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Use of Surfactants in Metal Cutting Fluids Formation

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 11 Use of Surfactants in
Metal Cutting Fluids
Formation
Nabel A. Negm, Satish V. Kailas, Anirudhan
Pottirayil, and Ali A. Abd-Elaal

Contents
Abstract................................................................................................................... 259
11.1 Introduction...................................................................................................260
11.2 Types of Cutting Fluids................................................................................. 262
11.2.1 Petroleum Oil-Based Cutting Fluids................................................. 262
11.2.1.1 Straight Oils (Petroleum Oil with Additives)..................... 262
11.2.1.2 Soluble Oils (60–90% Petroleum Oil in the
Concentrate)..................................................................... 263
11.2.1.3 Surfactants Used in Soluble Oils Formulation...................264
11.2.2 Chemical Cutting Fluids.................................................................... 267
11.2.2.1 Synthetic Fluids.................................................................. 267
11.2.2.2 Semisynthetic Fluids........................................................... 268
11.2.3 Bio-Based Cutting Fluids.................................................................. 269
11.3 Recent Advances in the Use of Surfactants in Cutting Fluids...................... 272
11.4 Conclusion..................................................................................................... 274
References............................................................................................................... 275

Abstract
An important industrial application of oil-in-water (O/W) emulsions is in
metal cutting operations such as turning, drilling, milling, sawing, and so on
during which an emulsion, made by mixing oil and water using suitable sur-
factants, is made available at the interface between the workpiece and the tool/
roller. Such emulsions, popularly known as metal cutting fluids, perform the
dual function of lubrication as well as cooling. The oil in the emulsion reduces
the friction between the mating surfaces while the aqueous phase dissipates
the heat generated in the contact. Furthermore, metalworking fluids facili-
tate easy chip removal, inhibit corrosion, and increase fire resistance. They
also improve the performance of the machining operations by increasing tool
life and producing better surface finish. A major limitation of metalworking

259

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 260 Surfactants in Tribology

fluids is that they lose their stability as well as lubricating properties over time.
Because of their exposure to chemically and biologically active environments,
high temperature, and high pressure, they ultimately need to be replaced. As a
result, large volumes of wastewater containing oil are periodically generated,
which must be treated properly before it is discharged into the environment.
The current trend is to optimize the metalworking fluid formulation by using
environmentally acceptable surfactants and other ingredients.

11.1 Introduction
During the machining process, friction between the workpiece and the cutting tool,
as well as between the cutting tool and the chip (ensuing metal from the workpiece
due to the cutting process) interfaces, creates a high temperature on the cutting tools.
A high temperature increases tool wear, decreases tool life, increases tool–workpiece
friction, increases surface roughness, and decreases the quality of the workpiece
product. This becomes even more severe during the machining of materials that are
difficult to cut, which generate high temperatures [1]. Various methods have been
reported to protect cutting tools from such generated heat. Choosing cutting tools
with hard coatings is an expensive alternative, but generally suitable for machining
certain materials such as titanium and heat-resistant alloys. During metal cutting,
the generated heat can be carried away by the cutting fluid, and the friction can be
reduced and facilitate chip formation. Cutting fluids are usually liquids that improve
the cutting condition and easily reach the working interface. In addition to cooling,
they also help to remove debris and other contaminants. Water-based metalworking
fluids (MWFs) should also provide good corrosion protection to both equipment and
workpieces. Overall, the application of cutting fluids should result in a higher rate of
material removal and increased productivity.
Similar fluids are employed in other metalworking operations (such as rolling,
forming, and stamping) to provide cooling and lubrication to both the workpiece
and the tool. In the past, MWFs were composed of neat oils or emulsions of water
and oil. However, the industry has increasingly sought to replace neat oil products
with water-based materials. MWFs are complex mixtures whose compositions dif-
fer depending on the type of metalworking process and the type of metals being
worked on [2]. Metalworking formulations may be classified as aqueous or non-
aqueous. Aqueous MWFs are oil-in-water (O/W) emulsions, which are made of oils
mixed with surface-active materials (surfactants) that help in dispersing the oil in the
continuous water phase [3]. Oils, since they are hydrocarbon compounds, are gener-
ally insoluble in water. However, the addition of suitable emulsifiers in the oil will
help reduce the interfacial tension between the hydrocarbon and water, and results
in dispersion of the oil in the water. These surfactants have both hydrophilic and
hydrophobic parts; they accumulate at the interface between the oil and water. At
such interfaces, the hydrophobic part of the surfactant (Figure 11.1) interacts with the
lipid (oil), while the hydrophilic part (usually the “head”) interacts with the water.
Various water-based MWF compositions exist, but a number of problems arose
in connection with the use of such compositions. New formulations are required for
fast metal processing, for difficult-to-machine materials, and for novel machining

