Black, A. M. Buswell et al., J. Am. Water
132. O. L. Crees, E. Whayman, A. L. Willersdorf:
Works Assoc. 49 (1957) 1414 – 1424.
Proc. Queensl. Soc. Sugar Technol., 44th
147. J. Eisenlauer, D. Horn, Z. Wasser Abwasser
Conf., 1977, p. 225.
133. V. Agius, R. Attard et al.: Proc. Queensl. Soc. Forsch. 16 (1983) 9.
Sugar Technol., 44th Conf., 1977, p. 277. 148. D. D. McCollister et al., Toxicol. Appl.
134. Miles Laboratories Inc., GB 53 764, 1982 Pharmacol. 7 (1965) no. 5, 639.
(D. F. Hershberger, M. M. Sternberg). 149. Report on Coagulant Aids for Water
135. Amer. Cyanamid, GB 1 438 484, 1976 (P. F. Treatment,Environmental Protection Agency,
Wilde). Office of Drinking Water, Cincinnati, Ohio,
136. E. Wottgen, A. N. Grigorian, D. Beck, B. A. Feb. 1978.
Tschernucha et al., DD 104 554, 1974. 150. Polyacrylamide zur Wasseraufbereitung,
137. J. Vostrcil, F. Juracka: Commercial Organic DIN 19 622 (Dec. 1977).
Flocculants, Noyes Data Corp., Park Ridge, 151. Federal Register, §121.1092 (Nov. 30th, 1963)
N. J., 1976. 12 747.
138. R. F. Packham, Br. Polym. J. 4 (1972) 152. H. Burkert, GWF Gas Wasserfach; Wasser
305 – 315. Abwasser 111 (1970) 282.
139. Flockungsmittel für Betriebswässer,
DIN 23 007 (March 1983).
 Floor Coverings 1

Floor Coverings
Gudrun Heisterberg-Moutsis, Du Pont de Nemours (Deutschland) GmbH, Östringen, Federal Republic of
Germany (Chap. 1)
Rainer Heinz, Du Pont de Nemours (Deutschland) GmbH, Östringen, Federal Republic of Germany (Chap. 1)
Thomas F. Wolf, Du Pont de Nemours (Deutschland) GmbH, Östringen, Federal Republic of Germany (Chap.
1)
Dominic J. Harper, Du Pont de Nemours (Deutschland) GmbH, Östringen, Federal Republic of Germany
(Chap. 1)
David James, Du Pont de Nemours (Deutschland) GmbH, Östringen, Federal Republic of Germany (Chap. 1)
Richard P. Mazzur, Armstrong World Industries, Lancaster, Pennsylvania 17604, United States (Chap. 2)
Volker Kettler, Witex AG, Augustdorf, Federal Republic of Germany (Chap. 3)
Hansgert Soiné, Witex AG, Augustdorf, Federal Republic of Germany (Chap. 3)

1. Textile Fiber Floor Covering . . . . . 2 1.5. Disposal and Recycling . . . . . . . . 11

1.1. Fiber Production . . . . . . . . . . . . 2 2. Resilient Floor Covering . . . . . . . 12
1.1.1. Staple Fiber . . . . . . . . . . . . . . . . 2 2.1. Introduction . . . . . . . . . . . . . . . 12
1.1.2. Bulked Continuous Filament . . . . . . 2 2.2. Linoleum . . . . . . . . . . . . . . . . . 13
1.1.3. Polymer Selection . . . . . . . . . . . . 3 2.3. Vinyl Flooring . . . . . . . . . . . . . . 13
1.1.4. Fiber Design . . . . . . . . . . . . . . . . 3 2.3.1. Raw Materials . . . . . . . . . . . . . . . 14
1.2. Yarn Preparation . . . . . . . . . . . . 4 2.3.2. Sheet Vinyl Flooring . . . . . . . . . . . 15
1.2.1. Staple Yarn Processing . . . . . . . . . 4 2.3.3. Tile Flooring . . . . . . . . . . . . . . . . 18
1.2.2. Twisting, Heat-Setting, and Intermin- 2.4. Rubber Tile and Sheet . . . . . . . . . 20
gling . . . . . . . . . . . . . . . . . . . . . 4
2.5. Specialty Flooring Products . . . . . 21
1.3. Production of Textile Floor Cover-
3. Laminate Flooring . . . . . . . . . . . 21
ings . . . . . . . . . . . . . . . . . . . . . 6
3.1. Development . . . . . . . . . . . . . . . 21
1.3.1. Flooring Types and Manufacturing
3.2. Construction . . . . . . . . . . . . . . . 22
Methods . . . . . . . . . . . . . . . . . . 6
1.3.2. Carpet Constructions . . . . . . . . . . 7 3.3. Materials . . . . . . . . . . . . . . . . . 22
1.3.3. Coloration and Finishing . . . . . . . . 8 3.4. Production and Installation . . . . . 22
1.4. Carpet Properties and Performance 9 3.5. Testing . . . . . . . . . . . . . . . . . . . 25
1.4.1. Carpet Esthetics . . . . . . . . . . . . . . 9 3.6. Environmental Aspects . . . . . . . . 26
1.4.2. Carpet Performance . . . . . . . . . . . 9 3.7. Economic Aspects . . . . . . . . . . . . 26
1.4.3. Test Methods . . . . . . . . . . . . . . . 11 4. References . . . . . . . . . . . . . . . . . 26

1. Textile Fiber Floor Covering in other regions of the world. World carpet fiber
production amounted to 2.1 × 106 t in 1999. On
Textile floor coverings have been highly ap- the basis of area, the main fiber materials used
preciated in the human environment ever since worldwide are nylon (55 %), polypropylene
textile manufacturing techniques were devel- (34 %), polyester (5 %), and wool (3 %). The
oped. They deliver an individually designed ar- majority of carpeting is used for residential fit-
tificial ground which can be soft, warm, sound- ted carpets and rugs (68 %); the remaining 32 %
insulating, and colored/patterned. is split between commercial installations (e.g.,
Global carpet production grew to offices, hotels, banks, schools, and retail stores),
2.5 × 109 m2 in 1999, of which 52 % was pro- automotive and transportation, and outdoor car-
duced in the United States, 27 % in Western Eu- peting [1].
rope, 9 % in the Asia/Pacific region, and 12 %

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a11 263
2 Floor Coverings

For the production of carpets, either bulked then cut into the desired staple fiber lengths and
continuous filament (BCF) or staple fiber can baled.
be used. Whilst BCF yarn experienced strong
growth in the mass market during the 1980s and
1990s, staple fiber retains a very strong position 1.1.2. Bulked Continuous Filament
in more upmarket segments. BCF yarns continue
to gradually substitute staple fiber yarns, the sub- Bulked continuous filament yarn is so named
stitution being driven by superior process eco- because the fibers are used in continuous form
nomics along the value chain. (not cut, as with staple from synthetic and nat-
ural fibers), and the fiber is crimped (or bulked)
during manufacture.
1.1. Fiber Production As with staple, filaments are extruded from
the melt and quenched. They are then collected
The production of synthetic fibers for use in into yarn bundles comprising tens of filaments.
carpet manufacture starts with polymers, which The yarn is then drawn, crimped (bulked), and
are made from monomers (or intermediates) de- heat-set. Bulk is usually achieved by compres-
rived from crude oil. For example, Nylon 66, sion of the heated yarn into a small hot chamber
the most prevalent fiber material, is made from whose dimensions determine the character of the
hexamethylenediamine and adipic acid. These bulk/crimp. After a residence time in the cham-
react with one another to form a monomer (in ber sufficient to ensure heat-setting, the yarn is
this case known as nylon salt), which is then cooled, straightened under tension, and wound
polymerized. The polymer is fed in the form onto packages. The advantage of heat-setting is
of solid pellets or chips into the fiber-forming that, despite being straightened, the fibers retain
melt spinning machine. Alternatively, polymer a “memory” of the crimp and recover a major
production and fiber spinning can be coupled part of it when subjected to a combination of
in a continuous melt-spinning operation. Melt heat and moisture in subsequent processing at
spinning is used for the majority of synthetic low tension. Generally, the character of crimp
fiber carpet yarns, including Nylon 66 and 6, achieved in BCF yarns is not the same as that of
polyester, and polypropylene. For a detailed dis- staple yarns; a wider range of bulk in the finished
cussion of fiber production and specific fibers, carpet can be achieved with BCF. Yarn proper-
see → Fibers, 3. General Production Technol- ties also depend on other production parameters,
ogy; → Fibers, 4. Synthetic Organic. such as draw ratio.

1.1.1. Staple Fiber 1.1.3. Polymer Selection

The molten polymer is extruded through shaped Polymer selection is one of the most important
holes to form filaments, which are then quenched determining factors in the balance of properties
(cooled) so that they solidify. The filaments are achievable in the carpet, as well as the cost and
collected in a large bundle, known as a tow or ease of fiber and subsequent carpet manufacture.
rope, consisting of hundreds of thousands of fila- Nylon (polyamide 6 and 66) is the major
ments. The rope is stored for further processing. carpet fiber polymer in use today, followed by
Natural fiber such as wool and, to a lesser polypropylene, polyester [poly(ethylene tere-
extent, cotton, sisal, and silk, have an inherent phthalate)], and wool. Nylon is widely used
crimp, which gives the fiber desirable value and because its molecular structure imparts out-
esthetic properties, such as bulk (i.e., volume or standing abrasion resistance, excellent recov-
space filling), and an ability to recover from de- ery from high strains, and excellent dyeabil-
formation. Furthermore, most natural fibers are ity, lending the polymer great versatility, per-
not continuous but instead have relatively short formance, and durability. Polyamide 66 is made
lengths. In a second processing operation, there- from hexamethylene diamine and adipic acid,
fore, the synthetic fiber tow is drawn, crimped whereas polyamide 6 is produced from capro-
while in a relaxed state and heat-set. The tow is lactam. While the two polymers are similar
 Floor Coverings 3

in many ways, the less symmetrical molecular this is best exploited by the polymer types
structure of nylon 6 results in a more open struc- most able to withstand abrasion.
ture and lower crystallization potential. – Luster or brightness, most commonly con-
Polypropylene (PP) has gained market shares trolled by the addition of a delustrant (usu-
over the last few decades because of lower raw ally TiO2 ) to the polymer, but also affected
material cost and the low technological entry by fiber cross section and by voids, striations,
barrier for fiber extrusion. Several carpet mills and spherulites, which may be induced in
have started to produce polypropylene fibers in spinning, and by crimping.
house (vertically or backward integrated carpet – Character and degree of bulk or crimp
manufacture). (The same is true to some ex- Fiber design and its impact on carpet properties
tent of Nylon 6 and polyester, but Nylon 66 is further discussed in Section 1.2.
yarns remain more difficult to produce, and their
manufacture is still exclusively the preserve of
specialized yarn manufacturers.) Polypropylene
carpets have lower appearance retention than
Nylon carpets, but are appropriate for less de-
manding applications. PP is usually produced as
pigmented (spin-colored, solution-dyed) staple
or BCF, since an economical route to a dyeable
PP fiber has not been established.
Polyester fibers are available mainly in sta-
ple form; polyester is less versatile in dyeing Figure 1. Carpet fiber cross sections
and less resilient in carpet than Nylon. A) Round; B) Trilobal; C) Square hollow filament
Wool, which has traditionally been regarded
as a premium fiber, tends (due to lower abrasion
resistance) not to perform as well as Nylon in 1.2. Yarn Preparation
like-for-like carpets, though carpets made from
wool tend to be more expensive. Wool quality The short, crimped staple fibers must be spun to-
can vary widely. gether to form a staple yarn before further use.
Both staple and BCF yarns can then be tufted di-
rectly as singles yarns into carpet from producer
1.1.4. Fiber Design packages. Alternatively, a number of further pro-
cessing steps can first be employed, depending
Fiber design is at least as critical to carpet proper- on the esthetic and performance characteristics
ties as polymer selection. The esthetic properties desired in the carpet. These include twisting and
and performance characteristics of a carpet are heat-setting, and intermingling.
determined by a variety of fiber-related factors.
These include:
1.2.1. Staple Yarn Processing
– Yarn thickness or size, which is measured for
BCF yarns in decitex (dtex = g/10 km) or de- Staple yarn production involves opening of the
nier (g/9 km), and varies typically from 600 fiber bales, possibly blending with other staple
to 2500 dtex (as singles yarns). Staple yarn fibers, carding (to align the individual fibers),
thickness is measured in Nm (metric count, drawing (drafting), and spinning or twisting (to
m/g) or c.c. (cotton count, 840 yards/lb). lock the fibers into the final yarn).
– The thickness of individual filaments within The use of staple allows the blending of fibers
a yarn bundle, often referred to as dpf or de- of different cross section, luster, or dyeability.
citex per filament. This relatively intimate blending at the fiber level
– Fiber cross section (Fig. 1), dictated by the provides different styling options from those
shape of the extrusion hole and various poly- achieved by plying or twisting different yarns,
mer and production parameters. All melt- as described below. Even different materials are
spun fibers can be shaped at extrusion, but blended to obtain desired carpet properties. For
4 Floor Coverings

example, an 80/20 wool/nylon blend provides twisting provides the tuft integrity (tuft defini-
markedly improved wear performance versus tion, texture) which is characteristic of saxony
100 % wool. Blending, of course, can also have and hard twist (friezé) carpet styles. The amount
a beneficial effect on the uniformity of the yarn of twist put into the yarn influences not only the
produced and therefore the final carpet. initial appearance or texture of the carpet, but
also the retention of this texture, which degrades
in use according to the severity of traffic expo-
1.2.2. Twisting, Heat-Setting, and sure. Increased twist level, however, increases
Intermingling yarn cost and results in loss of carpet bulk be-
cause of compression of the yarn crimp. The
Depending on the desired carpet esthetic and twist level used for a given style is therefore a
performance characteristics, yarns of the same balance of many factors. The yarns twisted to-
or different lusters, decitexes and/or dyeabil- gether are usually identical, but dissimilar yarns
ities may be combined by using a twisting may be paired to achieve additional styling flex-
and heat-setting process or an air entangle- ibility.
ment/intermingling process.

Twisting. Two (or sometimes more) singles Heat-Setting. The twisted yarn structure is
yarn packages are plied and twisted around each sufficiently stable to allow winding onto pack-
other to form a twisted yarn ready for heat- ages, but it must be heat-set to lock in the twist
setting. Direct cabling (Volkmann, Verdol: see and withstand the stresses of carpet dyeing and
Fig. 2) is the most common twisting technique. finishing and the traffic received in use. Also,
yarn

leanness

can occur because the crimp
has been pulled out in the various winding and
packaging operations. If the yarn is heated while
relaxed, much of this crimp, and hence yarn bulk,
can be recovered. Therefore, both bulk recovery
and setting of the structure are necessary so that
the yarn remains stable in its intended end-use
area.
For Nylon 66 or 6, setting can be achieved
in a hot dry atmosphere at 180 – 220 ◦ C or, al-
ternatively, in saturated steam at 120 – 140 ◦ C.
Machines made by Suessen and Superba em-
body these two continuous heat-setting pro-
cesses, which have now largely displaced the
earlier autoclave batch process. BCF is primar-
ily Superba steam set, while Suessen hot air set-
ting is the preferred method for staple in North
America.

Intermingling is another technique used to

increase styling options in carpet design. The
effect achieved is different to that obtained by
twisting and heat-setting. Two or more singles
yarns are unwound and passed together through
Figure 2. Operating diagram of a Verdol cable twister a small chamber to which compressed air is ap-
a) T 3 , plied yarn; b) Bucket yarn tensioner; c) Creel yarn plied. The yarns become intermingled or co-
balloon; d) Balloon restraining ring; e) Storage disk; f) Spin-
dle; g) T 2 , creel yarn; Tension (T ) is adjusted via weighted mingled with each other and are then rewound
disks or other devices at the package as a single yarn. They do not require subsequent
heat-setting. Intermingling is carried out pre-
Twisting has several purposes. While sim- dominantly with BCF yarns, and more often to
ple plying achieves a desired total yarn decitex,
 Floor Coverings 5

Figure 3. Production of tufted carpet

A) Cross section through a tufting machine, illustrating machine components and yarn path; B) The number of stitches per
unit length in the tufting direction, the distance between needles, and the yarn thickness determine carpet density; C) The
pile height is determined by the distance between the loopers and the backing cloth; D) Loop pile production; E) Cut pile
production
Reproduced with permission of Cobble
6 Floor Coverings

combine dissimilar rather than identical yarns, the contact for fixing the textile floor covering to
for example yarns with different dyeabilities. the ground on installation. In the past, residential
carpets in continental Europe (low pile weights)
usually had a foam secondary backing. Recent
1.3. Production of Textile Floor landfill regulations and restrictions, as well as ef-
Coverings forts to simplify carpet construction for environ-
mental reasons, have led to the introduction of
1.3.1. Flooring Types and Manufacturing textile layers (woven fabrics; nonwoven needled
Methods fleeces, often made from polyolefin or polyester
with a content of recycled material), which pro-
The major types of textile floor coverings are vide similar underfoot comfort and thermal and
tufted, woven, and nonwoven. Further manufac- acoustic insulation. These textile backings have
turing techniques include fusion bonding, flock- largely displaced foam. In countries where piles
ing, and knitting. are typically higher, where underlays are used
Tufting is currently the fastest, most econom- (UK, North America), and in commercial instal-
ical, and most automated method for producing lations, a very thin fabric provides the interface
carpets (Fig. 3). Needles held on a needle bar between the latex and the underlay or floor.
are each threaded with a pile yarn and pushed Woven carpets are produced by the Wilton
through a primary backing fabric. Under the or the Axminster method; the main differences
backing, a hook or looper catches and holds the between them are the design of the loom and
yarn to the desired pile height (Fig. 3 A – C). For the weave used. In Wilton production, the pile
cut-pile yarn, a knife cuts the loops as they ac- yarn is carried through the backing, whereas in
cumulate on the looper; for loop-pile yarn, the Axminster, the pile yarn is inserted in the back-
hook withdraws and leaves a loop (Fig. 3 D and ing.
E). Carpet density is determined by the number Flocked carpets and fusion-bonded floor
of stitches per unit length in the tufting direc- coverings with an upright pile use melt or normal
tion, by the spacing between needles, and by adhesives to anchor fibers or yarns to a backing
yarn thickness. (Fig. 4). Needled floor coverings (fleeces, non-
Thicker yarns require coarser needles with wovens) are produced by needle punching with
larger spacing. Common spacings between nee- optional subsequent fiber bonding. They can be
dles (gauges) range from 0.16 cm for European homogeneous or consist of more than one layer
fine velours up to 0.8 cm (1/16, 5/64, 1/10, 1/8, (heterogeneous).
5/32, 3/16, 5/16 inches). Pile heights vary bet-
ween 3 and 50 mm. Pile weights consequently
range from 300 to 2500 g/m2 . The average tufted
pile weight in Europe is 580 g/m2 versus ca.
1000 g/m2 in North America (worldwide aver-
age 840 g/m2 ). The needle bar of a tufting ma- Figure 4. Flocked-pile carpet
chine can be moved sideways, and this enables Reproduced by courtesy of ISO
the creation of tuft patterns if the needles are fed
with yarns of different types. A wider range of
patterning options is available on machines with
double sliding needle bars, full repeat scrolls,
and other modifications (e.g., Graphics, Cobble
Colortec, Tuftco).
The application of a latex lock coat to the un-
derside of the primary backing is the preferred
method of locking the filaments together and
into the primary backing. A secondary backing
is then usually applied to enhance dimensional
stability, strength, and lay-flat stiffness and to
Figure 5. Manufacturing principle of needled textile floor
protect the underside of the carpet. It provides covering
Reproduced by courtesy of ISO
 Floor Coverings 7