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 Use of Surfactants in Metal Cutting Fluids Formation 261

O
S O–Na+
O

SO3Na+

Figure 11.1  Chemical structures of typical sulfonate emulsifiers.

operations. This has forced lubricant manufacturers to formulate special lubricating

fluids that meet constantly changing market requirements. Cutting fluids have been
widely used in all machining operations. However, because of their damaging effect
on the environment, their applications have raised serious concerns [4–8].
The cutting fluids applied in machining processes have several functions [8–10],
including

1. Preventing the tool from overheating and thereby softening, which can
increase tool wear and reduce tool life
2. Keeping the workpiece cool and preventing inaccurate final dimensions
3. Reducing power consumption, wear of the tool, and the generation of heat
4. Providing a product with a good surface finish
5. Helping provide a satisfactory chip formation (related to contact length)
6. Washing away the chip swarf from the cutting area
7. Preventing corrosion of the workpiece, the tool, and the machine

The cooling effect of cutting fluids is one of the most important properties. It is
important to decrease the effect of temperature on the cutting tool and the machined
workpiece. Therefore, a longer tool life will be obtained due to less tool wear and the
dimensional accuracy of the machined workpiece will be improved [7,9,10].
The lubrication effect will cause an easy chip flow on the rake face of the cutting
tool because of low friction coefficient. Moreover, the influence of lubrication would
cause less buildup edge when machining some materials such as aluminum and its
alloys. As a result, smooth surfaces would be obtained when using cutting fluids in
machining processes [7,9,10].
The desirable properties of cutting fluids are

1. High thermal conductivity for efficient cooling

2. Good lubricating property
3. High flash point to prevent fire hazard
4. Must not produce a gummy or solid precipitate at ordinary working
temperatures
5. High oxidation stability
6. Must not promote corrosion or discoloration of the workpiece
7. Must afford some corrosion protection to newly formed surfaces
8. The components of the lubricant must not become rancid easily
9. Must not generate unpleasant odor from continued use

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 262 Surfactants in Tribology

10. Must not cause skin irritation

11. Appropriate viscosity that will permit free flow from the workpiece and
dripping from the chips

The following factors should be considered when selecting cutting fluids [4,11,12]:

1. Cost and batch life; that is, how long before disposal
2. Fluid compatibility with workpiece and machine components
3. Speed and depth of the cutting operation
4. Type, hardness, and microstructure of the metal being machined
5. Ease of fluid maintenance and quality control
6. Ability to separate fluid from the workpiece and cuttings
7. Applicable temperature operating range
8. Optimal concentration and pH ranges
9. Storage requirements
10. Ease of fluid recycling and disposal

11.2 Types of Cutting Fluids

The most common MWFs used today belong to one of three categories based on the
type of their oil composition [4,11]:

1. Petroleum oil-based fluids: including straight oils and O/W emulsions

2. Chemical fluids: including synthetic and semisynthetic
3. Bio-based fluids

Fluids vary in suitability for metalworking operations. For example, tapping

and thread-turning, which are generally low-speed high-torque applications, would
require straight oils (mixed with additives), while water-miscible fluids provide
cooling properties required for most turning and grinding operations, which are
the relatively high-speed operations that generate a lot of heat. Bio-based cutting
fluids have the potential to reduce the waste treatment costs due to their inherently
higher biodegradability and may reduce the occupational health risks associated
with petroleum oil-based cutting fluids since they have lower toxicity. Bio-based
fluids provide a healthier and cleaner work environment, with less mist in the air.
The following provides a description, advantages, disadvantages, and applications
of each type of MWF.

11.2.1  Petroleum Oil-Based Cutting Fluids

11.2.1.1 Straight Oils (Petroleum Oil with Additives)
This type of cutting fluid is called straight oil because they do not contain water, but
contain petroleum-based mineral oils. They contain additives designed to improve
various properties [13,14]. Some additives (e.g., rust and bacterial growth preven-
tion) are required for the easiest tasks such as light-duty (made or designed to resist
comparatively moderate loads, or stress) machining of ferrous and nonferrous metals

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 Use of Surfactants in Metal Cutting Fluids Formation 263