In needle punching, layers of loose fibers are 1.3.2. Carpet Constructions

passed under a bank of barbed needles (Fig. 5).
The needles catch filaments and entangle the lay- Carpets can be grouped into two major construc-
ers of fibers with each other. Special techniques tion classes: loop pile and cut pile (Fig. 6).
have been developed which allow the creation Loop pile carpets (Fig. 6 A) can have level
of needled pile floor coverings (e.g., Dilour). pile surfaces, patterned loops, or loops with two
In thermobonding, contact points between or three different pile heights to give a textured
fibers are melted together by heat treatment. effect. Styling beyond pile height and carpet
This requires fibers with low melting point, core- density is achieved by coloration of the carpet
sheath two-component fibers with low melting or yarn. Loop pile carpets, which achieve good
polymer sheaths, or melt adhesives. durability by virtue of the loop construction and
Bonding compounds (e.g,. latex) act as adhe- therefore do not require twisted, heat set yarns,
sives. Needled floor coverings can be fully im- are usually produced by direct tufting of BCF
pregnated or back coated. singles or intermingled yarns. However, many
A backing layer can be used to add volume, new loop styles now use twisted and often heat
enhance stability, allow for easier installation, set yarns.
etc. Cut pile carpets can be further subdivided
Fleeces are used as inexpensive commercial into a variety of different constructions. These
floor coverings in Europe and feature in special include saxony, hard twist (friezé), cut-and-loop,
applications such as outdoor and automotive car- shag, velour (velvet), and COC. Saxony car-
peting. pets (Fig. 6 B) use twisted, heat-set yarns hav-
ing 1.4 – 2.4 turns per centimeter (3.5 – 6 turns
per inch). This results in regular pinpoint tufts.
Friezé (hard twist) carpets (Fig. 6 C) contain
more highly twisted yarns, which are kinked be-
fore the heat setting process. This leads to irreg-
ular tuft-end formation on yarn cutting (during
tufting) and variable light reflection from either
bent or upright fibers at the pile surface. In Cut-
and-loop carpets (Fig. 6 D), some of the tufts are
cut and others remain whole loops, forming a
pattern. Shags are high pile, very low density
saxony carpets. The pile height exceeds 2 cm,
but the individual tufts lie flat rather than stand-
ing upright. Carpets of velour (velvet) construc-
tion (Fig. 6 E) use staple yarns with little or no
twist. The yarn stands upright in the carpet, and
adjacent tufts are not visible as single entities, so
that the surface appears uniform. Velours form
an important segment of the residential mar-
ket in continental Europe. COC is an acronym
for cross-over-cut and refers to constructions in
which Nylon singles yarns of different dyeabili-
ties or yarns of different color are directly tufted
with a sliding needle bar to form a pattern. They
are found primarily in the continental European
commercial sector. Velours and COCs are exam-
Figure 6. Types of carpet construction ples of the direct tufting of staple and BCF sin-
A) Loop pile; B) Saxony; C) Friezé (twist); D) Cut and loop;
E) Velour
gles yarns, respectively. In the United Kingdom
and North America, by contrast, staple yarns are
twisted and heat set and used to make the other
carpet structures described above. The majority
8 Floor Coverings

of BCF yarns used for cut-pile are also twisted mainly used for automotive carpets, which re-
and heat set before tufting. The vast majority of quire the highest standards of dye lightfastness,
staple fibers are used in cut pile carpets. only achievable with this class of dyes.
Standard polyester and polypropylene are
not commercially dyeable on current piece-
1.3.3. Coloration and Finishing dyeing equipment at atmospheric pressure.
To avoid high-temperature dyeing (> 100 ◦ C
Of all manufacturing operations in a carpet mill, at > 0.1 MPa), carrier-free dyeable polyester,
coloration and finishing have perhaps the most which is dyeable with disperse dyes, has been
significant effect on the visual and tactile prop- developed, and offers at least a limited styling
erties of the end product. Coloration can refer flexibility. Most PP is colored by addition of pig-
to dyeing or to printing of white (typically Ny- ments to the polymer melt during yarn manufac-
lon) carpet material. Both continuous and batch ture.
dyeing processes are in commercial operation.
Depending on the fiber selection, plain colors or Printing. White tufted Nylon carpets can be
multicolored effects can be achieved from one printed on flatbed screen printing machines or
dye liquor. In a printing process, multicolored rotary screen printing machines, which allow the
designs/patterns are produced by screen or spray highest production speeds (30 – 50 m/min). The
printing. Finishing can refer to the application of spray printing machines, Chromojet (Zimmer)
a chemical aftertreatment, such as a protective or Millitron (Milliken), similar in principle to an
stainblocking or anti-soil treatment. Shearing of ink-jet printer, run at lower speeds but are more
the pile to improve the final surface uniformity flexible in terms of design possibilities and de-
of the carpet is an example of a mechanical fin- sign change. Because the risk of poor color uni-
ishing process. The last finishing step for tufted formity is much lower in printing, many kinds
carpets is the application of a latex lock coat and of acid and metal-complex dyestuffs are in use
then a secondary backing. for standard prints. For the widely used resist
and displacement printing techniques, specially
Dyeing. Tufted carpets made from white Ny- selected groups of acid and metal-complex dyes
lon yarns are being increasingly dyed on contin- are used, in combination with appropriate resist
uous dyeing machines. Quick-change color ap- and blocking chemicals.
plicators (Küsters, Fleissner) are used to speed After color application the prints are run
process changes. In the continuous process, dye through a horizontal steamer for 3 – 6 min in sat-
liquor is poured evenly over the carpet running urated steam for color fixation, followed by wa-
below. After color application, the carpet runs ter rinsing, hydro-extraction, and drying.
into a steamer with vertical loops (festoons), and
is heated with saturated steam for 2 – 6 min, dur-
ing which the dyes are fixed onto the fiber. Wa- 1.4. Carpet Properties and Performance
ter rinsing, hydro-extraction, and drying follow. 1.4.1. Carpet Esthetics
In the less productive batch method, carpets are
dyed in winches (becks). Here, a section of car- Color, pattern, and structure are the most
pet runs in a loop through a full dyebath with obvious elements of the visual esthetics or
temperatures up to boiling point for 40 – 60 min. appearance of a carpet, and are dictated
Acid leveling dyes are used for most Nylon by polymer/fiber choice, carpet construction,
carpets in residential and commercial end uses. yarn choice (BCF/staple, singles/twisted, heat-
This class of dyes allows the best color unifor- set/intermingled), and coloration. Further im-
mity with good fastness properties in later end portant visual factors can be described in terms
use. For combinations of standard and chem- of luster, sparkle, glitter, sheen, clarity, bright-
ically modified Nylon (differential-dye yarns), ness, dullness, chalkiness, etc. These are in-
which allow multicolor effects from a sin- fluenced by fiber design (Section 1.1.4), the
gle dyebath, acid leveling, acid contrast, and shape of the fiber cross section (Fig. 1), mat-
cationic dyes are used. Metal-complex dyes are tness/brightness, crimp, yarn, and filament de-
citex.
 Floor Coverings 9

The tactile esthetics of a carpet are influ- or entanglement of the yarn. In saxony carpets,
enced by many of the same factors; filament and the most important factor is the twist level of the
yarn decitex (thickness/size), twist level of the yarn. A low twist level is ca. 1.4 turns per cen-
plied yarn, crimp level of the filaments, and car- timetre (3.5 turns per inch) in singles yarn and in
pet construction, including pile height and stitch plied yarn. A minimum of two turns above pri-
density. mary backing is recommended for good appear-
ance retention, which for cut-pile carpets like
saxonies is most apparent in the tip definition of
1.4.2. Carpet Performance the tufts.
Pattern and color contrast of a textile floor
The visual and tactile esthetics listed in Sec- covering also influence appearance retention by
tion 1.4.1 describe a new carpet. The perfor- hiding physical changes in the surface structure.
mance characteristics of a carpet in use are also The topic of appearance retention is compli-
very important, and requirements vary from end cated by the fact that some of the factors listed
use to end use. directly influence the amount of physical change
that occurs in the carpet in use, while others af-
Appearance Retention. Carpet appearance fect the degree to which the change is visible,
retention or “newness” retention in use has sev- and some affect both.
eral aspects. It includes the loss of texture due
to traffic (leading to damaged and opened tufts Static electricity can be generated by the
and consequent deterioration of surface texture), separation of the shoe sole and carpet pile ma-
fiber loss, and recovery from compression after a terial when walking on a carpet in a dry room
weight (e.g., furniture) is removed. Appearance climate. The increase in body voltage per step
retention also covers changes to colors and pat- depends on the charge generated between the
terns, whether due to fading (poor dye lightfast- separated materials (rate of charge vs. rate of
ness) or blurring (due to deterioration of surface dissipation) and on the relative humidity, which
texture of the carpet). Further end use specific has a marked effect on carpet resistance. This
requirements include, for example, the ability phenomenon is not limited to synthetic carpet
to withstand the high downward and rotational fibers, but occurs with wool as well. Significant
forces exerted by castor chair wheels (office en- body voltages can be created in several ways, in-
vironments), and bleach resistance (hospitals). cluding by rising from furniture. Dissipation of
Appearance retention depends on the nature charges (decay rate) is most effectively achieved
of the pile fiber (basic molecular structure as well by the addition of antistatic (conductive) fila-
as subsequent processing), on carpet construc- ments to the pile fiber in combination with a con-
tion, and on carpet installation. Fiber material ductive lock coating. Electric charge can then
plays an important role in all mechanical aspects, be dissipated from the body through the carpet,
whereby Nylon 66 has the best performance even under dry conditions, preventing build up of
and is hence the fiber of choice for high-traffic voltages likely to be perceived as electric shocks.
commercial installations and premium residen- An alternative, but less durable solution for car-
tial carpets. The fiber cross section, delustrant pet installations in low-traffic areas, is the use
content, bulk level, yarn decitex, and decitex of antistatic topical treatments. Computer rooms
per filament are significant factors. For exam- require particularly good antistatic protection.
ple, fiber cross section and filament decitex are
critical to wear performance. Carpet construc- Soiling refers to dirt on the carpet (rather than
tion and the appropriate choice of yarn are also staining) and is basically a surface-transfer phe-
important. The floor performance of velour and nomenon in which dirt from shoe soles is trans-
loop-pile carpets is dependent on the density of ferred to the fiber surface of the carpet and vice
the construction, determined by pile yarn mass versa. Airborne dirt usually plays a minor role.
and height. Using a bulkier yarn also increases Dirt consists mostly of a blend of small inert par-
the apparent density. The tightness of the yarn ticles, such as silicates, phosphates, oxides, and
structure is a significant factor as well. Perfor- carbonates, held together by various amounts of
mance can be improved by increasing the twist
10 Floor Coverings

fatty organic materials and moisture (agglomer- Color Fastness. In addition to dye lightfast-
ate size ca. 2 µm). It is first deposited at the top ness, wash and rubbing fastness, resistance to
of a carpet but gradually migrates into the pile fading in the presence of high NOx and ozone
as traffic exposure continues. levels is important for some end uses or geo-
Any fiber property that affects the size and graphical regions. Resistance to high sunlight
nature of the carpet’s exposed fiber surface will and temperature exposure is critical in automo-
have a direct effect on soiling. This is the rea- biles.
son why coarse fibers with smooth surfaces and
low surface area, in shapes that cannot trap soil, Health and hygiene issues carry increasing
are best suited to reduce the soiling propensity. weight in modern society. Textile floorings have
The chemical affinity of dirt particles for car- variously been blamed for poor indoor air qual-
pets is successfully reduced by surface applica- ity, the propagation of dust mites (to the excreta
tion of fluorochemical coatings (e.g., polyfluo- of which, some people are allergic) and the har-
roalkylurethanes). boring of other allergens and microbes. Many
In addition to reducing the amount of soil de- recent studies, however, show carpets to have
posited per traffic exposure, the visibility of soil a positive influence. For example, in combina-
can be reduced by proper carpet color selection, tion with adequate and regular cleaning, carpets
and by making fibers less transparent by addition act to trap dust out from the air, reducing the
of delustrants to increase light scattering. A par- amount of breathable dust (and potential aller-
ticularly effective way to hide soil through light gens) in the atmosphere, thus improving air qual-
scattering is to incorporate voids into the fibers. ity. Due to the relatively low humidity levels in
Hollow fibers with low surface area and three to carpets, they play a very limited role as breeding
six voids (e.g., Fig. 1 C) are therefore preferred grounds for dust mites, which prefer bedding and
for commercial carpet installations where high other furniture. Studies conducted on Nylon 66
traffic levels are expected. have demonstrated that it is essentially nontoxic
through both the expected dermal route to ex-
Staining. Another feature of carpet fibers is posure as well as by other possible but unlikely
their staining propensity. Nylon, which by virtue routes (oral and inhalation). Nylon 66 will not
of its chemical nature is the most flexible fiber support mildew or bacteria, nor is it eaten by
for all coloration methods – an advantage in of- moth larvae [5]. The role of carpeting in the pre-
fering consumer choice and at the production vention/mitigation of noise pollution, as a safe,
stage – is more prone to staining by, for example, non-slip surface, and as a thermal insulator is
food acids and beverages than some other sub- increasingly recognized.
strates. Stain-resist or stain-blocking systems are
applied which elevate Nylon’s stain resistance to
the level of polypropylene and polyester. Even 1.4.3. Test Methods
coffee stains can be avoided with suitable sys-
tems [2]. A system of carpet tests and classification
schemes has been developed. End use recom-
Flammability of carpets is largely deter- mendations for particular carpets are derived
mined by fiber material, carpet construction (the from these.
denser the better), latex fillers, and secondary While a global classification for textile floor
backing. Of all pile materials, wool can most eas- coverings is still pending, a common standard
ily be treated with flame retardants. Among the (EN 1307) has been agreed upon within Europe.
synthetic fibers, Nylon 66 performs best due to This involves certain basic requirements such as
its high ignition temperature, whereas polypro-
– Acceptable color fastness (to light: ISO 105-
pylene burns most easily. This is a further rea-
B02; to wet and dry rubbing; ISO 105-X12;
son for the limited use of polypropylene fibers in
to water: ISO 105-E01)
commercial installations. Carpets in transporta-
– Fiber bind [fuzzing and loss of mass (fiber
tion (particularly aircraft) end uses have very
loss), in preparation: ISO 11856]
stringent flammability requirements.
 Floor Coverings 11

It also introduces Use Classes (1 – 4) and complex and intimate mixture of many different
Luxury Rating Classes (1 – 5). and incompatible materials: various polymers,
Use Class reflects the resistance to wear (fiber adhesives, natural fibers, chalk, dyes, and dirt re-
loss; Lisson test ISO 12951 and appearance re- sulting from use (silicates, metal oxides, and or-
tention (Vettermann drum or Hexapod drum: ganic matter). Collection and identification and
ISO 10361, assessment of changes in appear- the nature of the product make effective recy-
ance: ISO 9405). The Luxury Rating depends cling anything but simple, but new legislation
on carpet type (tufted, woven, flocked), thick- and improving process economics are powerful
ness of pile (ISO 1766), mass of pile per unit area forces for change.
(ISO 8543) above primary backing, and number Several companies and major industry con-
of tufts per unit area (ISO 1763). sortia in North America and in Europe have in-
Further properties are listed in EN1307 for vested considerable effort in recent years, and
particular end uses. These include: significant progress has been made in the areas
listed below:
– Castor chair suitability (EN 985, ISO 4918
in preparation) – Some fiber manufacturers include melt-
– Electrical properties (walking test: ISO recycled plastics in new fibers.
6356, and vertical resistance: ISO 10965, at – Carpet construction is becoming simpler and
25 % relative humidity) more recovery-friendly with the substitution
– Acoustic properties (acoustic insulation of foam backing by more easily handled tex-
from impact noise: ISO 140-8; acoustic ab- tile fleeces (which themselves can include
sorption: ISO 354) recycled material)
– Thermal resistance (ISO 8302) – The polymer type in carpet pile and/or back-
– Suitability for use in periodically humid con- ing can now be identified with a new gener-
ditions such as bathrooms (dimensional sta- ation of spectroscopic analysers, either on-
bility: ISO 2551; higher color fastness to wet line or with portable instruments.
and dry rubbing: ISO 105-X12) – Mechanical separation processes have been
– Suitability for use on stairs (ISO 13746, in developed which are capable of separating
preparation) the different carpet materials with varying
– Fraying behavior (ISO 10833, in prepara- degrees of purity. These can then be recycled,
tion). usually through a remelting process and gen-
erally to lower grade end uses (car parts, syn-
Globally recognized tests do exist for soil-
thetic lumber, etc.). There are several such
ing (Kappasoil ISO 11378-1 and drum test ISO
recycle programs operational in both North
11378-2) and are in preparation for staining (ISO
America and Europe.
13750) and flammability (Radiant Panel ISO
– Chemical recycling is now available at least
9239-1). For appearance retention, there is more
at pilot plant level for nylon polymer types
reliance in North America on floor or “walker”
in post-consumer carpet waste [6]. Polyester
trials (in tandem with laboratory tests like the
can also be depolymerized, but there is as
Vetterman Drum) than is the case in Europe.
yet no process for carpet waste. PP cannot
Needled floor coverings have their own clas-
be depolymerized into its constituent build-
sification system in Europe (EN 1470 needled
ing blocks.
pile floor coverings: EN 13297).
A number of pilot collection and recycle
schemes are operating in North America and Eu-
1.5. Disposal and Recycling rope and include collection, sorting, separation,
remelting, chemical recycling, and energy re-
The majority of used carpets are currently still covery. Significant advances are to be expected
disposed of in landfill, though some are now by 2010.
incinerated with energy recovery. Carpets are a
12 Floor Coverings

2. Resilient Floor Covering cloth that was laid over board flooring to provide
a decorative, washable surface and to keep out
2.1. Introduction drafts from the cracks between the floor boards.
Several attempts, dating back as far as the 1600s,
Resilient flooring is a family of flooring products were made to establish an industry to manufac-
that includes such materials as linoleum, asphalt ture floor cloth and oil cloth. The invention of oil
tile, rubber and vinyl flooring. The term resilient cloth is recorded in a 1627 patent. A patent from
refers to the ability of these flooring materials to 1763 describes a floor covering made by coat-
deform and recover from the compressive forces ing fabric with a mixture of resin, tar, Spanish
caused by the dynamic action of foot fall, cart brown, beeswax, and linseed oil.
wheels and casters, and the static loads of appli- In 1844, a floor cloth made from India rub-
ances and furnishings. Resilience distinguishes ber, sawdust, and cork, named Kamtulicon, was
this group of flooring products from carpeting, introduced. At about the same time, waterproof
wood, ceramics, and stone. fabrics coated with rubber became quite popu-
lar and drove the price of rubber up to the point
Types of Resilient Flooring. Resilient where it became uneconomical for flooring use.
flooring is produced in two basic formats: sheet A patent was issued to Frederick Walton in
and tile. inthe case of vinyl flooring each has, 1860 for an oxidized linseed oil intermediate
with some exceptions, a distinctly different com- called linoxyn which made possible the produc-
position and manufacturing process, whereas tion of Linoleum, a name coined by Walton to
rubber flooring employs essentially the same differentiate it from the rubber-based Kamtuli-
process and formulation for both forms. con. In 1864 Linoleum was commercially intro-
duced in England by Walton, Taylor & Co. This
Economic Aspects. The market for flooring was essentially the beginning of the modern re-
is divided into two distinct segments: residential silient flooring industry.
and commercial. The total area of existing resi- Linoleum is based on a binder system of ox-
dential floor space in the United States in 1998 idized drying oils, resins, and gums, filled with
was about 17 × 109 m3 , of which an estimated ground cork, wood flour, whiting, and pigments.
16.2 % was covered with resilient flooring ma- Although it has excellent wearing characteris-
terial, the remainder being covered with carpet, tics, linoleum suffers from degradation by al-
wood, ceramic tile, etc. Most residential resilient kaline hydrolysis and is therefore unsuited for
flooring is used in kitchens and baths, and some applications where alkaline moisture is present,
in foyers and family rooms. e.g., on concrete subfloors in contact with the
The total commercial and institutional U.S. ground. It may also be damaged by frequent
floor space in 1998 was approximately 36 billion washings and stripping of wax polishes. Because
square feet (3.4 × 109 m3 , excluding warehous- of these limitations and the versatility of PVC-
ing, manufacturing areas, and parking garages. based flooring, its production was discontinued
Resilient flooring, both vinyl and rubber, consti- in the United States in 1973.
tuted about 25.5 % of this area, carpet 56.5%, In those applications where linoleum was not
and others (stone, wood, ceramic, etc.) 18 %. suitable because of its sensitivity to moisture
Market segments for resilient flooring in the and alkalinity, such as on subgrade concrete,
commercial and institutional area include mer- asphalt tile was used. This product was based
cantile, health care, education, light industry, of- on asphalt binders or, for lighter colored tiles,
fices, and banks. coumorone indene or hydrocarbon resins, filled
The total apparent hard surface flooring con- with asbestos and limestone. Asphalt tile is es-
sumption for 1998, including U.S. manufac- sentially obsolete today.
turer shipments and imports, but excluding ex-
ports, amounted to $ 5.4 × 109 , of which re-
silient flooring constituted 44.2 %. 2.2. Linoleum
History. [7–10]. The resilient flooring pro- Linoleum is experiencing a resurgence in pop-
duced today evolved from painted fabric or floor ularity in the North American market because
 Floor Coverings 13

of its use of natural and renewable raw materi- (2) it is clear and colorless, (3) it is inherently
als and its unique design capabilities. Expected fire resistant, (4) it can be effectively plasticized
sales in 1999 are about 3 % of the total U.S. to a wide range of flexibilities, and (5) it is not
resilient-flooring market [11]. adversely effected by moisture or alkali. When
moderately filled and plasticized it retains a high
Production. Linseed oil and dryers (i.e., cat- proportion of its inherent strength and durability.
alysts for oxidation) are combined and partially Vinyl or PVC flooring was first introduced
oxidized in a reactor. At a certain stage in the pro- by Dynamit Nobel in 1934 under the trade name
cess, melted resins are added to form linoleum Mipolam [10]. Today there are many types of
cement. When the right consistency and degree vinyl flooring in the market, both in sheet and
of oxidation is achieved, the linoleum cement is tile form.
extruded, cut into billets, dusted with wood flour, The U.S. custom is to refer to these products
and further aged to continue the oxidation pro- as vinyl flooring, whereas they are commonly
cess. It is then blended with the fillers and pig- called PVC flooring in Europe. This has led to
ments in a high-intensity mixer and calendered some confusion in the American market with im-
or milled into sheets. If the finished product is ported flooring products, which are sometimes
to be a solid color flooring material or desk top thought to be based on different polymers. These
material, it may be calendered directly to a back- terms should be considered synonymous in the
ing of jute or a glass scrim. To form variegated flooring trade.
colors, accent sheets are sliced or diced to ap-
propriate sizes and calendered with a base color
to form a jaspé. If this step gives the finished 2.3.1. Raw Materials
design, the material is calendered to a backing.
If a marbled pattern is desired, unbacked jaspé Poly(Vinyl Chloride) Resins. Both vinyl
sheets are cut into strips and cross-sheeted par- chloride homopolymers [→ Poly(Vinyl Chlo-
allel to the calender nip and calendered. The re- ride)] and vinyl chloride/vinyl acetate copoly-
sulting sheet is then laminated onto a backing. mers are used in the production of resilient
The linoleum must be cured. It is festooned in flooring. As a general rule, vinyl chloride ho-
tall ovens with about 18 – 28 m in each loop and mopolymers are used in sheet flooring and solid
cured at elevated temperature for 2 – 3 weeks. vinyl tiles, while vinyl composition tiles usually
The cured product is finish coated with acrylic contain copolymers of vinyl chloride and vinyl
or nitrocellulose lacquer, inspected, and cut to acetate.
length, generally the length of one loop. The weight-average molecular mass M w of
Historical processes include inlaid linoleum, the resins most useful in flooring ranges from
in which die-cut shapes from various colored 40 000 to 200 000. The higher molecular mass
and patterned sheets were laid into matching die- polymers are frequently used in flooring wear
cut spaces in base sheet; and stenciled linoleum layers because of their greater ultimate tensile
with “scratch mix” granules, mottled, and placed strengths and abrasion resistance, whereas the
into pattern position through thick metal sten- lower molecular mass polymers, because of their
cils. The scratch mix was produced by running lower melt viscosity, are most useful in produc-
a pin-studded roll against the linoleum compo- ing foams for cushioned flooring and saturants
sition while it was worked on a two-roll mill. for glass scrim reinforcements.
Flooring manufacture employs suspension-
and modified bulk-polymerized PVC in pro-
2.3. Vinyl Flooring cesses requiring intensive mixing, dry blending,
or calendering, and emulsion-polymerized resin
Although rubber flooring enjoys a significant in processes involving liquid coating of plasti-
market share, the dominant types of resilient sols.
flooring manufactured today have a binder sys-
tem based on poly(vinyl chloride), PVC. This Stabilizers. As with any compounded
material is well suited for this application be- poly(vinyl chloride) system, the flooring com-
cause: (1) it can tolerate high levels of inert filler, position must be protected against degradation
14 Floor Coverings

from the effects of both heat and ultraviolet ra- ganic filler to provide mass and thickness at a
diation during processing and during its service reasonable cost. Pigments are added to provide
life. The stabilizers most commonly used in color, opacity, and design.
vinyl flooring are soaps of barium, calcium, and Calcium carbonate (limestone) is the filler of
zinc, and certain organotin compounds. Lead choice in flooring formulations because of its
and cadmium soaps have been used in the past low cost, lack of color, and low plasticizer ab-
but, although effective stabilizers, they are not sorption properties [13]. Talc and clay are rarely
widely used today because of environmental used, because of their significant stiffening ef-
concerns and their tendency to form colored fect on plasticized vinyl. Asbestos was used in
sulfides, a phenomenon referred to as sulfur the past in vinyl asbestos and asphalt tiles, and
staining). Epoxidized oils such as soybean oil, some sheet flooring, but it is no longer used in
tallate esters, and other partially unsaturated flooring made in the United States.
oils are frequently used as costabilizers and Fillers provide not only bulk and mass at rea-
secondary plasticizers in compounds stabilized sonable cost but also increased dimensional sta-
with metallic soaps. Organophosphites are also bility, opacity, resistance to cigarette burns, im-
frequently used as chelating agents and antioxi- proved flame spread ratings, reduced smoke gen-
dants in conjunction with metallic soap systems. eration, and reduced memory and elasticity.
The particular blends of stabilizers used in Pigments used in flooring must be heat stable,
flooring are proprietary to the manufacturers be- lightfast and resistant to change in color from al-
cause of their subtle effects on other properties kaline moisture The preferred white pigment is
important to the production or performance of titanium dioxide. Most colored pigments are in-
the products. An example of interaction is the organic, but certain colors, primarily the blues
accelerating effect by zinc soaps on the decom- and greens and some yellows, are only available
position of the blowing agents used to expand as organic compounds.
the foamed layer in some vinyl flooring.
Other Compounding Ingredients. In
Plasticizers. The vinyl binder system in many public facilities, flooring must meet cer-
flooring is plasticized to provide flexibility and tain code requirements with regard to fire and
resilience, as well as to facilitate processing. smoke properties. Specific additives may be
Di(2-ethylhexyl) phthalate has been the most used to reduce the flame spread and smoke
frequently used plasticizer for flooring because generation of the products. Agents used for
of its relatively low cost, permanence, color, and this purpose include alumina trihydrate, anti-
overall balance of performance properties. How- mony trioxide, zinc oxide, boron compounds,
ever, because of current controversy regarding phosphate esters, and chlorinated hydrocarbon
long-term health effects of this plasticizer, it has plasticizers.
been largely replaced in the United States by di- The foam layer in cushioned flooring is chem-
isononyl, diisodecyl, and diisoheptyl phthalates. ically expanded by the thermal decomposition
Butylbenzyl phthalate, historically used for of azobis(formamide) blowing agents. Some
production of vinyl composition tile, is increas- formulations may also contain processing aids
ingly being used in plastisol coatings and foam- and lubricants depending on specific processing
able base. This is a very efficient, highly solvat- methods and requirements.
ing plasticizer, and when used in plastisol coat-
ings, viscosity-depressant plasticizers such as
TXIB (2,2,4-trimethylpentane-1,3-diol diisobu- 2.3.2. Sheet Vinyl Flooring
tyrate) and dodecylbenzene are frequently in-
cluded [12]. Cushioned Rotovinyls. Cushioned ro-
tovinyls are the most common form of sheet
Fillers and Pigments. With the exception of flooring on the market today and are used ex-
the clear wear layer in most residential and tensively in residential applications.
some commercial flooring structures, the stabi- The structure (Fig. 7) typically consists of a
lized and plasticized vinyl formulation, i.e., the backing of felt composition, glass scrim, or an
binder, is mixed with varying amounts of inor-
 Floor Coverings 15

extensible vinyl film; a foam layer for cushion- to create the desired pattern. Registered emboss-
ing and to facilitate pattern embossing; a ro- ing is usually achieved by incorporating agents
togravure printed pattern, and a transparent or in selected inks that interfere with the expansion
translucent unfilled vinyl wear layer. of the foam coat [14]. There are also sophis-
ticated systems for mechanically embossing in
register.
A transparent or translucent plastisol is
coated onto the printed gel coat, and the en-
tire structure is heated to a temperature adequate
Figure 7. Typical rotogravure sheet flooring structure
a) Felt composition backing; b) Foam interlayer; c) Ro-
for complete fusion of the plastisols and expan-
togravure print; d) Clear wear layer sion of the foam layer to produce the final prod-
uct. Some processes use mechanical embossing
Production. The production of cushioned ro- techniques to create overall textures in this final
tovinyls depends largely upon the use of vinyl step.
plastisols in which emulsion-polymerized PVC, Characteristics and Uses. The most com-
blending resins, pigments, stabilizers, and other mon width of cushion rotovinyls is 12 feet,
additives are dispersed in the plasticizer system. (3.66 m) although 6, 9, and 15 foot (1.83, 2.74,
When heated to approximately 180 – 200 ◦ C the and 4.57 m) widths are also produced. The back-
plasticizer(s) solvate the resins to form a tough ings, foam, and wear layer are available in var-
plastic film. Typical formulations employed are ious gauges depending on the intended appli-
shown in Table 1. cations. The composition and thickness of the
Table 1. Typical formulations for some vinyl flooring structures components are descrided in ASTM F 1303-97
[15]. The pattern design potential is virtually un-
Ingredients Formulation∗, parts by weight per limited because of the versatility of rotogravure
100 parts resin
printing.
A B C D E Cushion rotovinyl is today the most popu-
Vinyl resin(s) 100 100 100 100 100 lar resilient flooring product in the residential
Plasticizer(s) 30 60 30 35 40 market. Most products are promoted as not re-
Epoxidized oil 5 5 4 5 quiring waxing for normal use and many have
Processing aid 8
Stabilizers 2.5 2 2 3 2
surface coatings of polyurethane, urethane acry-
Fillers and pigments 30 210 70 640 late, or other proprietary cross-linking materials
Blowing agent 5 for improved stain resistance and sustained gloss
∗ A = clear coat for rotogravure flooring; B = foam coat for retention. These coatings may be cured by ultra-
rotogravure flooring; C = filled wear layer for inlaid vinyl violet light or conventional heat in the final stage
flooring and vinyl tile; D = homogeneous sheet flooring;
E = vinyl composition tile.
of production.
The foam interlayer provides underfoot com-
fort and warmth. It is also fairly effective in re-
Rotovinyl sheet flooring is built up of sev- ducing the transmission of impact sound from
eral layers of plastisol coatings applied to the the floor to the space below, and combined with
carrier by reverse-roll or knife-over-roll coat- appropriate subfloor structures, can be used to
ing. The backing felt or other carrier is coated achieve certain impact-isolation class require-
with a foamable plastisol containing the blowing ments in multifamily housing units.
agent [typically azobis(formamide)], which de-
composes at elevated temperatures to create the Inlaid Sheet Vinyl Flooring with Backing.
expanding gases. In some structures a nonfoam- Products in this category have a felt or filled
able base coat may first be applied. After coating, vinyl backing with an inlaid vinyl wear layer of
the foamable plastisol is gelled (partially fused) varying thickness, depending on intended end
at a temperature below the decomposition tem- use [15]. The heavier gauges are used primar-
perature of the blowing agent to form a smooth ily for commercial and institutional applications
printable substrate (Fig. 8). (Fig. 9).
The gelled foam coat is then decorated with
vinyl inks by direct or offset rotogravure printing
16 Floor Coverings

Figure 8. Rotogravure production line

a) Backing unroll; b) Infeed accumulator; c) Foamable plastisol base coat; d) Reverse roll coater; e) Gelling or fusing oven;
f) Rotogravure print station (4 – 7 stations); g) Drying heater with fume hood; h) Clear coat plastisol; i) Mechanical embossing
laminator (optional); j) Outfeed accumulator; k) Windup roll

are cast onto the backing and fused and con-

solidated by heat and pressure, with or without
an unfilled vinyl matrix surround, in flat-bed or
rolling presses. Deliberate imitative designs may
Figure 9. Typical inlaid vinyl sheet flooring structure
be achieved by using a stenciling operation to
a) Felt composition backing; b) Filled vinyl composition; position granulated color onto the carrier to pro-
c) Unfilled vinyl matrix duce a specific pattern.
Characteristics and Uses. Inlaid sheet vinyl
Production. A typical formulation for the flooring is normally supplied in widths of
filled component of the wear layer is shown 6 – 6.5 feet (1.8 – 2 meters). The inlaid construc-
in Table 1, column C. The resins used are pri- tion of these products makes them sturdy and
marily suspension PVC homopolymer, but some durable. Their more massive wear layer, sup-
copolymer may be used in accent colors to con- ported directly by the felt or filled vinyl back-
trol graining. The primary plasticizers are gen- ing, provides resistance to damage by cuts and
erally of the phthalate type, although some prod- punctures and thus makes them suitable for com-
ucts may contain phosphates and/or chlorinated mercial applications.
hydrocarbons to improve flammability ratings. These products have found widespread use in
The filler is usually calcium carbonate. health-care facilities, schools, and institutions.
The ingredients are mixed and fused in a They are used also in abusive residential appli-
high-intensity mixer or a reciprocating screw ex- cations such as dormitories and military hous-
truder and milled and/or calendered into sheets ing.
of plain or variegated color. These are then
fractured, cut, or ground into various shapes
Homogeneous Sheet Vinyl Flooring.
and sizes depending on the finished design re-
These products may also be referred to as solid
quirements. Different colors of particles are fre-
vinyl sheet flooring or PVC sheet flooring. They
quently combined to produce a mottled mix.
have been popular in Europe for many years,
To produce random inlaid design the particles
particularly for commercial and institutional
 Floor Coverings 17

applications, and since the 1980s have found ries, and clean rooms; veterinary clinics; outpa-
increased popularity in the United States. tient health care clinics; and in hospital proce-
Production. Homogeneous vinyl sheet floor- dure rooms, including surgeries.
ing is normally manufactured by a combination
of calendering, consolidating, and/or laminat- Layered Composite Flooring (Heteroge-
ing processes. A generalized formulation is pro- neous Sheet Flooring). Versions of solid vinyl
vided in Table 1, column D. The types of resins, flooring becoming increasingly popular in the
plasticizers, stabilizers, and fillers are similar to United States are composite structures having a
those discussed under inlaid vinyl flooring. clear wear layer of at least 20 mils (0.5 mm) in
The compounding ingredients are mixed and thickness over a printed pattern on a filled vinyl
fused in a high-intensity, high-shear mixer, backing. The product may or may not be rein-
(Fig. 10 A, e) and sheeted through one or more forced with glass scrim.
two roll mills (f, g). Previously prepared accent The compounding ingredients are similar to
colors are added to the web at one of the mill those mentioned for both residential rotovinyls
nips to produce sheets with the desired graining. and homogeneous vinyl sheet flooring. In those
The material is then calendered through a four- cases where the wear layers are produced by hot-
roll calender (i). If the resulting sheets are to be melt calendering, no viscosity reducing plasti-
built up to achieve the required finished gauge, cizers are necessary. The products are produced
they may be laminated together in a continuous by a combination of calendering the individual
or intermittent pressing operation to obtain the layers, plastisol coating or saturating the fiber
desired thickness (Fig.10). glass reinforcement, if employed, and laminat-
Characteristics and Uses. These floors are ing in a continuous belt laminator (Fig. 10 B).
produced primarily as roll goods, but some
manufacturers cut the stock into sheets, usu-
ally three feet (0.9 m) square, or into one foot 2.3.3. Tile Flooring
square (0.3 m) tiles. Roll widths vary from four
feet (1.22 m) to 6.5 feet (2 m). The most fre- Vinyl Composition Tile. (VCT) is the most
quently specified thickness for commercial ap- widely used resilient tile product today. Because
plications is 80 mil (2 mm), although 60 mil of the general concern over the use of asbestos,
(1.5 mm) gauge is also produced by some manu- it has superseded vinyl asbestos tile (VAT).
facturers. Depending on the structure and pro- Production. A typical formulation for VCT
cess employed in production, the pattern and is shown in Table 1, column E. The vinyl resins
graining is fairly consistent throughout the thick- normally used in VCT are vinyl chloride – vinyl
ness of the product. Some laminated structures, acetate copolymers having a vinyl acetate con-
while being of solid vinyl construction, may tent in the 6 – 13 % range. The copolymers may
have the pattern only in the top layer. Their con- also be blended with PVC homopolymer to
struction and performance requirements are de- achieve certain processing characteristics. Pro-
scribed in ASTM F 1913-98 [16]. cessing aids, typically low-melting hydrocarbon
This is the most durable type of vinyl floor- resins, are used to lower the fusion temperature
ing available today. It is formulated with fairly and to assist in the mixing process.
high molecular mass homopolymers and con- The plasticizer system consists of vary-
tains relatively little inert filler. This, combined ing blends of dihexyl phthalate, diisoheptyl
with its thickness and through-color construc- phthalate, diisononyl phthalate, and butylbenzyl
tion, results in excellent resistance to abrasion phthalate. Epoxidized soy oil is also commonly
and other mechanical damage from punctures, used as a coplasticizer/stabilizer. Manufacturers
cuts, and gouges. Its composition also provides carefully guard their actual formulations, par-
good chemical resistance. ticularly with regard to fillers and stabilizers be-
Because of these factors and the fact that this cause of their subtle, yet important effect on per-
flooring is installed with heat-welded seams, it formance properties.
is used in commercial and institutional areas The ingredients are combined in a high-
having rigorous performance requirements such power, high-shear, heated mixer, (Fig. 11 a) such
as industrial, medical, and educational laborato- as a Banbury mixer to blend and fuse the in-
18 Floor Coverings