[15,16]. For more severe applications, straight oils may contain friction modifiers
(typically up to 20% fatty oils) and extreme pressure (EP) additives such as sul-
fur, chlorine, or phosphorus compounds. These additives improve the oil’s ability
to coat the cutting tool, workpiece, and metal fines [17]. They also enhance lubri-
cation, improve the oil’s ability to handle large amounts of metal fines, and help
guard against microscopic welding in heavy-duty machining. For extreme condi-
tions, additive concentration (primarily containing chlorine and sulfurized fatty oils)
may exceed 20%. These additives strongly enhance the antiwelding property of the
lubricant [16].
The major advantage of straight oil MWF is the excellent lubricity it provides
between the workpiece and cutting tool [14]. This is particularly useful for low-
speed, low-clearance operations requiring high-quality surface finishes [15,16].
Although the cost is high, it provides the longest tool life for a number of metal-
working applications. Highly compounded straight oils are still preferred for severe
cutting operations such as crush grinding, severe broaching and tapping, deep-hole
drilling, and for the difficult-to-cut metals such as certain stainless steels and super-
alloys. Straight oils are the fluid of choice for most honing operations because of
their high lubricating qualities [17]. Straight oils offer good rust protection, extended
sump life, and have easy maintenance; they are less likely to cause problems if mis-
used. They also resist rancidity, since bacteria cannot thrive in the ore unless water
contaminates it [15].
The disadvantages of straight oils include a poor heat dissipating property and
increased fire risk [15,16]. They may also create a mist or smoke, which results in
an unsafe work environment for the machine operator. This is a big problem with
machines that do not have adequate shielding or when shops have poor ventilation
systems. Straight oils are usually limited to low-temperature and low-speed opera-
tions [13]. Another disadvantage is that the oily film left on the workpiece makes
cleaning more difficult, often requiring the use of potentially toxic cleaning solvents.
Straight oil products of different viscosities are available for each duty class and their
viscosity can be controlled and adjusted. The higher the oil viscosity, the better its
lubricity. However, highly viscous fluids tend to cling to the workpiece and tool. This
causes an increased loss in cutting fluid by drag-out and necessitates lengthier and
more costly cleanup procedures. It would be prudent to choose low-viscosity oils that
have been fortified by additives over the highly viscous straight oils.

11.2.1.2 Soluble Oils (60–90% Petroleum Oil in the Concentrate)

Soluble oil concentrates (also referred to as emulsions, emulsifiable oils, or water-
soluble oils) are generally comprised of 60–90% petroleum or mineral oil to which
emulsifiers and other additives have been blended [13,15,18]. 5–10% of the concen-
trate is mixed with water to form the MWF. When mixed, the emulsifiers cause the
oil to disperse in the water, forming a stable “O/W” emulsion [2,17]. The emulsion
also causes the oils to cling to the workpiece during machining. Emulsifier particles
scatter light, giving the fluid a milky and opaque appearance.
Soluble oils offer improved cooling capability and good lubrication due to the
blending of oil and water [17]. They also tend to leave a protective oil film on mov-
ing components of machine tools and resist emulsification of greases and oils [2].

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 264 Surfactants in Tribology

Soluble oils are a general-purpose product suitable for light- and medium-duty oper-
ations of ferrous and nonferrous metals. Although they do not match the lubricity
of straight oils, friction modifiers and EP additives such as chlorine, phosphorus, or
sulfur compounds can extend their machining application range to include heavy-
duty operations. Most cutting operations handled by straight oils, including broach-
ing, trepanning, and tapping, may be accomplished using heavy-duty soluble oils.
Soluble oil cutting fluid formulations have several disadvantages. The presence
of water makes soluble oils more susceptible to rust, bacterial growth and rancid-
ity, unemulsified oil contamination, and evaporation losses. Soluble oils are always
formulated with additives to provide additional corrosion protection and resistance
to microbial attack. Maintenance costs to retain the desired characteristics of solu-
ble oils are relatively high. Other disadvantages of soluble oils include soluble oils
when mixed with hard water tend to form precipitates on parts, machines, and filters
[15,16]; due to their high oil content, soluble oils may be the most difficult water-­
miscible fluids to clean from the workpiece. Misting of soluble oils may produce a
dirty and unsafe work environment through slippery surfaces and inhalation haz-
ards. As a result of these disadvantages, soluble oils have been replaced in most
operations with chemical cutting fluids.