Figure 10. Production of homogeneous sheet vinyl flooring

A) Production line for calendered sheet vinyl flooring: a) Bulk storage silos; b) Plasticizers; c) Metering; d) Premixer; e) In-
tensive mixer; f) Two-roll mill no. 1; g) Two-roll mill no. 2; h) Accent color feed; i) Four-roll calender
B) Laminating system for calendered sheet flooring: a) Unroll; b) Carrier fabric; c) Press belt; d) Laminating drum; e) Em-
bosser; f) Roll up for backing; g) Annealing and cooling chamber; h) Windup roll
∗ Adapted from [12, p. 27].

gredients together. A heavy doughlike mass is an oven or by radiant heater, and consolidating
formed and dropped from the mixer onto a two- in the sheeting calender (f). Tile having an em-
roll mill (c). Accent colors (b), of the same or bossed surface texture is embossed by passage
similar composition are added to the mill nip in between another pair of rolls (i) with tooled em-
the manufacture of grained or jaspé sheet. bossing on the top roll.
When the mixing is complete and the grain- After exiting the finishing calender or, if used,
ing judged right, the stock is cut (doctored) off the embosser, a factory finish of wax or synthetic
the mill roll and folded into blankets to create polish may be applied (j) to the hot sheet to pro-
more uniform graining when passed through the vide uniform gloss, and prevent blocking of the
sheeting calender (f). The continuous web exit- tile in storage. The sheet is then cooled (k) and
ing from the sheeting calender is passed through die-cut in a punch press (m) to the finished size.
a second finishing calender (h) to reduce it to The cut tiles are then inspected and packed (n).
the final gauge and provide a smooth face. For Rejected tile and frame scrap from the punching
the production of tile having a surface applied operation is recycled (o) to the mixer.
design, previously prepared accent chips are ap- Characteristics and Uses. Vinyl composi-
plied (g) to the face of the tile between the first tion tile is produced in several gauges, sizes,
and second calender. Through-grained tile may and styles for differing intended end uses. For
also be produced by casting pre milled and frac- residential applications, VCT is offered in ser-
tured color chips onto a carrier belt, heating in vice gauge, which is approximately 1/16 of an
 Floor Coverings 19

inch (ca 1.5 mm) thick. These tiles are frequently sible to describe a specific manufacturing pro-
embossed and may contain surface applied pat- cess here. In many respects the processes are
terns and grainings. Most residential tiles today similar to those used in the production of homo-
have a printed decorative pattern with a clear geneous sheet vinyl flooring (see page 17)
vinyl wear layer laminated to a solid color vinyl Characteristics and Uses. Vinyl tile is more
composition tile backing and embossed in reg- varied in construction than is vinyl composition
ister. Many also have high-performance no-wax tile. Appliqué tiles consist of two distinct layers,
finishes, as described for sheet flooring (Sec- a base layer in one color and a overlay cut to re-
tion 2.3.2). semble brick or other pavers. Other styles have
Most commercial tile is 1/8 of an inch through-grained marble or mottle designs, while
(3.2 mm) thick, however 3/32-inch (2.4-mm) tile still others are solid-color pavers. The overall
is also available for use in light commercial thickness is usually 1/8 inch and it is available
applications. Tile for commercial applications in both 9 × 9 inch (0.2 m) and in 12 × 12 inch
is usually of the through-grained variety rather (0.3m) sizes.
than surface applied designs. The standard size Vinyl tile is considerably more flexible than
of VCT is 12 × 12 inch (305 mm square), but vinyl composition tile and has different speci-
other custom sizes may be available. fication requirements, particularly with regard
In the manufacture of vinyl composition tile, to recovery from indentation and flexibility. Be-
particular attention is given to the dimensional cause of its high binder content it has signifi-
stability, size, squareness, and the quality of the cantly higher resistance to abrasive wear and is
edge cutting. These qualities are essential for more resistant to impact damage. Conversely, its
successful installation of the tile floor. Structure higher binder content makes it less resistant to
and performance requirements of VCT are con- damage from accidental cigarette burns.
tained in ASTM F 1066-95a [17]. The initial cost of vinyl tile is significantly
Vinyl composition tile is considered to be the higher than VCT, but because of its flexibility, re-
standard or base-grade commercial finish floor- silience, and high degree of abrasion resistance,
ing. It has the lowest relative installed cost and this product is very suitable for areas subjected
has established a good performance record for to high pedestrian and cart traffic. Many vinyl
this use. The major outlet today is the mercan- tiles are offered in imitative patterns of brick,
tile market. It is used almost exclusively for the slate, and ceramic pavers and are frequently used
general floor area of grocery stores, supermar- in mercantile settings to highlight special mer-
kets, and discount department stores. It is also chandising areas in the store.
used extensively in schools, health-care facili-
ties, and to a lesser extent in offices, banks, and
light industry. 2.4. Rubber Tile and Sheet
Vinyl Tile. Vinyl tile may be referred to as Rubber tile and sheet flooring was introduced
“solid vinyl tile”, “homogeneous vinyl tile” and in the 1920s and was widely used through the
even erroneously, “pure vinyl tile”. The pri- 1950s, particularly for applications unsuited to
mary difference between vinyl composition tile linoleum and asphalt tile. Its popularity declined
(VCT) and vinyl tile is the binder content. Vinyl through the 1960s and 1970s because of the rel-
tile generally has a binder content in excess of ative success of vinyl tiles and sheet flooring.
34 % of the formula weight [18]. There is no In the mid-1980s it made a comeback in certain
minimum binder content requirement for vinyl specific applications, due partly to the popularity
composition tile. of the raised-disk design used for slip retardance
Production. The formulation of solid vinyl in areas of heavy pedestrian traffic.
tile is very similar to that used for the filled
component of inlaid sheet flooring or some ho- Production. Modern rubber flooring uses
mogeneous flooring. See Table 1, column C for styrene – butadiene rubber (SBR) as the pri-
a typical formulation. mary binder. Other rubbers that may be incor-
Since there are many proprietary methods porated with the SBR include Neoprene and ni-
used for the production of vinyl tiles it is not pos- trile rubbers as well as ethylene propylene diene
20 Floor Coverings

monomer elastomers (EPDM). A typical rub- sistance is required or where that particular dec-
ber flooring formulation contains the rubber or orative effect is desired.
rubber blend, a high-styrene resin as hardener, Rubber flooring composition is also used ex-
perhaps a hydrocarbon oil extender, fillers and tensively for molded stair tread, risers, and land-
pigments, and vulcanizing agents such as sulfur ings in public stair ways.
and zinc oxide. The preferred fillers for rubber
flooring are clays and talcs because of their rein-
forcing nature. Limestone whiting may be used 2.5. Specialty Flooring Products
as an extender in some compounds.
The ingredients are blended typically in a Conductive flooring is used in areas where
Banbury mixer, followed by sheeting through explosive or flammable vapors or dusts may
a two-roll mill. The sheet from the mill, along exist, or where control of static electricity for
with previously compounded accent colors is sensitive electronic equipment is needed. These
rolled into a “pig” that is fed to a four-roll cal- products obtain their conductivity by the use
ender; there, the accent colors produce the mar- of conductive carbon black in the formulation
bleized graining, and a relatively smooth sheet which somewhat limits the color and design ca-
approaching the final gauge of the product is pabilities. Conductive flooring is manufactured
prepared. to meet the requirements of the National Fire
For the manufacture of tile and nonroll goods, Protection Association (NFPA) for explosive or
this sheet is cut into slabs that are press cured at flammable environments [19].
elevated temperature for 10 – 12 min in multiple
or stack presses. Roll goods are cured in a con- Static-Dissapative Flooring. For the con-
tinuous press such as a Rotopress. trol of static electricity for electronics applica-
After curing, the material is allowed to age a tions, flooring products are available that are less
day or two before cutting to the finished size. The conductive than conductive flooring. The resis-
back of the tile may be sanded or have embossed tance to ground need only be in the range of 106
ribbing to provide better grab of the installation to 109 ohms, which can be achieved by incorpo-
adhesive. rating quaternary ammonium compounds in the
The wearing surface may be smooth or may formulation.
have a molded embossing such as round disks,
raised squares, or other configurations to furnish Slip-retarding flooring is used on ramps or
slip-retarding characteristics and provide special in areas where the floor will be subject to fre-
design effects. quent wetting such as entryways, vestibules,
food-preparation areas, etc. This flooring may
Characteristics and Uses. Rubber flooring
have raised areas or deep embossing to help pre-
is very durable, with excellent resistance to abra-
vent hydroplaning when wet; alternatively, min-
sion, recovery from indentation, quietness un-
eral particles such as carborundum, quartz, or
der foot, and the best resistance to accidental
other mineral aggregates may be incorporated
cigarette burns of all the modern resilient floor-
in the surface to provide increased friction with
ing products. It also has better resistance to po-
shoe soling. Combinations of these two config-
lar organic solvents, such as acetone and other
urations may also be used.
ketones, esters, and cyclic ethers. However, it
has poorer resistance to aliphatic and aromatic
hydrocarbons and vegetable oils than do vinyl
products. 3. Laminate Flooring
Rubber flooring is frequently specified in
light industry and laboratories, where its unique For some years high-precision manufacturing
solvent resistance is required. It is also used methods have been available for the production
in health-care facilities and schools, where its of flooring elements that can be laid – mainly as
good wear resistance and resilience are needed. floating floors – with surfaces ready to be walked
Raised-disk rubber flooring has found wide- on. These can be products with wood surfaces
spread acceptance in areas where wet slip re- (parquet flooring) or laminated elements.
 Floor Coverings 21

A distinction is made between flooring el- considerable continuing growth in production

ements that are laminated during manufacture capacities. Meanwhile, laminated flooring ele-
and those which are combined with laminated ments are sold by large building suppliers at
materials [high-pressure laminate (HPL) or con- prices below 10 DM/m3 . Stable market devel-
tinuous pressed laminate (CPL)] in a separate opment will be assured not only by favorable
operation. The former are produced exclusively prices, but also by products that are suitable for
on high-density fiberboard (HDF) substrates, do-it-yourself floor laying.
whereas particleboard can also be used for the
latter. Because nowadays very thin decorative
laminate sheets can be produced, these are often 3.2. Construction
indistinguishable from films.
The construction of laminated flooring elements
is very simple. To the bottom of the HDF sub-
3.1. Development strate is applied the protective film, and to the top
of the substrate are applied either the patterned
The first laminated floors were produced by Per- film alone, the patterned film plus the overlay,
storp in Sweden in the 1970s. This major manu- or the underlay plus the patterned film plus the
facturer of decorative laminates uses only ma- overlay (Fig. 11).
terials produced in its own factory, which are
applied by the short-cycle pressing technique
to particleboard. For many years, Perstorp was 3.3. Materials
the only commercial manufacturer. Then, as ru-
mours grew of allergic reactions to textile floor The substrate is the load-carrying element of the
coverings, wood-based materials, whose health design. It must be as dense and hard as possible
credentials were unquestioned, became more to resist loading pressures from furnishings. Re-
important. cently, melamine-resin-bonded HDF has been
used for high-quality products because of its
considerably better resistance to moisture rel-
ative to urea-resin-bonded products. The under-
lying protective film increases the stability of
the element, ensures constructional symmetry,
and prevents the ingress of moisture from below.
An underlay prevents the often dark background
color of the substrate from showing through
light-colored patterned films and reinforces the
whole assembly against high-pressure loads.
The main function of the patterned film is
decorative. It also has a load-bearing function
and is responsible for the wear-resistance prop-
erties if it is not covered by an overlay. In the
former case, it is resin-treated in two stages, first
by conventional impregnation and then, after a
short intermediate drying stage, with an addi-
Figure 11. Construction of a laminate flooring tile (Witex) tional melamine resin layer.
a) Very hard resin coating; b) Tongue-and-groove joint with The overlay consists of carrier papers of
extra impregnation to give water resistance; c) HDF sub-
strate; d) Resinized patterned film, e.g. ,with the appear- pure α-cellulose containing micronized corun-
ance of wood or stone, stable to UV light; e) High-strength dum powder, which is added during the produc-
film for extra hardness and impact resistance; f) Resinized tion process. These special papers are patented
protective film affords dimensional stability and are produced in the United States. They en-
After many years of rapid market growth abled high-quality laminated flooring elements
and healthy profits, there is now stagnation and to be manufactured for the first time.
22 Floor Coverings

3.4. Production and Installation act as embossing matrices. A rapid changeover

gives great flexibility in the short-cycle pressing
Pressing. Hydraulic presses are the princi- process. The plate-changing operation is there-
pal machines used in the manufacturing pro- fore also automated. The equipment for this pur-
cess, and these are also used in the production of pose has access to a compartmented magazine
self-supporting decorative laminated plates, for that normally stores 15 different matrices. The
which all three types of commonly used presses changeover cycle requires only 10 min. It is op-
are used: multiplate presses with cooling, one- erated by a movable arm, which uses suction to
plate presses without cooling, and double-band pick up the plate that has been taken out of the
presses with or without cooling. Direct lami- compression space by the discharge equipment
nation is by far the most important process in and places it on the band conveyor which takes
the manufacture of flooring elements, mainly it to the plate magazine. After the old plate has
by short-cycle pressing. However, some double- been placed in the magazine, a new plate is taken
band presses have been installed recently. out by reversing the process.
In short-cycle pressing, pressing times of There are two fundamentally different dou-
10 – 20 s (depending on the number of films to ble-band pressing systems in competition with
be applied) and pressures of 3 MPa are normally each other. One operates with a surrounding
used. Up to two cycles per minute at pressing sealed cushion of compressed air, and the other
temperatures of 180 ◦ C are currently achieved. with free-flowing oil films on which the stainless
The following operations are performed fully steel bands slide. For coating operations with
automatically: relatively simple process parameters, the much
– From height-adjustable holding racks, usu- cheaper version with the air cushion can be con-
ally with three compartments, film is with- sidered, while for high-pressure coating materi-
drawn by pulling devices. When the protec- als the other system is recommended because of
tive film is in position, the substrate is of- its ability to meet demanding requirements.
fered up to it by means of a movable arm Double-band presses are now available in ev-
with suction pick-up, and the film is applied ery working width demanded today. In contrast
from above in a second station. The film to the short-cycle pressing technique, in which
is applied as precisely as possible to mini- the films are seldom fed from rolls, double-
mize film overlap and reduce formation of band presses are always supplied from rolls of
waste by splintering. For flooring elements, film. This is one of the advantages of continuous
especially with patterned strip flooring, the pressing. Film storage and feeding mechanisms
symmetry of the pattern across the width is occupy very much less space than is required
very important. The printed areas at the joints in short-cycle pressing technology. As flooring
must be in exact alignment. products are produced in large quantities, the
– The short-cycle presses of various machine rolls of film can be used continuously without
manufacturers differ only in their feed sys- interruption, and the management of left-over
tems, whereby speed is of the greatest impor- materials on rolls is minimized.
tance. Here, the critical dwell time, which The process parameters are approximately
begins with the application of heat in the the same as those in short-cycle pressing tech-
compression space and ends when sufficient nology. The feeding rate, which determines the
pressure is reached, plays an important role. production capacity, is ca. 18 m/min. Assuming
It is ca. 2 s. Such short times can only be a heated film length of 2000 mm, this would give
achieved with the aid of equipment that al- a pressing time of ca. 6.5 s. This extremely short
ternately feeds materials and discharges the pressing time can only be realized if the films are
tiles at high speed. impregnated in-house with adherence to strict
– The final operations are to clean the edges of conditions. These include the quality and age of
the tiles, to check the surfaces visually, and the resin for the impregnation process and also
in some cases to cut the tiles and stack them. the storage time of the impregnated films. The
Changing the pressing plates plays a very film resins must have sufficient time under pres-
important role in short-cycle pressing technol- sure to enable them to flow. Only then can the
ogy, as the stainless steel pressing plates also required fully densified surfaces be achieved.
 Floor Coverings 23

Production capacity is an important criterion Two types of multibladed saws are used. One
for choosing between short-cycle and double- operates with a single motor which drives a cen-
band pressing. Thanks to the continuous im- tral, replaceable drive shaft to which the saws are
provements being made to digital servo-motors attached, usually by quick-release bushes; the
and other control systems, the speed of the short- other has a drive for each saw blade, and these
cycle pressing technique is continually being in- can be rapidly adjusted to different widths by
creased, so that charging times play a continually digital controllers. Inoperative motors are stored
diminishing role. Thus, it was only a question of in parking stations. Depending on the format of
time until the 18 m/min or even 20 m/min of the the sheets, lengthwise cutting can precede sev-
double-band presses could be matched by long eral transverse cuts. The cut products are con-
short-cycle presses, albeit at the cost of increased ditioned for up to two more days to relieve the
space requirements. A major press manufacturer stresses that are an inevitable consequence of the
in Westphalia has delivered a short-cycle press cutting process.
of 13 m operating length to Italy. It is expected to
operate at two cycles per minute. Double-band Formatting and Profiling. Variants of the
technology will respond with an extended com- above process all aim to reduce the condition-
pression area. However, as the hardening reac- ing time. These include direct linking of the
tion takes place essentially over the first meter, cutting saw with the profiling production line.
this imposes strict demands. In all cases, this involves risks. Whether these
Embossed pressing bands are much more outweigh the gain in rationalization is a ques-
expensive than the equivalent pressing plates. tion that must be considered. After cutting, the
Also, changing the pressing band is much more workpieces always lie with the patterned side up-
time-consuming and difficult. However, flooring wards. On placing the tiles in the profiling line,
elements without embossing are of lower qual- the patterned sides are turned to face downwards
ity, both visually and for practical purposes. The so that the underside of the element is subject to
wide range of embossing patterns that can be the tolerances of the profiling step.
produced by pressing plates is not available with Profiling is performed by two angled double-
bands, simply because of the exorbitant costs ended profilers. The first, for the lengthways
of the latter. However, the continuous process machining, can be replaced by a grooving ma-
achievable by continuous presses gives consid- chine. Modern production lines have high out-
erable potential savings in the consumption of puts. The newest plant can produce 120 ele-
electrical and thermal energy. ments per minute, sort them, pack them into car-
tons, stack the cartons on palettes, and load the
Conditioning and Cutting. After pressing, palettes into containers.
the laminated plates are allowed to stand so that The design of the milling stations is decisive
internal stresses caused by unevenly distributed for the fit of the profiles. An absolutely level sur-
moisture and temperatures can even out. Short- face of the fitted flooring, with gap-free joints
cycle products are generally stacked for about both lengthwise and crosswise, is the criterion
5 d. Attempts are being made to shorten this time by which the customer will eventually judge the
by using star coolers. Double-band presses with quality. A precisely level surface can only be
cooling give products that are much easier to cut achieved if the workpieces are milled to give a
and which only require about half the time for close fit one with another over the entire batch.
stress relief. With high feed rates, there can be undesired fric-
After conditioning of the full-sized products, tional heating, which can be aleviated by a care-
they are precisely cut to the required dimensions. fully controlled air cushion. The profiles must
Patterned products have a clearly visible symme- not only mate cleanly, but above all must show
try line that was applied applied during pressing. high repeatability. From one consignment to the
Prior to the multibladed saws, alignment devices next, year after year, there must be no flaws of
adjust the position of the sheet until two optical any kind.
sensors indicate that the symmetry axis has been The sharpness and life of the tools play an
reached. important role. Overlays filled with corundum
powder lead to tool wear because of their very
24 Floor Coverings

abrasive properties. Hence, only diamond tools

are used, and these are replaced at high speed
with the aid of a quick-action chuck. Polycrys-
talline and monocrystalline diamond fragments
(PCD and MCD, respectively) are under discus-
sion for this application. It would appear that
the extremely expensive MCD tools are not cost-
effective, although their useful life is many times
that of PCD tools.