11.2.1.3 Surfactants Used in Soluble Oils Formulation

The surfactants commonly used in MWF manufacturing industry for the preparation
of soluble oils include polyetheramines, linear alcohols, alcohol ethoxylates, alcohol
alcoxylates, alkylphenol ethoxylates, fatty acid ethoxylates, castor oil ethoxylates,
ethylene oxide copolymers, phosphate esters, sodium isethionate, glycols, glycol
ethers, primary amines, and tertiary amines [19]. Although polyetheramines, linear
alcohols, alcohol ethoxylates, alcohol alcoxylates, alkylphenol ethoxylates, fatty acid
ethoxylates, castor oil ethoxylates, ethylene oxide copolymers, and phosphate esters
are used as emulsifiers, linear alcohols, alcohol ethoxylates, alcohol alcoxylates, gly-
cols, and glycol ethers are used as coemulsifying agents, though in some cases, a few
alcohol ethoxylates and alcohol alcoxylates can function as an emulsifier as well as
coemulsifying agents.
A more systematic classification of surfactants includes [20] (1) nonionics, (2)
cationics, (3) anionics, and (4) zwitterionics (amphotherics). Common nonion-
ics are fatty alcohols ROH (Figure 11.2a), fatty esters R(CO)OR′ (Figure 11.2b),
glycerol esters H(CHOR)(CHOR′)(CHOR′)H, glycol esters R(CHOR)(CHOR′)H,
alkyl phenols R–Ph–O–PEO–H (Figure 11.2c), acetylenic glycols R[(COH)CH3]
C ≡ C[(COH)CH3]R, alkanolamines and alkanolamides, polyethoxylated mer-
captans RS–PEO–H, sorbitol, and sorbitan derivatives (Figure 11.2d). Cationic
surfactants include alkylamines R(NR′)R″, quaternary amines R[(N+R′)R″]R′″,
imidazolines, and dialkylamine oxides R–[(NO)R′]R″. Anionic surfactants include
subdivided as (a) carboxylates, (b) sulfonates, (c) sulfates, and (d) phosphates.
Common carboxylates include (i) salts of fatty acids (R(CO)O−Na+), (ii) salts of mul-
tiple acids (HO(CO)(CHOH)(CO)O−Na+), (iii) sarcosine derivatives (R(CO)(NCH3)
CH2(CO)O−Na+), and salts of Tall oil acids (Figure 11.2e). Examples of sulfonates are
sodium alkyl sulfonates (RSO3− Na + ) , alpha-olefin sulfonates, linear alkylbenzene
sulfonates (R(CHR ’)PhSO3− Na + ), aromatic sulfonates (Figure 11.2f), isethionates

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 Use of Surfactants in Metal Cutting Fluids Formation 265

(a) (b)
H HH HH H
H C C C
H H HH HH H O H H
C C C H
H HH HH C O H C C C C C
H H H
C C C C C C O
H HH H H HH HH HH H

(c) (d) OH H
H H
O
H H H H
H
C O H H
H CH2 OH C
O C H HO OH
C
8 H H H
H H 9 H

(e)
COOH
CH3 H H
H H
H
H
(f )
H H O
H
H CH2 CH2 S O– Na+
H CH3
CH3 CH2 O
H H H
H CH3 H H
H CH
H H
H H CH3

Figure 11.2  Common types of surfactants. (a) Fatty alcohol, (b) fatty ester, (c) octyl
phenol ethoxylate, (d) sorbitan, (e) tall oil acid, and (f) alkyl naphthalene sulfonate. (From
http:/­/­www.­erpt.­org/­032Q/ ­Nelsc-­0 0.­htm.­)

(R(CO)OCH2 CH 2 SO3− M + ), sulfosuccinates (RO(CO)CH 2 CH(SO3− M + )(CO)OR ),

and taurates (R(CO)(NR ′)CH 2 CH 2SO3− ) .
Sulfates have a typical structure RO(SO2)O−M+, with sulfur bonded to oxygen,
while sulfonates mentioned above have a structure of the form R(SO2)O−M+ with sul-
fur bonded to carbon directly. Common sulfates include alcohol sulfates (ROSO3− M + )
, alkyl phenol sulfates (RPhOPEOSO3− M + ) , and sulfated triglycerides. Phosphates
could be organic such as alcohol phosphates (RO[(PO)OR]O−M+) and inorganic
phosphates (M+[O(PO)O−M+]nO−M+). Zwitterionics have positive and negative
charges and the common types are inorganic phosphates (M+[O−(PO)O−M+]nO−M″+,
M+[O−(PO)OM+]nO−M+), betaines (R[N+(CH3)2](CH2)x(CO)O), and phospholipids
(R(CO)OCH2 [CHO(COR]CH2 O(PO2− )X + ) .
Sulfonates (Figure 11.2f) are a class of chemicals used for household, industrial,
and institutional cleaning applications; personal care; MWFs; industrial processes;
emulsifying agents; corrosion inhibitors; and additives in lubricating oils [21]. Some

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 266 Surfactants in Tribology

of the desirable properties of sulfonates for use in lubricating oil applications include
low cost, compatibility with oils during emulsion formation, water tolerance, high-
temperature stability, and prevention of rust formation. Sulfonates that are used in
lubricating oil applications have been classified as neutral, low over based, or high
over based. Sulfonates are lubricating oil additives comprising a major amount of an
oil of lubricating viscosity and a minor amount of a poly alkenyl sulfonate composi-
tion (in the form of alkali metal, group 1A, or earth alkali metal, group 2A, salts)
having a total benzene ring number in the molecule of up to 60 units.
Sodium petroleum sulfonates are widely used as the primary emulsifier in formu-
lating emulsifiable lubricating compositions used for cutting fluids, hydraulic fluids,
and metalworking lubricants. A detailed discussion related to the performance char-
acteristics of cutting fluid emulsions based on petroleum sulfonate surfactant made
from the light gas oil fraction of petroleum in machine operations is given in Ref.
[22]. The petroleum sulfonate was fractionated by the solvent extraction procedure
to obtain three sulfonate fractions having different average molecular weights and
different specific gravities. The average molecular weights of the three sulfonated
fractions were: A: 567 g/mol, B: 496 g/mol, and C: 397 g/mol. The results of the
tests showed that petroleum sulfonate fraction C produced the most efficient cutting
fluids, followed by fraction B. Results of using sodium salt forms of sulfonates or
sulfonic acid derivatives are also reported in Ref. [23], and were found to provide
efficient emulsification performance for the oil in the MWFs.
The products obtained from the thermal reaction of hydroxyl fatty acids (ricinoleic
acid oligomers, 12-hydroxystearic acid oligomers, oleyl alcohol, dehydrated castor
oil fatty acids, and dimer acid) with maleic anhydride showed applicability as water-­
soluble cutting fluids [24]. For example, aqueous solutions of triethanolamine salts
with ricinoleic acid oligomers, 12-hydroxystearic acid dimer, and 12-hydroxystearic
acid hexamer showed good antirust properties in water-based cutting fluid formula-
Q1 tions. In the same manner, aqueous solutions of triethanolamine salts of half esters
of maleic anhydride, succinic anhydride, and phthalic anhydride with hydroxyl fatty
acids gave good antirust and antiwear properties for water-based cutting fluids.
Derivatives of undecanoic acid were prepared from ω-bromoundecanoic acid and
ω-aminoundecanoic acid, and their characteristic properties as cutting fluid addi-
tives were tested [25]. The results of using triethanolamine salts of undecanoic acid
having an ether substituent in the ω-position demonstrated effective rust-inhibiting
and antiwear properties in water-based cutting fluids. Surfactants from succinic acid
and its derivatives that contain a branched aliphatic group on the 2 or alpha position
were disclosed in the invention by Ashjian et al. [26]. These surfactants showed resis-
tance to bacteriological degradation in the cutting fluids formulations. Furthermore,
it has been shown that these novel surfactants can be employed to prepare novel O/W
emulsions with mineral oils. These emulsions are effective for machining opera-
tions and also provide improved resistance to biodegradation, without the use of
conventional biocides. The bioresistance of the cutting fluid emulsion was enhanced
by using a branched aliphatic hydrocarbon oligomer or polymer as the lubricating
component in the formulation. Cutting fluid emulsions formulated using succinic
acid and its derivatives were effective fluids in prolonging tool life and facilitating
machining operations.

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 Use of Surfactants in Metal Cutting Fluids Formation 267

A cutting fluid for hard water has been formulated from paraffinic oil, monoetha-
nolamine borate, and a cationic/nonionic surfactant [27]. Its dilution with hard water
yields very stable O/W emulsion, with an average droplet diameter of 50 nm, regard-
less of the water hardness or the weight ratio of hard water to concentrate. The high
stability of these emulsions is due to a strong interaction between droplets caused by
the presence of the cationic surfactant at the droplet surface. From a practical point
of view, the ability to produce stable cutting fluid emulsions at a wide range of dilu-
tions, regardless of the hardness of water, might allow the user to fine-tune the lubri-
cating and cooling properties of the fluids and, therefore, optimize its performances
during the metalworking process.

11.2.2  Chemical Cutting Fluids

Chemical cutting fluids are either synthetic or semisynthetic fluids. They are chemi-
cal formulations that contain very little or no oil. Chemical cutting fluids rely on
additives for lubrication and friction reduction [15], and to improve wettability. At
temperatures above approximately 200°C, these additives become ineffective and
EP additives such as chlorine, phosphorus, and sulfur compounds are utilized. These
compounds react with freshly machined metal to form chemical layers that act as
solid lubricants and protect against welding during heavy-duty machining opera-
tions. Fluids containing EP additives significantly reduce the heat generated during
cutting and grinding operations.

11.2.2.1 Synthetic Fluids
Synthetic cutting fluids contain no petroleum or mineral oil [16,28]. Generally, they
consist of additives, including rust inhibitors dissolved in water. Synthetics are avail-
able as concentrates, which are diluted with water to form the MWF. Synthetic flu-
ids are designed for high cooling capacity, good lubricity, corrosion prevention, and
easy handling. Owing to their higher cooling capacity, synthetics tend to be preferred
for high-heat, high-speed turning operations such as surface grinding. They are also
desirable when low foam generation is required. Heavy-duty synthetics are useful
during handling of most machining operations. Synthetic fluids can be further classi-
fied based on their composition as simple, complex, or emulsifiable synthetics [15,16].
Simple synthetic concentrates are primarily used for light-duty grinding operations
(low temperature is produced) [2]. Complex synthetics may be used for moderate
to heavy-duty machining operations. Machining may also be performed at higher
speeds and rates when using complex synthetics. Both simple and complex synthet-
ics form transparent solutions when mixed with water in a coolant sump, allowing
machine operators to observe the workpiece. Emulsifiable synthetics contain oils and
other compounds similar to soluble oils, allowing these fluids to function better dur-
ing heavy-duty machining applications. Owing to their wettability, good cooling, and
lubricity, emulsifiable synthetics are capable of handling heavy-duty grinding and
cutting operations on tough, difficult-to-machine, and high-temperature alloys [28].
The appearance of emulsifiable synthetic fluids ranges from translucent to opaque.
Synthetic fluids comprise one or more of the following: amines and nitrites for
rust prevention; nitrates for nitrite stabilization; phosphates and borates for water