Water-Resistant Finishing. As it is not yet

standard to use melamine-bonded HDF as sub-
strate, the profiles are impregnated with water- Figure 12. Laying of laminate flooring
resistant material after both lengthwise and a) Laminate flooring; b) Wool-felt board; c) Vapor barrier;
crosswise machining. The water-repellent ma- d) Flooring plaster; e) Heating tube; f) Screening; g) Insu-
lation; h) Moisture barrier; i) Concrete floor
terial is applied evenly over the whole length of
the joint without allowing it to spread over the The floated surface forms a large unit with
surface; it is then allowed to soak in and dry. material-corresponding shrinkage or growing,
The water-resistant material must not affect the and water imbibition values. It must therefore
adherent properties of the adhesive used for the always be kept at a distance of at least 10 mm
installation of the floor. from walls and pillars, and these gaps can be
covered with matching edge strips. Both adhe-
Packaging. A quantity of floor tiles equiva- sive and mechanical fixing of flooring elements
lent to approximately 2 m2 of flooring has be- are used. The former still dominates the market,
come established as a suitable package size. but will probably be replaced by dry methods.
Packaging is carried out in the profiling produc- The poly(vinyl acetate) adhesive must exude up-
tion line, and is therefore subject to demands wards through the joints along their entire length
for high production rates. Few manufacturers to prevent water penetration. With mechanically
use completely automatic packing equipment. fixed elements, this additional protection is not
The cheapest method is to secure the pack- provided, and a water-resistant finish or water-
ages, which usually contain eight flooring ele- resistant substrate is necessary. The fixing adhe-
ments, with sealing tape. These, together with sives must be moisture-proof, tough, elastic, and
the product information, which is also automat- of high strength.
ically packed, are then shrink-wrapped to give
protection from dirt and moisture. Packing in
cartons gives greater protection against dam- 3.5. Testing
age. The elements can either be placed, from
above, in an automatically prefolded carton or be Laminate flooring was defined in early 2000 in
packed in a slip-lid carton. Here, too, additional the European Standard EN 13 329 and its specifi-
foil wrapping is advisable. The product infor- cations and properties were described. Laminate
mation and preferably also the patterned surface flooring is described as having closed pores, and
should always be visible from outside, for ex- this property can be measured by testing its sen-
ample, through a window. sitivity to staining by certain test materials (e.g.,
graphite). According to EN 438, laminate floor-
Installation. Laminate flooring is laid by ing is Grade 3, but it should preferably be Grade
floating on sheeting that deadens impact sound 4.
and protects from moisture (Fig. 12). In accor- Before the appearance of the laminate floor-
dance with the guidelines for laying PVC floor- ing standard EN 13 329, the abrasion resistance
ing, the base, usually concrete, must be well was determined and used as a single value in
dried and even, as these thin flooring materials accordance with EN 438. Because of the un-
are not capable of bridging over large disconti- suitability of the testing of highly wear-resistant
nuities.
 Floor Coverings 25
Table 2. Abrasion resistance classes for laminate flooring

Level of use
Domestic Commercial
Moderate General Heavy Moderate General Heavy

Class 21 22 23 31 32 33
Abrasion AC1 AC2 AC3 AC3 AC4 AC5
resistance

laminate flooring by methods developed for fur- 13329, maximum edge-swelling values being
niture, values of 4000 – 20 000 revolutions were 18 % for commercial and 20 % for domestic use.
quoted as test results. In the new standard the Other test specifications of relevance for lam-
wear resistance test has been improved, and the inated floorings are listed below:
test for highly wear resistant overlays has been
EN 309 Wood Particleboards – Definition and
modified. Classification
The new test results enable the products to be EN 311 Particleboards – Surface Soundness of
grouped according to their abrasion resistance, Particleboards – Test Method
EN 316 Wood Fibreboards – Definition, Classification
so that each type of overlay can be assigned to and Symbols
an abrasion-resistance class (Table 2). EN 318 Fibreboards – Determination of Dimensional
The well-known hardness tests such as Changes Associated with Changes in Relative
Humidity
Brinell and ball indentation values are of only EN 438 Decorative High Pressure Laminates
limited suitability for determining the hardness (HPL) – Sheets Based on Thermosetting Resins
of a laminate floor. These tests therefore do not EN 685 Resilient Floor Coverings – Classification
EN 12529: Castors and Wheels – Castors for
feature in the European laminate standard. The 1998 Furniture – Castors for Swivel
French laminate standard NFB 54 020 gives a Chairs – Requirements
minimum value of 4 or 5 MPa.
Laminate floors are produced with a wide
range of gloss values. Two or three years
ago these were in the 10 – 15 range, but now 3.6. Environmental Aspects
more and more producers offer gloss values of
18 – 20. These high values enable reproduction Laminate floorings are built up of layers of var-
to be even more realistic. ious materials. This often leads to the assump-
As a result of overlay technology and the ex- tion that “plastic floor coverings” are difficult to
istence of melamine resins, laminate floorings dispose of in an environmentally friendly man-
are very resistant to heat and are therefore resis- ner. However, laminate floorings can be disposed
tant to a glowing cigarette (better than Grade 4 of like furniture and with as few problems. In
of EN 438). As a rule, laminate floorings meet both cases, because of the high wood content,
the requirements of B1 of DIN 4102 Part 14. the most appropriate disposal route is controlled
Taking all their properties into consideration, combustion, the heating values being good.
laminate floorings stand up very well in compar- VOC emissions from the product are very
ison to other floor coverings. Past criticisms with low, so that a laminate floor is classified as a very
respect to moisture sensitivity and footstep noise low emission material. Formaldehyde emissions
are to be set against the developments in mod- are in the range 0.02 – 0.04 ppm, i.e., on the or-
ern laminate floorings. Special backing coatings der of those of natural wood.
and nonswelling substrates are reducing footstep Milling operations produce wood dust and
noise and improving edge instability. shavings. The usual national recommendations
Whereas attempts are still being made to de- apply to these materials. When the material is
velop a scientific test for footstep noise, test- cut during the course of installation on a build-
ing methods for edge-swelling behavior and the ing site, dust emissions can vary. Saws should
measurement of dimensional stability by mod- preferably be provided with dust-extraction
ified testing procedures are described in EN equipment.
26 Floor Coverings

Figure 13. European sales (including exports) of laminate flooring (in 106 m2 )

3.7. Economic Aspects 7. Frederick Walton: The Infancy and

Development of Linoleum Floorcloth, London
The European market for laminate floorings con- 1925.
tinues to grow rapidly and is forecast to be 8. G. Forster et al., Linoleum , Verlag moderne
180 × 106 m2 in the year 2000 (Fig. 13, while Industrie, Landsberg 1996.
the German market is expected to level out at ca. 9. R. F. Lonzillotti: The Hard Surface
40 × 106 m2 . In western Europe, laminate floor- Floor-Covering Industry, State College of
ing had a ca. 6.8 % share of the total flooring mar- Washington Press, Pullman, Washington,
1955.
ket in 1998, corresponding to ca. 100 × 106 m2 .
10. B. Berkley: Floors, Selection and
Maintenance, LTP Publishers, Chicago 1968.
11. Floor Covering Weekly 47 (1998) no. 28.
4. References 12. A. S. Wilson, Plasticizers, Principles and
Practice, Institute of Materials, London 1995,
1. Carpet Market Overview, DuPont, 1999. p. 36.
2. R. C Buck: New Nylon Stain Resist 13. A. W. McKee: “Study of the Effects of Fillers
Technology. 36th International Man-Made in Compounding Plastic Flooring,” Soc. Plast.
Fibers Congress, Dornbirn, Austria, 1997. Eng. J. 18 (1962, Feb.) no. 2, 186 – 190.
3. M. P. W. Wilson: The Chemical and Physical 14. Congoleum-Nairn Inc., US 3 293 094;
Properties of Polyamides: a Review, 37th 3 293 108, 1966 (R. Frank Nairn et al.).
International Man-Made Fibers Congress, 15. Standard Specification for Sheet Vinyl Floor
Dornbirn, Austria, 1998. Covering with Backing, ASTM F 1303-97.
4. M. P. W. Wilson (1999) Designing Carpet 16. Standard Specification for Sheet Vinyl Floor
Fibers for Esthetics and Performance. 38th Covering without Backing, ASTM F 1913-98.
International Man-Made Fibers Congress, 17. Standard Specification for Vinyl Composition
Dornbirn, Austria. Floor Tile, ASTM F 1066-95a.
5. P. L. Hauck: Carpets and Hygiene, Recent Key 18. Standard Specification for Solid Vinyl Floor
Learning’s, TIFCON 1994. Tile, ASTM F 1700-96.
6. P. L. Hauck: Sustainable Growth and 19. Standard for Health Care Facilities, National
Environmental Excellence are Interdependent, Fire Protection Assn., NFPA 99, Quincy,
TIFCON 1999. Mass. 1984, p. 24.
 Flotation 1

Flotation
See also → Solid – Solid Separation, Introduction
Baki Yarar, Colorado School of Mines, Golden, Colorado 80401, United States

1. Introduction . . . . . . . . . . . . . . . 2 2.4.2. Adsorption – Desorption of Organic

1.1. Interfacial Energies Reagents . . . . . . . . . . . . . . . . . . 10
and Contact Angle . . . . . . . . . . . 2 3. Electrical Phenomena . . . . . . . . . 11
1.2. Hydrophobic and 4. Bubble – Particle Interactions . . . . 14
Hydrophilic Solids . . . . . . . . . . . 3 5. Flotation Processes . . . . . . . . . . . 15
2. Flotation Reagents . . . . . . . . . . . 3 5.1. The Gamma Flotation Process . . . 16
2.1. Functional Classification of Flota- 5.2. Design of Flotation Operations . . . 17
tion Reagents . . . . . . . . . . . . . . . 3 5.3. Flotation Machines . . . . . . . . . . . 18
5.4. Industrial Applications . . . . . . . . 20
2.2. Chemical Classification . . . . . . . . 4
5.4.1. Sulfide Mineral Flotation . . . . . . . . 21
2.3. Surface and Solution Chemistry . . 7 5.4.2. Nonsulfide Flotation . . . . . . . . . . . 24
2.3.1. Solubility . . . . . . . . . . . . . . . . . . 7 5.4.3. Coal Flotation . . . . . . . . . . . . . . . 25
2.3.2. Surface Activity . . . . . . . . . . . . . . 8 5.4.4. Flotation of Precipitates and Ions . . . 26
2.4. Interactions between Flotation 5.4.5. Use of Oil Droplets instead of Air Bub-
Reagents and Solids . . . . . . . . . . 8 bles . . . . . . . . . . . . . . . . . . . . . 27
2.4.1. Adsorption – Desorption of Inorganic 6. Future Trends . . . . . . . . . . . . . . 27
Reagents . . . . . . . . . . . . . . . . . . 10 7. References . . . . . . . . . . . . . . . . . 28

Symbols γ SL = solid – liquid interfacial tension

ε = dielectric constant
C = equilibrium concentration of surfactant
ζ = zeta potential
in solution
η = viscosity of aqueous medium
E = electric field between electrodes apply-
θ = contact angle
ing the field
πD = disjoining pressure
k = Boltzmann constant
p = pressure inside a bubble
po = pressure of the bulk of the liquid
Pa = probability of particle-bubble adhesion 1. Introduction
Pc = probability of particle-bubble collision
Pf = probability of flotation General Aspects. Flotation is one of the
Ps = probability of formation of a stable well-established physicochemical separation
particle-bubble aggregate processes, widely applied in mineral concentra-
S = spreading coefficient for air on solid tion and recovery operations; other applications
T = temperature include water treatment and purification, the re-
Ve = electrophoretic velocity of particle cycling of secondary materials, and the recovery
W = work of adhesion of ionic and colloidal materials from aqueous so-
Γ = surface excess concentration of surfac- lutions.
tant measured in quantity per unit area Various forms of this process are known as
(e.g., molecules/cm2 ) froth flotation, ion flotation, precipitate flotation,
γ = specific surface energy of liquid film piggyback flotation, flotoflocculation, skin flota-
γ0 = specific surface energy of an infinitely tion, column flotation, and two-liquid flotation
thick film of a liquid [1–8]. Gamma flotation is based on the control
γ LG = liquid – gas interfacial tension of liquid – vapor interfacial tension to facilitate
γ SG = solid – gas interfacial tension the particle – bubble adhesion process [9].

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b02 23
2 Flotation

Because most flotation processes are applied

γSG −γSL =γLG cosθ (1)
with water as the principal liquid, and the widest
area of applications is in the field of mineral pro- W =γLG (1 − cosθ) (2)
cessing, mostly systems containing water and S =γSL − (γLG +γSG ) (3)
minerals are discussed here.
where γ SG = solid – gas interfacial tension,
γ SL = solid – liquid interfacial tension, γ LG = liq-
uid – gas interfacial tension, θ = contact angle,
1.1. Interfacial Energies and Contact S = spreading coefficient for air on solid, and
Angle W = work of adhesion. For particle – bubble ad-
hesion the conditions W > 0, S > 0, and θ > 0
The flotation process relies primarily on the fact are satisfied.
that hydrophilic particles are wetted by water, Figure 2 describes the mechanical equilib-
whereas hydrophobic particles are wetted by oils rium among the three interfacial tensions indi-
and air bubbles; therefore, if air bubbles are in- cated as vectors applied to point C, known as the
troduced into an aqueous slurry, the bubbles ad- three-phase contact point; the contact angle θ is
here to the hydrophobic solid particles. As a measured in the liquid phase. The two variables
result, air – solid aggregates are carried to the cos θ and γ LG are readily accessible by experi-
surface, forming a froth layer; this explains the ment. Contact angles on minerals in various me-
name froth flotation. The froth layer can be re- dia are given in Table 1. The significance of the
moved manually or mechanically; the result is contact angle arises from the fact that it is a mea-
the separation of hydrophobic from hydrophilic sure of surface wettability; θ > 0 indicates a hy-
particles. For further information on detergency, drophobic solid. Contact angle values of θ > 10◦
see also → Laundry Detergents, Chap. 2.1. usually indicate that particles can form bubble –
particle contacts strong enough to resist turbu-
lence in a conventional flotation cell, enhancing
the probability of flotation as decribed in Chap-
ter 4.

Table 1. Contact angles of solids in water and various aqueous

media

Solid Contact Solution conditions

angle
(degrees)

Colemanite 43 5×10−3 M oleate ∗

solution
Copper metal 93 in 50 mg/L oleate ∗
solution
Fluorite 91 in 10−5 M oleate ∗,
pH = 8.1
Galena 60 in 10−3 M ethyl xanthate
solution
Graphite 96 water
Figure 1. Processes occurring in a flotation cell (Schematic) Ilmenite 80 treated with oleate ∗,
A) Flotation cell a) Froth overflow; b) Froth layer; c) Pulp; pH = 8, T = 75 ◦ C
d) Rotor for pulp agitation Colorado oil shale with 59.5 water
B) Mineralized air bubbles within flotation cell 28 % organic carbon
Paraffin wax 108 water
Silica 81 2.5 mg dodecylammonium
The principal processes occurring in a slurry- chloride per L solution,
containing vessel known as a flotation cell are pH = 10
shown in Figure 1. Equation (1), known as the Teflon 160 water
Teflon 0 methanol – water solution
Young–Dupré equation, and Equations (2) and with surface tension
(3) are used to describe the relationship of phys- <20 mN/m
icochemical variables to particle – bubble adhe- ∗ Sodium oleate.
sion.
 Flotation 3

Frothers. Frothers promote the formation of

a metastable froth phase that facilitates the re-
moval of particles carried by air bubbles to
the top of the flotation cell. They also reduce
the induction time; that is, they allow collid-
ing particles and bubbles to establish contact
Figure 2. Equilibrium contact angle more rapidly. The usual induction times in sul-
a) Captive bubble in water; b) Hydrophobic solid
fide flotations are of the order of milli- or mi-
Cosθ= γSGγ −γSL
LG croseconds [12]. Examples of frothers are pine
oil, long-chain alcohols, and polyoxypropylene
derivatives.
1.2. Hydrophobic and Hydrophilic
Solids Auxiliary Reagents. These reagents include
depressants, which are used to prevent solids
Although most naturally occurring minerals are from becoming hydrophobic, and activators,
hydrophilic, some are hydrophobic. Examples which promote the adsorption of reagents onto
of the latter include graphite, sulfur, antimonite selected solids. For example, high pH impedes
(Sb2 S3 ), molybdenite (MoS2 ), talc, and high- the flotation of sulfide minerals by xanthates.
rank coals such as anthracite. Many polymers, Thus, reagents used to increase pH, e.g., NaOH
such as Teflon and Nylon, are also hydrophobic. or Ca(OH)2 , would be depressants in this con-
Hydrophilic materials can be made hy- text. Sulfide ions similarly impede the flotation
drophobic by the adsorption of chemicals. For of sulfides in the same system, and Na2 S used
example, calcite (CaCO3 ) can be readily made as a source of sulfide ions would act as a de-
hydrophobic by treating it with low concentra- pressant. Other depressants include starch and
tions of sodium oleate (C17 H33 COONa). Sil- quebracho.
ica (SiO2 ) can be made hydrophobic by treat- On the other hand, sphalerite (ZnS) does not
ment with dodecylamine (C12 H25 NH2 ). A solid readily become hydrophobic in the presence of
made hydrophobic by chemical treatment can xanthates unless copper (II) ions are introduced
revert to the hydrophilic state on further chem- into the aqueous pulp. In this case CuSO4 , used
ical change. For example, galena (PbS), in to supply copper (II) ions, is an activator. Other
contact with 25 mg/L potassium ethyl xanthate examples of activation are provided by divalent
(potassium O-ethyldithiocarbonate) [140-89-6] ions such as barium or calcium in the flotation of
(C2 H5 OCSSK) solution, is hydrophobic at pH silica by fatty acids. In this case, silica is inert to
below 10.8, but hydrophilic at higher pH. Teflon these reagents unless a divalent cation is intro-
is highly hydrophobic in most aqueous media, duced into the pulp at alkaline pH. Thus, CaCl2
but behaves like a hydrophilic solid if the sur- or Ba(NO3 )2 used as sources of these divalent
face tension is reduced below 20 mN/m by the cations and NaOH used to raise the pH would
addition of methanol [10]. Chemicals used to af- be activators of silica for flotation by fatty acids.
fect the hydrophobic – hydrophilic properties of The terms collector and frother do not precisely
solids are known as flotation reagents. describe the action of such reagents in all sys-
tems.
Although oleic acid acts primarily as a col-
2. Flotation Reagents lector in the flotation of solids such as scheel-
ite (CaWO4 ) it also exhibits excellent frothing
2.1. Functional Classification of properties when present in sufficient quantities.
Flotation Reagents On the other hand, nonanol [143-08-8], a well-
known frother, is the sole reagent required for
Collectors. These are used primarily to make the flotation of talc or high-rank coals, where
solids hydrophobic and promote adhesion to air it acts simultaneously as frother and collector.
bubbles or oil droplets. Common examples are The same is true for activators and depressants.
fatty acids, sulfonates, xanthates (dithiocarbon- For example, sodium sulfide was cited previ-
ates), amines, and dithiophosphates.
4 Flotation

ously as a depressant for sulfide minerals in the into all categories of the functional classifica-
presence of xanthate reagents. In fact, heavily tion. The organic reagents can be classified as
oxidized (tarnished) sulfide minerals are treated follows:
with sodium sulfide before the introduction of
Polar:
xanthates for flotation, making Na2 S an activa-
anionic: polar group is an anion, e.g., oleate,
tor in this type of flotation pulp (see Fig. 3).
CH3 (CH2 )7 CH=CH(CH2 )7 COO−
cationic: polar group is a cation, e.g., RNH+3
amphoteric: anionic or cationic, depending
on pH, e.g., alkylaminocarboxylic acids,
RNH(CH2 )x COOH
nonionic: polar group is not ionized, e.g.,n-
hexanol, CH3 (CH2 )4 CH2 OH
Nonpolar: e.g., saturated hydrocarbons

Table 2. Inorganic auxiliary flotation reagents

Compound Composition Common

Applications

Lime CaO pH regulator,

depressant
Sodium carbonate Na2 CO3 pH regulator,
(soda ash) dispersant
Sodium hydroxide NaOH pH regulator,
(caustic soda) dispersant
Sodium sulfide Na2 S sulfide depressant and
ore sulfidizer
Sodium bisulfide NaHS sulfide depressant and
ore sulfidizer
Sulfuric acid H2 SO4 pH regulator
Sodium cyanide NaCN sulfide depressant
Calcium cyanide Ca (CN)2 sulfide depressant
Sodium dichromate Na2 Cr2 O7 PbS depressant
Cupric sulfate CuSO4 ZnS, FeAsS, Sb2 S3
activator
Lead acetate Pb (CH3 COO)2 Sb2 S3 activator
Sodium ferrocyanide Na4 Fe (CN)6 depressant in Cu – Mo
sulfide circuits
Potassium KMnO4 FeS2 depressant in
permanganate FeAsS flotation
Sulfur dioxide SO2 activated ZnS
depressant
Sodium thiosulfate Na2 S2 O3 SO2 source in acid
circuits
Sodium silicate Na2 SiO3 siliceous gangue
Figure 3. Activation Processes dispersant
A) Activation of malachite [CuCO3 · Cu (OH)2 ] by sodium Sodium fluosilicate Na2 SiF6 depressant in
sulfide a) In the presence of 0.43 mol/L ethyl xanthate; b) In iron-flotation circuits
the presence of 0.43 mol/L isoamyl xanthate a, b Sodium e.g., (NaPO3 )6 dispersant
B) Activation of ZnS by CuSO4 in the presence of 25 mg/L polyphosphates
potassium ethyl xanthate c Sodium fluoride NaF activator in silicate
a With permission of [7]. b Excessive quantities of sulfide flotation
Nokes reagent complex mixture of general depressant in
reduce the recovery. c Redrawn from [11].
molybdenite
P2 S5 , As2 O3 , flotation circuits
Sb2 O3 , NaOH, etc. except for MoS2

2.2. Chemical Classification

Organic flotation reagents are also classified
Flotation reagents may be inorganic or organic. by functional group, including fatty acids, car-
The former are largely used as auxiliary reagents boxylic acids, thiols, xanthates, sulfates, sul-
(Table 2), whereas the latter (Tables 3 and 4) fall fonates, and amines.
 Flotation 5
Table 3. Organic reagents commonly used as flotation collectors
6 Flotation
Table 4. Organic chemicals used in flotation as depressants, slime depressants, and flocculants

Figure 4. Micelle formation

A) Spherical micelle B) Straight-chain surfactant (amphipatic) molecule
a) Polar end; b) Nonpolar end C) Laminar micelle
 Flotation 7

The following organic reagents are commonly taining more than eight carbon atoms are insol-
used as flotation frothers: uble in water and are used as frothers.
Most ionic or polar flotation reagents are
sufficiently soluble in water. Solubility is lim-
ited mainly by the tendency of such compounds
to form molecular aggregates in the aqueous
medium known as micelles when present in high
concentrations (Fig. 4, see previous page). The
concentration at which micelles form is known
as the critical micelle concentration (cmc).

2.3.2. Surface Activity

The ability of reagents to alter the liquid – vapor

interfacial tension, γ LG , of aqueous solutions is
called surface activity (see also → Surfactants).
For example, although the surface tension of dis-
tilled water is about 72 mN/m at room tempera-
ture, the introduction of a flotation reagent such
as sodium dodecyl sulfate at a concentration of
0.005 mol/L reduces this value to 48.5 mN/m.
Such organic reagents contain two chemical
groups: a nonpolar moiety, usually a saturated
hydrocarbon, and a polar moiety, which may be
ionic (e.g., −COO− , −SO− −
3 , −SO4 ) or non-
ionic (e.g., −OH, −NH2 , >C=O).
The quantitative relationship between the
concentration of an amphipatic molecule and its
effect on the surface tension at concentrations
below the cmc is described by the Gibbs adsorp-
tion equation:
dγLG T
=− Γk (4)
dC C
where γ LG = solution surface tension,
C = equilibrium concentration of surfactant in
2.3. Surface and Solution Chemistry solution, k = Boltzmann constant, Γ = surface
excess concentration of surfactant measured in
2.3.1. Solubility quantity per unit area (e.g., molecules/cm2 ), and
T = temperature.
Inorganic reagents used in flotation are always Based on Equation (4), the variation of so-
highly soluble in water whereas organic reagents lution surface tension can be discerned to be as
may not be. Nonpolar oils, for example, are in- shown in Figure 5, which predicts that some sub-
soluble in water and must be added to the flota- stances ought to increase surface tension, creat-
tion cell or the preceding conditioning tank, at ing a surface deficiency, as opposed to surface
high shear created by intense agitation of the excess concentration. This condition is met by a
pulp. Alternatively, these reagents can be pre- number of inorganic compounds shown in Fig-
pared as emulsions or sometimes dissolved in an ure 6.
alcohol such as methanol before addition to the Not all amphipatic flotation reagents exhibit
flotation system. Straight-chain alcohols con- pronounced surface activity, as demonstrated by
8 Flotation

Figure 5. Variation of solution surface tension by solutes

according to the Gibbs adsorption equation (Schematic)
A) Effect of organic surfactants on γ LG and Γ . Condition
of surface excess concentration
B) Effect of inorganic solutes on γ LG and Γ . Condition for
surface deficiency.
γ H2 O = Surface tension of pure water; γ = Surface tension
of solution; Γ = Surface excess concentration

Figure 6. Compounds that lower the surface ten-

sion of water are not necessarily surface ac-
tive, although their structures may indicate am-
phipatic properties. Short-chain alcohols, ace-
tone, and simple ethers fall into this category
(see Fig. 7 on top of next page).
Figure 6. Effects of inorganic salts and organic flotation
reagents on the surface tension of water
a) Sodium hydroxide a ; b) Sodium chloride a ; c) Potas-
2.4. Interactions between Flotation sium ethyl xanthate b d) Polyoxyethylene n-decanol with 30
ethylene oxide groups b ; e) Cetyltrimethylammonium bro-
Reagents and Solids mide c ; f) Sodium oleate d ;
a Drawn from data in [13]. b With permission from [14]. c

As a general rule, for alteration of the hydropho- Drawn from data in [15]. d Redrawn from data in [16].
bic – hydrophilic properties of solids in a flota-
tion pulp, adsorption or desorption at the sur- Silica, treated with trimethylchlorosilane
face is a prerequisite. Thus, for a solid to be- (Si (CH3 )3 Cl) shows hydrophobic – hydrophilic
come hydrophobic or hydrophilic it must first transitions that depend on time, pH, and tem-
take up ions or molecules from the medium or re- perature [17]. In all the experimental cases re-
lease them into it. Alternatively, a solid made hy- ported for this system, whether the solid was
drophobic by the adsorption of a reagent changes hydrophilic or hydrophobic, the organic reagent
only by the action of other species which alter the was present at the solid surface. The variation
surface properties. This may or may not require of hydrophobic – hydrophilic properties was at-
the desorption of the species originally present. tributed to the tenacity of the aqueous layer at the
For example, at a given pH, a given sulfide min- solid – liquid interface; the desorption of species
eral requires a minimal concentration of flotation that confer hydrophobic characteristics is not al-
collector before stable bubble – particle contact ways essential for a solid to exhibit hydrophilic
(flotation) can occur [8] (Fig. 8, see next page). properties.
 Flotation 9

Figure 7. Surface tension of aqueous solutions of acetone

and methanol
a) acetone; b) methanol

Naturally hydrophobic solids need to be con-

sidered a special case of this general rule, be-
cause they may require no surfactant uptake
from the medium to become hydrophobic, but
can be made hydrophilic by adsorbed reagents. Figure 8. Role of carbon chain length in flotation
For example, most wetting agents, e.g., Aerosol A) Sphalerite (ZnS) in the presence of various chain-length
OT, (sodium dioctylsulfosuccinate) [577-11-7], xanthates at pH = 3.5 ∗
a) 6 Carbons, hexyl xanthate; b) 4 Carbons, isopropyl xan-
eliminate the natural hydrophobicity of graphite. thate; c) 2 Carbons, ethyl xanthate
B) Quartz (SiO2 ) flotation by alkylammonium acetate solu-
tions; chain lengths indicated at their natural pH ∗∗
∗ With permission [18]. ∗∗ With permission [19].

2.4.1. Adsorption – Desorption of Inorganic

Reagents

In general, the chemical reactions of inorganic

flotation species in aqueous solution can be
described in terms of solubilities. The classi-
cal equilibrium constant (solubility product) ap-
plies:
MA2
M 2+ + 2 A− (5)


2
Ksp = M2+ A− / [MA2 ] (6)

Figure 9. Cation concentrations derived from the dissolu- where M 2+ indicates the cation (metal) concen-
tion of some metal hydroxides at different pH [21]
∗ Calculations made assuming that the solubility product
tration in solution, A− the anion concentration,
expression given in Equation (6) applies; more elaborate and K sp the solubility product. Figure 9 shows
calculations including other hydrolytic species can also be the relationships of hydrolysis and precipitation
made [22, 23] that occur in the aqueous phase for various ions
10 Flotation

in accordance with the solubility product princi- spectroscopy shows that the calcium oleate
ple. Traces of ions or their hydrolysis products formed by the interaction of oleic acid with
many play important activator roles in flotation calcite or fluorite is not identical to the calcium
[20]. salt of oleic acid, Ca (C17 H33 COO)2 , obtained
from CaCl2 and sodium oleate [28].

2.4.2. Adsorption – Desorption of Organic Hydrophobic Bonding. Association of the

Reagents hydrocarbon ends of amphipatic substances
leads to the formation of micelles (Sect. 2.3.1).
Organic reagents and solids suspended in a flota- Similarly, many saturated hydrocarbons, such
tion pulp interact by one or more of the mech- as kerosene or fuel oils, are readily adsorbed
anisms given below. Some processes, such as on naturally hydrophobic solids, e.g., graphite
hydrogen bonding, are also important in the sol- or freshly cleaved bituminous coal. Such in-
ubilization of polar substances in aqueous me- teractions are mainly a result of London – van
dia. der Waals forces. Furthermore, the hydrocarbon
ends of surfactants, such as dodecylbenzenesul-
Hydrogen Bond Formation. This bond fonate, and dodecylbenzenesulfate, associate at
(strength ca. 21 – 29 kJ/mol), usually associated the solid – liquid interfacial region, resulting in
with the physical properties of ice and water, low-energy structures known as hemimicelles
is favored when a group contains hydrogen at- [29].
tached to a highly electronegative element such The strength of association is a function of
as F, O, S, or N. Thus, the adsorption of an amide the hydrocarbon chain length and is of the order
group, present in proteins or nonionic polyacry- of 1 kT per −CH2 -group (where k = Boltzmann
lamide (a depressant), on fluorite or silica is due constant and T = temperature). The unique bond
to this bond [24, 25]. The interaction of elemen- that leads to such adsorptions and molecular as-
tal sulfur and alcohols probably also takes place sociations is called the hydrophobic bond. Al-
by hydrogen bond formation. though the term has been criticized [30], it has
been generally accepted.
Electrostatic Interactions. Such interac-
tions are nonspecific, occurring between groups Multiple Dipole Interaction Bonds
that carry electrostatic charges of opposite sign. (Crystal-field Interactions). The adsorption
Bond formation occurs by charge attraction. of tannins (depressants in flotation) or poly-
A typical example in flotation systems is the acrylamide on fluorite has been attributed to the
adsorption of amines that carry cationic po- formation of a bond in which an active group
lar groups on silica, which carries a net nega- of the reagent is held in the crystal field of the
tive electric charge at pH > 2. Many treatments adsorbing solid [31]. Little information on such
of reagent – solid interactions in flotation sys- bonds is available.
tems tend to exaggerate the importance of elec-
trostatic interactions, overlooking other mecha- Collector Fitting into Solid Lattices. The
nisms. separation of similar salts, such as NaCl and
KCl, by the use of amines is a well-established
Chemical Bond Formation. Chemical industrial practice. Although a number of mech-
bonds are characterized by their strength (typ- anisms have been suggested for the selective in-
ically greater than ca. 42 kJ/mol) and usually teraction between KCl and primary amines, the
lead to the formation of saltlike structures at most widely accepted is that the amine fits into
solid – liquid interfaces. A surface compound is spaces on the KCl lattice vacated by K+ because
not necessarily identical to a compound formed the ionic sizes of −NH+ +
3 and K are compara-
in the bulk of the solution [26, 27]. Examples ble. Thus, KCl is made selectively hydrophobic,
of such bonds include the interaction of fatty whereas NaCl is not (Fig. 10).
acids, which carry the polar carboxylate group In many systems more than one mechanism
(−COO− ), with sparingly soluble solids such may act simultaneously and synergistically. The
as calcite (CaCO3 ) or fluorite (CaF2 ). Infrared
 Flotation 11

term adsorption is used here for the accumula-

tion of a dissolved species on a solid particle. The
term sorption is preferred by some authors. The
terms physical adsorption or physisorption and
chemisorption are also used to distinguish bet-
ween bonds with strengths less than 20 kJ/mol
and those greater than 42 kJ/mol, respectively.

Figure 10. Schematic representation of the selective adsorp-

tion of amine ions on sylvite (KCl) [32]
A) Potassium chloride (KCl)
B) Sodium chloride (NaCl)
a) Cl− b) NH+ +
3 ; c) K ; d) Na
+

3. Electrical Phenomena
The main phenomena to be considered in this
connection are those associated with the solid –
liquid interfacial region. On contact of the solid
with the aqueous medium, ionization, ion dis-
solution, or ion adsorption occurs, resulting in
charging of the particle surface. Hydrolysis in
the aqueous medium may also alter the charac-
ter of the ionic species passing into it. The pre-
dominant phenomena here relate to the fact that
cations are hydrated more than anions and that Figure 11. Crystal structures and mode of cleavage of min-
thermal energy promotes ion mobilization in the erals
system. Ruptured bonds and the lattice parame- A) Fluorite (CaF2 ) and its cleavage plane
ters also affect the properties of the solid – liquid a) Calcium; b) Fluorine
B) Graphite
interface. The cleavage of fluorite, graphite, and C) Chalcopyrite (CuFeS2 ) which cleaves irregularly, some-
chalcopyrite are shown in Figure 11. times at the (011) plane
Within short periods of contact, a double a) Copper; b) Iron; c) Sulfur
layer (usually referred to as the electric double
layer), consisting of the charged surface of the consists of a surface with fixed charge whereas
solid and counter ion, is established. Although the ionic cloud countering it is diffuse [33]. The
earlier theories considered this charge arrange- overall system, consisting of the solid and the
ment to be in the form of a simple plate capaci- ionic medium surrounding it, conforms to the
tor, colloid science showed that the double layer principle of electroneutrality.
12 Flotation

Zeta potential is widely used to describe the

role played by the electrical double layer in flota-
tion. It corresponds to the potential that exists at
the so-called shear plane, which is created when
a charged particle moves under the influence of
an external electric field.
Zeta potential can be measured by elec-
trophoresis, sedimentation potential, streaming
potential, and electroosmosis. In the first two of
these methods the shear plane is created by the
motion of the particle; in the other two, the par-
ticle (more precisely, a porous bed consisting of
many charged particles) is fixed [34, 35]. Equa-
tion (7) correlates the zeta potential with the Figure 12. Relationship between iep and flotation properties
of goethite (FeO (OH)) [36]
electrophoretic mobility of the particles under • = Sodium dodecyl sulfate or -sulfonate;
= Dodecyl-
the influence of an external electric field: ammonium chloride;
= iep
∗ Courtesy USBM; zeta potential measurements made in
4πη Ve 10−4 M NaCl; note that minimum flotability occurs at the
ζ= (7)
ε E pH of iep and anionic reagents act as collectors at ζ > 0
whereas cationic reagents collect goethite at ζ < 0.
where
ζ = zeta potential
η = viscosity of the aqueous medium
ε = dielectric constant
V e = electrophoretic velocity of particle
E = electric field between electrodes applying
the field
At 25 ◦ C and η = 0.895 mPa · s, Equation (7) re-
duces to
ζ = 12.8 V e = 12.8 u where u = electrophoretic
mobility.
The significance of the zeta potential becomes
apparent where electrostatic interactions play a
major role in flotation reagent adsorption, as
shown in Figure 12. The condition at which ζ = 0
is known as the isoelectric point (iep), some-
times, less accurately, the zero point of charge
(zpc). In principle, although an iep can be de-
fined for each solid for numerous conditions,
the variable most frequently used to describe the
ionic conditions at which iep occurs is pH.
Adsorption mechanisms correlate with zeta
potential; that is, physical adsorption affects the
magnitude of the zeta potential. A change of sign
in the presence of an appropriate concentration Figure 13. Representation of the fact that zero zetapotential
does not necessarily indicate zero surface potential (ψ o ) [35,
of adsorbate (see Fig. 13) is taken as an indi- p. 221]
cation of a chemisorption-type reagent uptake Dashed line = Inner Helmholz plane; wiggled line = Shear
[38]. As seen from Figure 13, the iep does not plane
necessarily indicate zero potential at the surface ∗ Although ψ o1 and ψ o2 are positive and ψ o3 is negative,
all conditions indicate ζ = 0; inner Helmholz plane passes
of the particle, only that the potential at the shear through the centers of unhydrated, specifically adsorbed
plane is equal to zero. ions.
 Flotation 13

Depending on the mechanism of reagent – cles. Particle flotability can be treated as a prob-
solid interaction, many systems exhibit corre- ability [39]:
lations between system variables and zeta po-
tential (Fig. 14). Pf = Pc ·Pa ·Ps (8)
where
Pf = probability of flotation
Pc = probability of particle – bubble collision
Pa = probability of particle – bubble adhesion
Ps = probability of formation of a stable parti-
cle – bubble aggregate
In some methods, such as vacuum flotation,
where dissolved gases become the bubble
source, or in situ bubble-generation processes,
where acids generate bubbles of carbon dioxide
from carbonate-containing pulp, the probability
treatment needs to be modified. Equation (8),
however, is widely applied, because most flota-
tion systems rely on extraneously introduced air
bubbles. Particle – bubble aggregates are shown
in Figure 15.

Figure 14. Correlation of commonly measured flotation and

surface chemical variables in the quartz-dodecylammonium
acetate system
– = % Recovery; – · – = Zeta potential; ◦–◦ = Con-
tact angle; • – · · – • = Monolayer
∗ With permission [37].

Figure 15. Different forms of particle – bubble aggregates

The following isoelectric points (ζ = 0) are [7, 41]
observed in the absence of other substances. A) Particle attached to bubble
B) Multiple bubble attached to large particle (common in
AgCl pAg+ = 4
vacuum flotation)
AgBr pAg+ = 5.4
C) Particle – bubble flocculation in pulps containing fine par-
Ag2 S pAg+ = 10.2
ticles
CuSiO3 · 2 H2 O pCu2+ = 4, at pH = 7
CaF2 pCa2+ = 3
Fe2 O3 pH = 6.5 and 8.2 Solids to be floated carry an aqueous film,
FeS2 pH = 7 which may have a thickness as low as tens of
FeS2 pH = 5 (30 mg NaCN/L)
PbS pH = 3.5
nanometers [40]. The stability of this film deter-
SiO2 pH = 2 – 3.7 mines whether a particle will adhere to a bub-
SiO2 neutral pH in the presence of ble on collision within the slurry: if the film
3×10−3 mol dodecylam-
monium acetate/L
thins, ruptures, and recedes, adhesion is facil-
itated. The time taken for the film to undergo
these processes is known as the induction time.
Film stability has been quantified in terms as
4. Bubble – Particle Interactions disjoining pressure [27].