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 268 Surfactants in Tribology

softening; soaps and wetting agents for lubrication; phosphorus, chlorine, and sulfur
compounds for chemical lubrication and EP operations; glycols to act as blending
agents; and biocides to control bacterial growth.
Synthetic fluids have the following advantages that contribute to their superior
service life [2,15]: excellent microbial control and resistance to rancidity for long
periods of time; nonflammable, nonsmoking, and relatively nontoxic; good corro-
sion control; superior cooling quality; high stability when mixed with hard water;
reduced misting problems; and reduced foaming problem.
Synthetics fluids are easily removed from the workpiece and chips, allowing for
easy cleaning and handling of these materials. In addition, since the amount of fluid
clinging to the workpiece and chips is reduced, less makeup fluid is needed to replace
coolant lost due to drag-out. Good settling property allows metal fines to readily
drop out of the suspension, preventing it from recirculating and clogging the cooling
system. Overall, synthetic fluids are easier to maintain as they offer long service life
if maintained properly and can be used for a variety of machining operations.
Although synthetics are less susceptible to problems associated with oil-based
fluids, moderate to high agitation conditions may still cause them to foam or gener-
ate fine mists [13]. A number of health and safety concerns, such as misting and
dermatitis, also exist with the use of synthetic fluids [15]. Additives used to enhance
the lubricity and wettability of emulsifiable synthetics may increase the tendency of
these fluids to emulsify oil, excessively foam, and leave semicrystalline to gummy
residues on machine parts (particularly when mixed with hard water) [2]. Synthetic
fluids are easily contaminated by other machine fluids such as lubricating oils and
must be monitored and maintained to be used effectively.

11.2.2.2 Semisynthetic Fluids
As the name implies, semisynthetic fluids, also referred to as semichemical fluids, are
essentially a hybrid of soluble oils and synthetics. They contain small dispersions of
mineral oil, typically 2–30%, in a water-dilutable concentrate [29]. The remaining por-
Q2 tion of a semisynthetic concentrate consists mainly of emulsifiers and water. Wetting
agents (alkyl phenol ethoxylates), corrosion inhibitors, and biocide (cationic surfactants)
are also present. Semisynthetics preform the chemical emulsions, since the concentrate
already contains water and the emulsification of oil and water occurs during its produc-
tion. The high emulsifier content of semisynthetics tends to keep suspended oil globules
small in size, decreasing the amount of light scattered by the fluid. Semisynthetics are
normally translucent, but can vary from almost transparent (having only a slight haze)
to opaque [30]. Oil molecules in semisynthetics tend to gather around the cutting tool
and provide more lubricity. As the solution cools, the molecules redisperse.
Semisynthetics are suitable for use in a wide range of machining applications and
are substantially easier to maintain than soluble oils. They provide good lubricity for
moderate- to heavy-duty applications. They have better cooling and wetting proper-
ties than soluble oils, allowing users to cut at higher speeds and faster feed rates [31].
Their viscosity is less than that of soluble oils, providing better settling and clean-
ing properties. Semisynthetics provide better control over rancidity and bacterial
growth, generate less smoke and oil mist (because they contain less oil than straight
or soluble oils), have greater longevity, and provide good corrosion protection.

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 Use of Surfactants in Metal Cutting Fluids Formation 269

Some of the disadvantages of semisynthetic fluids include the following:

Water hardness affects the stability of semisynthetics and results in the formation Q3
of hard water deposits. Semisynthetics foam easily because of their cleaning addi-
tives and generally offer less lubrication than soluble oils.

11.2.3  Bio-Based Cutting Fluids

Vegetable oils are viable, renewable, and environmentally benign oils. The increased
need for renewable and biodegradable lubricants can be traced to stronger environ-
mental concerns and growing regulations over contaminations and pollution. In
2012, an estimated annual growth rate of 11–16% for environmentally benign lubri-
cants was expected in the U.S. market, compared to only 7% for the overall lubricant
market [32]. Reports indicate that nearly 54 million metric tons of lubricants were
used globally in 2005, with a projected increase of 1.2% over the next decade [33].
Owing to their advantages, the consumption of MWFs is increasing in the machin-
ing industry. It is reported that the European Union alone consumes approximately
760,000 tons of MWFs per year of which at least two-thirds need to be disposed
[34]. Because of their widespread use, MWFs pose significant health and environ-
mental hazards throughout their life cycle. It has been reported that [35–39] about
80% of all occupational diseases of metalworking operators were due to skin con-
tact with the MWFs. In the United Stated alone, it is reported that about 700,000–
1,000,000 workers are exposed to MWFs annually [40]. Conventional cutting fluids
are complex chemical mixtures that may be irritant or allergic. Even more harmful
microbial toxins are generated by bacteria and fungi present in water-soluble MWFs
[41]. To overcome these challenges, various alternatives to mineral-based MWFs
are currently being explored by scientists and tribologists. Such alternatives include
synthetic lubricants, solid lubricants, and vegetable oil-based lubricants. Currently,
about 85% of lubricants being used around the world are mineral oil based [42]. The
major negative effects of mineral oil-based lubricants are linked to their use, which
results in surface water and groundwater contamination, air pollution, soil contami-
nation, and, consequently, agricultural product and food contamination [43].
Hence, there is a growing public interest in environmentally friendly lubricants
due to the environmental problems associated with conventional mineral oil-based
lubricants. Even though the toxicity of mineral oil-based lubricants is low, their accu-
mulation in the environment may cause long-range damage. A large proportion of
the lubricants pollute the environment during or after their use. In many countries,
there are well-defined guidelines and legislations to encourage the use of environ-
mentally friendly lubricants [44]. Several organizations around the world are working
to certify such lubricants by evaluating their potential benefits for the environment.
Examples include the German “Blue Angel,” the U.S. “Green Seal,” and the Canadian
“Environmental Choice” [45]. Mineral oil-based lubricants contain many types of
additives such as antioxidants, antiwears, detergents, dispersants, antifoams, EP
agents, friction modifiers, and viscosity improvers. Some of these additives are toxic
and harmful to humans, wildlife, and the environment [46]. The environmental and
toxicity issues of mineral oil-based lubricants and their additives as well as their rising
cost related to a global shortage have led to renewed interest in the use of vegetable

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 270 Surfactants in Tribology

oils. Soybean, canola, sunflower, coconut, sesame, castor, and other vegetable oils are
environmentally friendly and can be formulated into industrial fluids [47,48].
Vegetable oils generally possess excellent lubricating properties, such as good
inherent lubricity, low volatility, high viscosity index, excellent solvency for additives
and easy miscibility with other fluids. The growing demand for biodegradable mate-
rials has opened an opportunity for using vegetable oils as alternatives to mineral oil-
based materials [49–51], especially for machining operations. As a result, research
on biodegradable functional fluids emerged as one of the priorities in lubrication in
the early 1990s. This has led to a growing number of environmentally friendly fluids
and lubricants in the market [52]. Vegetable oils, especially rapeseed [53] and canola
[54], are some of the more promising candidates as base stocks for biodegradable
lubricants. They are biodegradable and less costly than synthetic base stocks. They
often show quite acceptable performances as lubricants [55–58]. Vegetable oil-based
cutting fluids are potential candidates for use in industry. Activities are in progress to
develop new bio-based cutting fluids from vegetable oils around the world.
The majority of vegetable oils consist primarily of triacylglycerides, which have
molecular structure with three long-chain fatty acids attached at the hydroxyl groups
via ester linkages. The fatty acids in vegetable oil triglycerides are between 14 and
22 carbons long, with varying degrees of unsaturation [59,60]. The triglyceride struc-
ture of vegetable oils provides qualities desirable in a lubricant. Long, polar fatty
acid chains provide high-strength lubricant films that interact strongly with metallic
surfaces, reducing both friction and wear. The strong intermolecular interactions are
also resilient to changes in temperature, providing a more stable viscosity, or high vis-
cosity index. The similarity of vegetable oil structures means that only a narrow range
of viscosities are available for their potential use as lubricants The strong intermolecular
interactions while providing a durable lubricant film also result in poor low-temperature
properties. The fluid also remains biodegradable with low toxicity throughout all stages
of its life. Lubricant formulations are being developed based on the benefits and limi-
tations of vegetable oils. Without additives, vegetable oils outperform mineral oils
in antiwear and friction [61], scuffing load capacity [62], and fatigue resistance [63].
Fully formulated vegetable oil lubricants, in comparison to mineral oil counterparts,
display a lower coefficient of friction, equivalent scuffing load capacity, and better
pitting resistance, but also poorer thermal and oxidative stability [64–67]. Vegetable
oils are effective as boundary lubricants due to the polarity of the base oil, allowing
interactions with the lubricated surfaces. At extreme loads, vegetable oil-based lubri-
cants were reported to be significantly less effective [68]. Belluco and de Chiffre [69]
evaluated the performance of some mineral and vegetable oil-based cutting fluids in
a range of machining operations. They reported that vegetable oil-based formulations
displayed equal or better performance than the referenced commercial mineral oil
in all operations. In summary, vegetable oils display many desirable characteristics,
which make them very attractive lubricants for many practical applications.
The limitations of vegetable oils as base stocks for lubricants include weakness of
the oxidative stability, poor cold-temperature performance, and incompatibility with
elastomers. Most vegetable oil-based lubricants have a maximum operating tempera-
ture of 60°C. Some vegetable oil-based lubricants are stable up to 104°C [69,70].
Therefore, vegetable oils have to be formulated for their individual characteristics.