The ultimate objective of a flotation process is πD =p −

∞ po (9)
the selective removal of solid particles from the γ =γ0 πD dh (10)
aqueous medium, which is accomplished by the h
adhesion of air bubbles to the hydrophobic parti- where
14 Flotation

π D = disjoining pressure Disjoining pressure depends on the summa-

p = pressure inside bubble tion of electrical double-layer effects (π E ), sol-
po = pressure of the bulk of the liquid vation effects (π s ), and London – van der Waals
γ = specific surface energy of the liquid film forces (π v ); i.e., π D = π E + π s + π v , as well as on
γ0 = specific surface energy of an infinitely the heterogeneity of the solid surface [42]. The
thick film of the same liquid role of frothers is to make π D more positive, i.e.,
The conditions for film stability are shown in reduce film resistance to rupture.
Figure 16.

For stable films: ∂π D
<0

∂π T
∂h
5. Flotation Processes
For unstable films: ∂h T > 0
D

The phenomena described so far relate to the

froth flotation process. The following variations
and techniques are also used:

Collectorless flotation:
froth flotation using the natural hydrophobicity
of some minerals

Two-liquid flotation:
variant of froth flotation, using oil droplets in-
stead of air bubbles and an oil layer instead of
froth

Column flotation:
variant of froth flotation, employing columns 3 –
9 m high with 0.3 – 1.5 m cross-section

Microbubble flotation:
variant of column flotation, employing bubbles
10 – 50 µm in diameter

Dissolved-air flotation:
air bubbles are generated by applying vacuum
to air-saturated slurries

Gamma flotation:
liquid – vapor surface-tension control is used to
separate hydrophobic particles

Piggyback flotation:
also known as carrier flotation: uses the mutual
coagulation of solids; when one is floated,
the other (usually more difficult to float on
its own) is also collected

Skin flotation:
Figure 16. The concept of disjoining pressure [40] hydrophobic particles are removed without
A) Schematic representation of a disjoining film between a froth, but at a layer approximately one par-
particle and a bubble
B) Relation of film stability to disjoining pressure
ticle thick
a) Stable film; b) Metastable film; c) Unstable film
 Flotation 15

5.1. The Gamma Flotation Process

The gamma flotation process is characterized by

emphasis on the control of solution surface ten-
sion. The critical surface tension of wetting of
solids is based on a plot of the cosine of contact
angle θ against the surface tension of the solu-
tion in contact with a solid [43]. Each hydropho-
bic solid exhibits cos θ = 1 (zero contact angle)
at a given solution surface tension as shown in
Figure 17. Difficulties in contact-angle measure-
ments on powdered solids, as used in flotation
practice, can be overcome by a technique where
flotation recoveries are plotted against solution
surface tension [10, 44, 45]. The γ LG at which
flotation recovery is equal to zero is taken as
the critical surface tension of wetting, γ c , of the
solid under investigation. The two techniques
[43–45] are equivalent [10]; the proof of this
constitutes an independent demonstration of the
thermodynamic basis of the flotation process
[46].

Figure 17. Schematic of critical surface tension of wetting Figure 18. Schematic of physical basis of the gamma flota-
by contact-angle measurement tion process [9]∗
A) Adhesion tension vs. solution tension for two solids with
different critical surface tension or wetting
Figure 18 shows the use of critical surface B) Relation of flotation recovery to solution surface tension
tension differences of two hydrophobic solids for two solids with different critical surface tension or wet-
by controlling the surface tension of the solu- ting
γ c1 = Critical surface tension of wetting of solid 1;
tion in which they are suspended. This method γ c2 = Critical surface tension of wetting of solid 2;
is called gamma flotation [9]. The value of the ∗ Lines a, b, and c obtained by substituting values into the
process has been demonstrated for a number adhesion tension equation, e.g., [γ LG cos θ].
of flotation systems including oil shale, sulfide ∗∗ In the shaded area solid 1 with γ c1 floats, whereas solid
2 with γ c2 is completely wetted by the aqueous solution.
16 Flotation

Figure 21. Flotation in high surface tension solutions ∗ [9]

a) NaCl; b) Na2 SO4
∗ This method is also known as salt flotation [7, p. 338, 339],
[13].

Figure 19. Separation of Colorado oil shale sizes fractions

by exploiting the kinetic aspects of gamma flotation [47]
a) <13 µm; b) 18 – 13 µm; c) 26 – 18 µm; d) 38 – 26 µm;
e) 48 – 38 µm

Figure 22. System variables that affect the flotation process

[9]

salts raise the surface tension of water to val-

Figure 20. Separation of a mixture of silica and magnetite ues above the usual 72 mN/m. Figure 21 demon-
by gamma flotation ∗ strates the relationship between solution surface
a) SiO2 ; b) Fe3 O4 tension modified by salts and flotation results
∗ Powders have been initially made hydrophobic by treat- obtained with various coals [9].
ment with appropriate surfactants and mixed after filtration
[49]

minerals, and others [48–50] (see Figures 19 5.2. Design of Flotation Operations
and 20). Salt flotation, which has been used in
coal processing, is a variant of gamma flotation Flotation testing is generally preceded by geo-
in which the natural hydrophobicity of coal is logical, engineering, and mineralogical work.
exploited and the surface tension of the solution The overall flotation system is a complex com-
is controlled by salts. Figure 6 shows that some bination of variables outlined in Figure 22, but
 Flotation 17

laboratory testing is based on mineral character- 5.3. Flotation Machines

istics and reagent properties. Recovery is “the
percentage of total values contained in the ore Flotation machines consist of a chamber (cell)
which is recovered in the concentrate”; grade equipped with entry and exit ports and an agi-
refers to “assay of values in the concentrate.” tation assembly that keeps the pulp in constant
Recovery and grade tend to vary inversely. motion during the separation. These machines
Laboratory tests are designed to establish fulfill the following functions: (1) mixing and
crushing and grinding conditions and optimize agitation of the slurry, (2) aeration and promo-
such variables as pulp density, reagent addition, tion of particle – bubble collisions, (3) formation
pH, and auxiliary reagent concentration before of a froth layer and its removal for product re-
the pilot plant stage. An important laboratory covery, and (4) continuous discharge of tailings,
test is the “locked-cycle test”, which simulates consisting of components not collected in the
pilot plant conditions (Fig. 23) [1]. froth layer [53].
The design of a flotation machine (or cell) is
largely empirical and aims at maintaining high
throughput subject to the previously stated cri-
teria; the Wemco flotation machine is shown in
Figure 24. Flotation cells can reach volumes of
20 – 25 m3 [54]. Figure 25 is an outline of con-
temporary flotation machine types; Figure 26
shows cell geometries and paddle designs in
mechanically agitated flotation machines. Flota-
tion machines used in water treatment are not al-
ways mechanically agitated but may rely on the
quieter conditions provided by the generation of
air bubbles in the system.

Figure 24. Wemco flotation machine ∗

a) Motor; b) Weir level; c) Rotor submergence; d) Rotor top;
e) Adjustable collar; f) False bottom; g) Draft tube; h) Rotor;
i) Disperser; j) Hood; k) Stand pipe; l) Air inlet duct
Figure 23. Schematic of locked-cycle test [51] ∗ With permission [53]

Flotation machine variables, such as volume, Such methods include vacuum flotation, in
area, throughput, aeration rate, and cell layout which air-saturated water is subjected to a vac-
are considered at the plant-design stage. Sim- uum for bubble generation. Pressure flotation, on
ulation studies using computer modeling tech- the other hand, does not require the application
niques have gained increasing acceptance [1, of vacuum, since air bubbles are released after
52]. The final plant layout provides for prod- saturation of water under pressure. Electroflota-
uct handling, filtration, dewatering, tailings dis- tion has also been used to a limited extent. In
posal, and plant-water recycling. this method hydrogen and oxygen bubbles are
generated by electrolysis [57].
18 Flotation

Figure 25. Types of flotation machines, their modes of operation, and representative manufacturers [54–56]

A new version of an old flotation cell has Peripheral speed: S = π ND ∝ Da (a ∼ 0 – 0.5)

led to the development of column flotation (see Power (constant viscosity and density)
Fig. 27) [58–60]. Column cells seem to perform Net power consumption: P ∝ N 3 D5 /N c D2c
best with highly hydrophobic solids. They are (c ∼ 0 – 0.33)
used for the recovery of sulfides and coal, and Aeration
to recover valuable particles rejected in the tail- Air-flow number: N (Q) = Q/AND ∝ Df (f ∼ 0)
ings of conventional, mechanically agitated, bat- Impeller diameter is the parameter of machine
teries. Column flotation offers the following ad- size
vantages: Geometry: L ∝ D1−r ; A ∝ D 2 (1−r) ;
n (1−r)
V∝D
1) reduction of gangue entrainment in froth,
Power: P ∝ D(a+1) (3−c)−1
2) increase of bubble residence times in the
Aeration: Q ∝ Da+f+2 (1−r)
pulp,
Power intensity or specific power:
3) improved selectivity,
P/V ∝ D (a+1) (3−c)−n (1−r)−1 ∝ D b
4) energy economy per unit weight of values
Nominal residence time of air:
recovered, and
V/Q ∝ D (2−n) (r−1)−(a+f) ∝ Dq
5) improved control and instrumentation.
N = Impeller rotational speed in rpm;
The following relationships are used in the de-
D = Impeller diameter; L = Tank length. Expo-
sign of flotation machines [56]:
nents are experimental parameters characteristic
Geometrical of specific machine design.
Effective volume: V ∝ L n (n ∼ 2 – 3)
Froth area: A ∝ L 2
Impeller/tank aspect ratio: D/L ∝ Dr (r ∼ 0 –
0.5)
Impeller speed
 Flotation 19

Figure 26. Schematic of impeller and tank geometries of mechanically agitated flotation cells [55]
a) Air port; b) Diffuser; c) Impeller; d) Standpipe; e) Shaft; f) Propeller; g) Aerating impeller; h) Recirculation well; j) Pulp
entry; k) Rotor; m) Disperser hood

5.4. Industrial Applications and sulfur removal from coal, separation of sol-
uble minerals such as halite (NaCl) and sylvite
Various methods of separation exploit differ- (KCl) from each other, and recovery of fine gold
ences in size, relative density, and magnetic and [6–8, 61].
electrostatic properties. Flotation, however, ex- Water-treatment applications include the re-
ploits two unique controllable properties of par- moval of oily components and colloidal matter
ticulates (Table 5): (1) it operates at very fine from industrial waters, water recycling, and the
particle sizes, and (2) it is based on inherent or removal of color and metal ions.
modified surface properties of solids.
Since its discovery in the late 19th century, Mineral Flotation. Minerals containing
the flotation process has been used principally valuable elements can be recovered econom-
in the minerals industry. At present, it is used ically by flotation (Table 6) in the following
to treat several thousand million tonnes of ore stages:
annually. Most of the minerals-related applica-
tions aim at recovering ore values, rejecting the Crushing and grinding. These steps reduce
rest as tailings. particle size and mechanically liberate the
Applications of flotation in the minerals in- desired minerals. Some deposits, such as
dustry are diverse and include recovery of sul- beach sands or placers, do not require crush-
fide minerals, upgrading phosphates ores, ash ing, which is usually effected by jaw or gyra-
20 Flotation

tory crushers. For grinding, equipment such Table 5. Physical properties of particulates and size ranges suitable
as ball mills and rod mills is employed. for separation technology
Classification and sizing. As can be seen
Physical property Physical separation Approximate
from Table 5, the optimal size range for flota- technique particle size range,
tion is 10 – 500 µm. Coal particles can be mm
floated at the upper limit, and copper sul- Color or radiation sorting 10 – 100
fide particles at the lower. Particles of non- Size dry or wet screening 0.01 – 10
sulfide minerals finer than 50 µm, however, Size, shape, wet or dry cyclones 0.005 – 1
density
interfere with flotation. Such fines are sepa- sedimentation and 0.003 – 3
rated by hydrocyclones, sedimentation tanks, hydraulic classification
and other classification equipment; they are centrifugation 0.001 – 0.05
Density heavy media 1 – 10
discarded as slimes (Figure 28). Size, density jigging 5 – 50
Conditioning. In the conditioning opera- tabling 0.005 – 3
tion the ore powder is slurried with water Magnetic wet or dry magnetic 0.001 – 5
susceptibility separation
and flotation reagents, forming the flotation Surface or bulk electrostatic separation 0.05 – 5
slurry. In the flotation step, air is introduced conduction
to transfer hydrophobic particles to a froth Surface chemistry flotation 0.001 – 0.5
spherical agglomeration 0.01 – 0.5
layer, which is skimmed away mechanically selective coagulation and 0.05 – 0.001
by paddles. selective flocculation

The solids content of the pulp, known as pulp

density, averages 20 – 40 %, but may be 3 – 10 %
in some systems, such as coal flotation. In the
preparation of potable water, the solids content
may be well below 1 %.
The mineral flotation process is carried out in
interconnected batteries of flotation cells, where
slurry flow occurs by gravity and the level of the
slurry is controlled by gates or weirs.
The arrangement of flotation cells, some-
times with intermittent grinding of the products,
leads to flotation circuits of which five basic
types have been identified [62] (Fig. 29).

5.4.1. Sulfide Mineral Flotation

Sulfide minerals such as those of copper

(CuFeS2 ), lead (PbS), and zinc (ZnS) are com-
monly found in the same ore. Xanthates (dithio-
carbonates) and dithiophosphates are used as
collectors in sulfide mineral flotation; frothers
include pine oil and synthetic commercial com-
pounds such as Dowfroth 250. Some qualified
generalizations apply to sulfide mineral flota-
tion:
Figure 27. Pilot plant size flotation column 1) Xanthates and dithiophosphates are collec-
a) Wash water flow meter; b) Conditioner; c) Valve; d) Con- tors for sulfides.
centrate discharge; e) Porous glass diffuser; f) Air regulator;
g) Air flow meter; h) Tails discharge 2) The chemisorption of xanthates and the pres-
ence of oxygen are essential for the flotation
of sulfide minerals such as galena [63–65].
 Flotation 21
Table 6. Elements contained in minerals recovered by flotation

Element Mineral Composition Element Mineral Composition

Al bauxite Al2 O3 · xH2 O (Fe,Mn,Ti) Mn pyrolusite MnO2

Al kaolinite Al2 Si2 O5 (OH)4 Mo molybdenite MoS2
As arsenopyrite FeAsS2 Na halite NaCl
Au native gold P fluorapatite Ca5 F (PO4 )3
B colemanite Ca2 B6 O11 · 5 H2 O S native sulfur
Ba barytes BaSO4 Si quartz SiO2
C diamond carbon Sn cassiterite SnO2
C graphite carbon Sr strontianite SrCO3
Ca calcite CaCO3 Th fergusonite (Y,Ce,U,Th,Ca) (Nb,Ta,Ti) O4
Cr chromite FeO · Cr2 O3 Ti rutile TiO2
Cu chalcopyrite CuFeS2 U carnotite K 2 O · 2 U 2 O3 · V2 O5 · 2 H 2 O
F fluorite CaF2 V vanadinite Pb5 ClV3 O12
Fe hematite Fe2 O3 W scheelite CaWO4
Hg cinnabar HgS Y monazite (Ce,Y) PO4
K sylvite KCl Zn sphalerite ZnS
Li spodumene LiAl (SiO3 )2 Zr zircon ZrSiO4
Mg magnesite MgCO3

Figure 28. Characteristics of slimes [7]

This correlates well with the electrochem- conditions. The ratio of concentration of xan-
istry of the system and the stability of species thate to hydroxide for such a critical transi-
that collect at the solid surface (Fig. 30). tion usually conforms to the Barsky relation-
3) Other variables being constant, an increase ship: [X− ]/[OH− ] = constant
in chain length for a homologous series of 5) The ions OH− , S2− , CN− , Cr2 O2−
7 are com-
reagents strengthens them as collectors; this mon sulfide mineral depressants for selectiv-
rule also applies to other minerals; see Fig- ity control in flotation; Cu2+ is an activator
ure 14. for ZnS in flotation by xanthates. Figure 31
4) At a given constant collector concentration, is a flow diagram of a sulfide flotation plant.
a critical pH for each sulfide mineral deter-
mines the boundary of flotation – no flotation
22 Flotation

Figure 29. Flotation circuit configurations ∗

A) Type 1; B) Type 2; C) Type 3; D) Type 4; E) Type 5
∗ With permission [62].
 Flotation 23

5.4.2. Nonsulfide Flotation

Nonsulfide ores include those of iron, phos-

phate, fluorite, magnesite, and beach sand. Some
ores may contain sulfur-bearing minerals as sec-
ondary components. Collectors in these systems
are generally fatty acids and their salts, sul-
fonates, and sulfates. Amines are also used, es-
pecially in iron-bearing ores and in silicate flota-
tion. Figure 32 shows the separation of lead car-
bonate, barium sulfate, and calcium fluoride in
a 100 t/d plant; the main gangue is siliceous ma-
terial.
Phosphate-ore concentration plant flow
sheets are shown in Figures 33 and 34. Their
difference lies in the run-of-mine grades and the
complexity of gangue minerals.
Figure 30. E h -pH Diagram of thermodynamically stable An interesting application of nonsulfide min-
species and associated experimental data in the galena – eral flotation is the separation of soluble salts
oxygen – xanthate flotation system [42] from brines (Fig. 35). Primary amines are well-
x = Strong bubble contact; o = Feeble bubble con-
tact;v = Oxidizing depression by potassium chromate; established selective collectors and have long
∧ = Reducing depression by sodium sulfite-ferrous mixture; been used in the production of KCl from the
. . . . . = Xanthate (10−3 M) – dixanthogen (saturated); Dead Sea. In some cases, clays interfere with
- - - - - = Galena – dixanthogen system in equilibrium with
10−3 M xanthate ion; E = Electrical potential

Figure 31. Flow sheet of plant treating 30 000 t/d of molybdenite ore, Henderson Mill, Colorado ∗
a) Gyratory crusher; b) Self-cleaning magnet; c) Ore storage bin; d) Semiautogenous mill; e) Pump box; f) Thickener;
g) Cleaner; h) Tailing pond; i) Concentrate holding tank; j) Pump; k) Disc filter; l) Dryer
∗ Courtesy of Denver Equipment Co.
24 Flotation

Figure 32. Flow sheet for PbCO3 , CaF2 , and BaSO4 concentration ∗
a) Coarse ore bin; b) Apron feeder; c) Jaw crusher; d) Belt conveyor; e) Fine ore bin; f) Ball mill; g) Cyclone; h) Conditioner;
i) Reagent feeders; j) Sampler; k) Flotation machine; l) Concentrate thickener; m) Pump; n) Disc filter; o) Screw conveyor;
p) Elevator and storage bins; q) Fluorspar filter; r) Dust cyclone; s) Dryer
∗ Courtesy of Denver Equipment Co.

the flotation and need to be depressed by the ad- whole mass subjected to flotation without re-
dition of starch, lignin, or cellulose derivatives. course to primary gravity separation. The natu-
ral hydrophobicity of freshly ground coal is an
asset which minimizes the use of collectors. A
5.4.3. Coal Flotation small quantity of MIBC or pine oil (50 – 100 g
Coal is cleaned by gravity separation to reduce per tonne of mineral) acts as both collector and
ash and pyrite content [69]. These methods in- frother.
clude jigging, tabling, and heavy-media separa- On extended storage, or if the coal seam has
tion. The fines (ca. 400 µm, 35 mesh) are treated been in contact with air for geological time peri-
by flotation. To liberate ash and sulfur-bearing ods, coal loses its hydrophobicity and is referred
components, the run of mine coal is sometimes to as “weathered coal”. In such cases, MIBC, low
ground to ca. 600 µm (28 mesh) or finer, and the pH, and the addition of hydrocarbon oils such as
 Flotation 25

Figure 33. Flow sheet for phosphate ore flotation in Brazil ∗

a) Slime thickener; b) Rod mill; c) Ball mill; d) Cleaner; e) Rougher; f) Scavenger; g) Conditioner; h) Concentrate regrinder;
i) Concentrate thickener; j) Tailing thickener; k) Tailing pond
∗ The main mineral of value is apatite; the gangue contains barytes, iron oxides, and silicates; fatty acid flotation generates
concentrates assaying an average of 36 % P2 O5 , with recoveries of 62 – 63 %; with permission [66].

kerosene or fuel oil make coal matter floatable 5.4.4. Flotation of Precipitates and Ions
[42,70].
Sometimes, pyrite is first removed by conven- Precipitate flotation is based on the same prin-
tional sulfide mineral flotation using xanthates ciples as mineral flotation. For example, in the
as collectors. This is followed by the flotation of preparation of potable water, the adjustment of
coal matter and the rejection of ash-forming ma- pH to precipitate ferric ions as hydroxides elim-
terials such as silica, silicates, and carbonaceous inates most of the iron and colloidal matter by a
shale. subsequent flotation step. In this case, the water
Unlike other minerals, coal exhibits a high contaminants render the hydrolysis product suf-
degree of variation with respect to origin, age, ficiently hydrophobic for bubble – particle adhe-
rank, moisture content, degree of weathering, sion to permit flotation under quiescent condi-
physical and chemical structure, and nature of tions.
gangue. As a result, it is difficult to develop a Alternatively, dissolved ions can be electro-
unified flotation strategy from sample to sam- statically attached to selective cations, which in
ple. Even samples of the same origin undergo turn can be collected in a foam layer (Fig. 37).
surface chemical changes to different extents on The recovery of Au, Pd, Pt, and Ir by such foam
prolonged storage. fractionation methods, as well as the removal of
Nonetheless, generalized strategies are pos- uranium from aqueous solutions by the use of
sible (Table 7). Figure 36 shows a flow sheet of amines, has been demonstrated [73–75].
coal flotation [71]. Figure 38 shows a foam fractionation (ion
flotation) assembly. At times of increasing en-
vironmental concern, the removal of heavy
metal ions and toxic substances such as PCBs
26 Flotation

Figure 34. Flotation flow sheet for Finnish low grade apatite ore ∗ [67]
a) Silo; b) Feed bin; c) Rod mill; d) Ball mill; e) Hydrocyclone; f) Cone classifier; g) Conditioner; h) Pressure filter
Head ore = 3.9 % P2 O5 ; Concentrate grade = 36.5 % P2 O5 ; Recovery = 75 – 79 %
∗ Gangue minerals include calcite, dolomite phlogopite [(KMg3 (AlSi3 ) O10 (OH,F)2 ], and mica.

(polychlorinated biphenyls) seems a promising assemblies similar to those used in conventional

area for further application of ion flotation and flotation technology.
foam fractionation techniques. This method has been used for alumina
(Al2 O3 ), hematite (Fe2 O3 ), cassiterite (SnO2 ),
and artificial diamonds, by first making the pow-
5.4.5. Use of Oil Droplets instead of Air ders hydrophobic with an amine or a sulfonate,
Bubbles followed by extraction into an oil phase [76,
77]. The thermodynamics of the system apply
Surfaces to which air bubbles can adhere are equally well to the now well-established process
also readily wetted by hydrocarbon oil droplets of coal cleaning by oil agglomeration.
in preference to water. This has been demon-
strated thermodynamically and experimentally.
Although micrometer-size solid particles may 6. Future Trends
adhere nonselectively to air bubbles, the replace-
ment of air by hydrocarbon oils provides better The decline in the mining and metallurgical in-
selectivity, as proved experimentally. These con- dustries has shifted emphasis away from conven-
siderations have given rise to the development of tional flotation technology. Nonetheless, under-
two-liquid flotation for extraction of finely di- standing of the fundamentals of flotation is by
vided solids into an oil phase (oil extraction) in no means complete and development of sophis-
 Flotation 27

Figure 35. Potash treatment flow sheet as practiced by the Potash Corporation of Saskatchewan, Canada [68]

ticated instrumentation is leading to combined of flotation chemicals is also under development

research on materials science and on surface fun- and wider application of flotation in recycling
damentals of flotation [78]. industries is at its early stages.
As new applications, such as control of the
so-called pulp potential, control of redox condi-
tions, E h , use of critical surface tension of wet- 7. References
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Engineering Foundation Publ., New York
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28 Flotation

Figure 36. Flotation flow sheet applicable to oxidized coals Figure 38. Schematic of continuous-flow foam fractionation
or low pyrite-content coal ∗ column [72]
a) Cyclone; b) Conditioner, 6 %; c) Conditioner, 25 %; a) Ion storage; b) Surfactant storage; c) Pump; d) Mix tank;
d) Fine rougher float, 6 %; e) Coarse rougher float, 15 %; e) Saturator; f) Moisture trap; g) Flow meter
f) Drier; g) Disc filter
∗ With permission [71].

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 Flotation 31

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Flour → Cereals and Cereal Products

Flouranthene → Hydrocarbons
 Fluid Mechanics 1

Fluid Mechanics
David V. Boger, Department of Chemical Engineering, The University of Melbourne, Parkville, Victoria
3052, Australia
Y. Leong Yeow, Department of Chemical Engineering, The University of Melbourne, Parkville, Victoria 3052,
Australia

1. Introduction . . . . . . . . . . . . . . . 3 4.1.1. Bingham Type Behavior . . . . . . . . 27

2. Basic Equations of Fluid Mechanics 5 4.1.2. Shear-Thinning (Pseudoplastic) Fluids 28
2.1. Continuity Equation . . . . . . . . . . 5 4.1.3. Shear-Thickening (Dilatant) Fluids . . 29
2.2. Cauchy Equations of Motion . . . . 6 4.1.4. Fluids with Time-Dependent Viscosity
2.3. Energy Transport Equation and ( Thixotropic Fluids) . . . . . . . . . . . 29
Bernoulli Equation . . . . . . . . . . . 8 4.2. Fully Developed Tube Flow . . . . . 30
2.4. Constitutive Equations and Classifi- 4.2.1. Volumetric Flow Rate – Pressure Drop
cation of Fluids . . . . . . . . . . . . . 9 Relationship . . . . . . . . . . . . . . . . 31
3. Newtonian Fluids . . . . . . . . . . . . 10 4.2.2. Generalized Treatment . . . . . . . . . 31
3.1. Deviatoric Stress and Viscosity . . . 10 4.2.3. Velocity Distribution . . . . . . . . . . . 32
3.2. Navier – Stokes Equations . . . . . . 11 4.2.4. Friction Factor – Reynolds Number
3.3. Applications of Navier – Stokes Relationships . . . . . . . . . . . . . . . 33
Equations . . . . . . . . . . . . . . . . . 12 4.3. Viscoelastic Fluid Mechanics . . . . 34
3.3.1. Flow in Pipes . . . . . . . . . . . . . . . 12 4.3.1. Steady Shear Behavior of Viscoelastic
3.3.2. Concentric Cylinder Flow . . . . . . . 14 Fluids . . . . . . . . . . . . . . . . . . . . 36
3.3.3. Creeping Flow Past a Sphere . . . . . . 16 4.3.2. Behavior of Viscoelastic Fluids in Os-
3.4. Some Other Important Flows . . . . 18 cillatory Shear Flow . . . . . . . . . . . 37
3.4.1. Flow Through Granular Beds . . . . . 18 4.3.3. Examples of Constitutive Equations
3.4.2. Fluidization . . . . . . . . . . . . . . . . 19 for Viscoelastic Fluids . . . . . . . . . . 38
3.4.3. Gas – Liquid Flow . . . . . . . . . . . . 20 4.3.4. Extensional Behavior of Viscoelastic
3.5. Mechanical Energy Balance for Fluids . . . . . . . . . . . . . . . . . . . . 40
Macroscopic Systems . . . . . . . . . 22 4.3.5. Accelerating and Decelerating Flows
3.5.1. Fully Developed Tube Flows . . . . . . 23 of Viscoelastic Fluids . . . . . . . . . . 42
3.5.2. Accelerating and Decelerating Flows 23 5. Numerical Methods in Fluid Me-
3.5.3. The Orifice Plate and Similar Flow chanics . . . . . . . . . . . . . . . . . . . 46
Rate Measurement Devices . . . . . . 25 5.1. Finite Difference Method . . . . . . . 46
4. Non-Newtonian Fluids . . . . . . . . . 26 5.2. Finite Element Method . . . . . . . . 48
4.1. Classification of Fluids According to 5.3. General Remarks . . . . . . . . . . . . 51
Viscosity Behavior . . . . . . . . . . . 27 6. References . . . . . . . . . . . . . . . . . 51

Symbols: e rate of strain tensor

exx , exy ,eij components of rate of strain tensor
A cross-sectional area, surface area, ampli-
Ev frictional loss
tude of oscillation
Ev ex losses in valves, fittings, etc.
C loss coefficient
Ev fd losses in fully developed flows
Cd drag coefficient, discharge coefficient
f friction factor
d distance
F force vector
D diameter
Fd drag force
De extrudate diameter
Fi component of force vector
Dhy hydraulic diameter
G volumetric flow rate in gas phase
Dp particle diameter
G
storage modulus
Dv vane diameter
G

loss modulus
e surface roughness, end correction

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b01 05
2 Fluid Mechanics

h elevation Γ , Γ m torque
H gap between plates δij Kronecker delta
Hv vane height ε porosity
i unit vector in x direction ε̇0 constant extensional rate
I identity matrix η viscosity
j unit vector in y direction η el extensional viscosity
JG superficial gas phase velocity η pl plastic viscosity
JL superficial liquid phase velocity η0 viscosity parameter of Meter, Maxwell,
k thermal conductivity, parameter in the and Oldroyd-B models
power-law equation η
dynamic viscosity
k unit vector in z direction η

component of complex viscosity
K
intercept in the log – log plot of τ w versus θ azimuthal coordinate
8 V /D λ bulk viscosity, time constant
L length, volumetric flow rate in liquid λel extensional viscosity
phase λ1 relaxation time
Le equivalent length λ2 retardation time
L0 initial length  density
n flow-behavior index of power law equa- p particle density
tion τ deviatoric stress tensor
n unit outward pointing normal τij component of deviatoric stress tensor
n
slope of log – log plot of τ w versus 8 V/D τ rz , τ rθ shear stress
N1 first normal stress τw wall shear stress
p isotropic pressure τy yield stress
q heat flux vector τ 1/2 parameter of Ellis and Meter model
Q volumetric flow rate Φ interpolation function
r radial coordinate ψ1 first normal stress coefficient
r0 plug radius ψ2 second normal stress coefficient
Rc , Rx , Ry residuals Ψ stream function
R, R1 , R2 radius ω 1 , ω 2 , ω angular velocity, vorticity
Re Reynolds number Ω angular velocity
Re
generalized Reynolds number for time-
independent fluid
S path joining two points 1. Introduction
t time
T temperature The traditional approach for writing an article
T stress tensor or a text book on fluid mechanics has been to
Tij , Txx , Txy , Txz stress components deal with the Newtonian fluid and the resulting
u velocity vector mechanics associated with such materials. Thus
uf fluidizing velocity the basic tools (in a sequence of events such as
ui , ux , uy , ur , ut , u0 velocity components those illustrated in Figure 1) are treated in de-
U, U 0 , U∞ velocity tail to illustrate how to solve a Newtonian fluid
V average velocity, volume mechanics problem. The laws of conservation
W mass flow rate of mass (continuity equation) and conservation
W s shaft work of momentum (Cauchy momentum equations or
x position vector equations of motion) are established for a gen-
xi components of position vector eral system and in multidimensional form. From
z elevation these equations it then becomes clear that the
α parameter in Meter model solution to any fluid mechanics problem is not
γ shear strain possible unless a relationship is developed bet-
γ0 amplitude of sinusoidal shear strain ween the stress tensor and rate of deformation
γ̇ shear rate tensor, or, between the stresses and velocity gra-
γ̇ 0 amplitude of sinusoidal shear rate dients in the system. Such an equation is termed
 Fluid Mechanics 3

the constitutive equation. For Newtonian fluids In Chapter 2 the basic equations for fluid
the relationship between the stress tensor and the mechanics – the continuity equation, the Cauchy
rate of deformation is linear, the proportionality equations of motion, and the energy transport
constant is the viscosity. Substitution of this re- and Bernoulli equations – are established. Chap-
lationship into the Cauchy momentum equations ter 3 deals with Newtonian fluids and Newtonian
leads to the Navier – Stokes equations. Thus the fluid mechanics where the Navier – Stokes equa-
Navier – Stokes equations, in conjunction with tions are developed. In addition, the mechanical
the viscosity, form the basis for the solution of energy balance is established for macroscopic
classical fluid mechanics problems. Much of the systems in order that pipe flow systems can be
effort in classical fluid mechanics is devoted to designed. The emphasis in the article is directed
establishing methods of solution of the Navier – toward pipe flows because the process engineer
Stokes equations. These methods can be analyt- is more concerned with flow in conduits than in
ical in nature and in recent times, of course, are other geometries. Little emphasis is placed on
numerical. While one whole section of this ar- the details associated with turbulence because
ticle is devoted to numerical methods because process engineers are primarily concerned with
of their importance in modern fluid mechanics, turbulent flow in pipes of Newtonian fluids and
no attention is directed towards classical analyt- are not concerned with design of aerofoil struc-
ical methods such as those used in the solution tures, etc.
of boundary layer and slow flow (creeping flow) Chapter 4 concentrates on non-Newtonian
problems. The emphasis is directed towards the fluids. In this chapter fluids are classified accord-
industrial chemist, process scientist, and chemi- ing to their viscosity behavior and are examined
cal engineer who encounter a vast range of mate- in some depth in fully developed tube flow. Vis-
rials in today’s industries where the Newtonian coelastic fluid mechanics are also summarized –
fluid is only one small subset of a vast array of the steady shear and dynamic shear behavior of
fluid behavior which can be observed. Figure 2 viscoelastic fluids are reviewed and examples of
illustrates the range of behavior that can be en- simple constitutive equations are given. The ar-
countered in terms of the viscosity of fluids and ticle is completed with a brief examination of
in terms of whether materials are classified as be- numerical methods in fluid mechanics.
ing inelastic or viscoelastic fluids. It is clear from The emphasis of this article is shifted toward
examination of Figure 2 that a vast range of be- non-Newtonian fluid mechanics, the sequence of
havior in terms of the viscosity of materials can events and tools of importance are illustrated in
be and is observed. An industrial chemist or pro- Figure 3. Here the basic conservation of mass
cess engineer will encounter low molecular mass (continuity equation) and the conservation of
liquids and gases (Newtonian materials) but will momentum (Cauchy momentum equations) re-
also be dealing with polymer solutions, poly- main the equations of fundamental importance,
mer melts, rubbers, mineral suspensions, food but, the relevant constitutive equation in most
products, pharmaceuticals, and energy products cases is still unknown. Thus the Navier – Stokes
such as coal oil and coal water fuels, etc. In such equivalent set of equations in many cases is
systems the viscosity can be constant, but more not known and because any number of consti-
likely will vary with shear rate or rate of flow. tutive equations are available it is not entirely
Viscosity can be a function of shear rate and clear what basic flow property information is
time of shear; or it can be a function of shear required for the most general viscoelastic ma-
rate, time, and thermal history and each of these terial. It is only now (1990) that fluid mechanics
viscosity behaviors can be observed in inelas- problems are solved for the first time for vis-
tic and/or viscoelastic fluids. In addition many coelastic fluids. The solutions evolving now for
materials will not flow until a certain stress is such problems will be extremely important in the
exceeded (e.g., toothpaste). This stress, termed future. It is also of considerable importance to
yield stress, can be present in both inelastic and keep abreast of the numerical software packages
viscoelastic fluids. Therefore, it is important to which have been developed in this area particu-
be aware of the vast range of material behavior larly in regard to the processing of polymers [1],
present in industry. [2].
4 Fluid Mechanics

Figure 1. Newtonian fluid mechanics

Figure 2. Schematic classification of fluid behavior

2. Basic Equations of Fluid

Mechanics
The basic equations of fluid mechanics can be
derived from a small number of fundamental
physical laws such as conservation of mass, of
momentum ( Newton’s second law), and of en-
ergy. Although very general statements of these
laws can be written down (applicable to all sub-
stances, solids as well as fluids), in fluid mechan-
ics these laws are formulated in terms of physical
Figure 3. Non-Newtonian fluid mechanics variables such as velocity u, pressure p, temper-
TH = Thermal history ature T , and density . The resulting statements
may be less general but they are more directly
applicable in analyzing fluid mechanical prob-
lems.
 Fluid Mechanics 5

2.1. Continuity Equation at time t and its density  (x + δx, t + δt) at a later
time t + δt when it is occupying position x + δx,
The requirement that mass be conserved at every it can be seen that D/Dt is the rate of change
point in a flowing fluid imposes certain restric- in density experienced by a fluid element as it
tions on the velocity u and density . Consider an moves about in space. D/Dt should not be con-
arbitrary region in space, of volume V , bounded fused with ∂/∂t which is the rate of change in
by surface A, through which the fluid flows (see density at a fixed point in space. The substan-
Fig. 4). The rate of increase in mass within this tial derivative operator can also be applied to
region is given by the volume integral the velocity u, temperature T , or other proper-

ties associated with a fluid element with a similar
∂
dV (1) physical interpretation of the result.
∂t
V

The rate at which fluid is leaving the region

is given by the surface integral of the out-
ward pointing normal velocity multiplied by the
fluid’s density taken over the surface A



u·ndA= ∇· (u) dV (2)
A V

where n is the unit outward pointing normal at

any point on A. The divergence theorem has been
used to convert the surface integral into a volume
integral. Mass conservation requires the sum of
the rate of accumulation in V and the rate of
outflow from V to be zero:

  Figure 4. Fluids flowing through an arbitrary region in space
∂ of volume V and surface area A
+∇· (u) dV = 0 (3)
∂t
V A number of special cases of the continuity
equation are frequently encountered. For exam-
Since V is arbitrary, the integrand itself must ple, under steady-state conditions the equation
vanish at every point in space: reduces to
∂
+∇· (u) = 0 (4) ∇· (u) = 0 (7)
∂t
Equation (4) is usually referred to as the con- Much of the subsequent analyses will be re-
tinuity equation. It is a statement of mass con- stricted to fluids that are incompressible and ho-
servation in terms of fluid velocity and density. mogeneous. For such fluids the continuity equa-
Expanding the second term and regrouping, the tion takes on a particularly simple form
equation can be written as
∇·u= 0 (8)
∂
+u·∇+∇·u= 0 (5)
∂t In many practical problems the fluid flow can
or be regarded as approximately two-dimensional.
For such problems, Equation 8 (in cartesian co-
D ordinates) takes on the form
+∇·u= 0 (6)
Dt
∂ux (x,y) ∂uy (x,y)
where D/D t is used to represent the operator + =0 (9)
∂ ∂x ∂y
∂t +u·∇.
It is known as the substantial derivative op- Equation (9) and, hence, mass conservation are
erator. By following the change in the density identically satisfied if the velocity components
 (x, t) of a fluid element occupying position x are given by