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 Use of Surfactants in Metal Cutting Fluids Formation 271

Table 11.1
Typical Characteristics of Bio-Based Oils as Compared to Petroleum Oils
Petroleum Bio-Based
Property Method Unit Oil Oil
Lubricity ASTM D6079 – Low High
Oxidative stability index (OIS) OSI Time @ 110°C Hours 300 50
Viscosity index – – 100 200
Hydraulic stability ASTM D2619 – High High
Conductivity ASTM D2624 Ohm Low High
Saturation ASTM D1959 g(I2)/100 g(oil) Saturated Unsaturated
Flash point ASTM D93 °C 93 232
Pour point IP 35 °C −37 −37

Early developers of the vegetable oil-based lubricant used the same chemistry that
was used for mineral oil lubricants. This approach was not effective since the char-
acteristics of vegetable oils are vastly different from those of mineral oils. Table 11.1
shows the comparison between the properties of mineral oil- and vegetable oil-based
cutting fluids.
The major performance issues such as poor low-temperature properties and low
resistance to oxidative degradation are addressed by various methods such as (i)
reformulation of additives, (ii) chemical modification of vegetable oils, and (iii)
genetic modification of the oil seed crop [70–72]. Coconut oil blended with 2% zinc-
dialkyl-dithio-phosphate showed a substantial reduction in friction and wear when
the new formulation was tested on an internal combustion engine test rig [72,73].
Olive and soybean oils formulated with dibutyl 3,5-di-t-butyl-4-hydroxybenzyl
phosphonate (DBP) showed a dual function of hydrogen scavenging and protective
film formation, thus reducing wear [74,75]. Phosphate esters containing benzotri-
azole group blended with rapeseed oil showed excellent load carrying capacity, good
antiwear, and reduced friction properties [75–77].
Improvements in vegetable base stocks, performance chemistry, and formula-
tion expertise have allowed for the development of biodegradable cutting fluids with
performance similar to or better than conventional petroleum-based fluids. When
chemists began to look at colloidal systems around 1905, the scientific basis of cut-
ting fluids formulation began to unfold [77,78]. The growing body of knowledge on
colloid and surfactant chemistry led to the compounding of various “soluble oils”
using natural fatty oils. This led to the granting of a patent to Hutton [79] for the
process of producing water-soluble oils. Emulsions of vegetable oils were prepared
using ionic and nonionic surfactants for use as MWFs [74,80]. The conditions for an
enhanced mutual miscibility for soybean oil or modified soybean oil and water to
prepare emulsions for vegetable oil-based components were investigated. Oil modi-
fication was achieved using ozonation and sulfurization reactions. The viscosities of
the modified oils were considerably higher than the starting vegetable oil.
Various vegetable oil-based metal cutting fluid formulations using oils like soy-
bean, palm, coconut, castor, groundnut, and canola oil have been tried successfully

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 272 Surfactants in Tribology

and their performances in various metal cutting operations have been reported [43].
Belluco and de Chiffre [10] have reported that formulations using rapeseed and
Limnanthes alba oil performed on par with conventional petroleum-based fluids dur-
ing drilling. L. alba is a species of flowering plant in the meadowfoam family known
as white meadowfoam, and it is the source of meadowfoam seed oil. A similar result
was observed using a sunflower oil-based formulation for drilling applications [78].
A higher tool life during lathe turning has been observed using both sunflower and
canola oil formulations [81]. Formulations based on sunflower and canola oils have
also been found to help improve tool life and cutting performance during milling
operations relative to semisynthetic cutting fluid [82]. Castor oil-based formulations
have been found to perform well as grinding fluids [83].
In general, bio-based MWFs provide the following advantages: high biodegrad-
ability, low pollution of the environment, compatibility with additives, low produc-
tion cost, low toxicity, and high flash points.
Some of the disadvantages of bio-based MWFs include low thermal stability, low
oxidative stability, a high freezing point, and poor corrosion protection.

11.3 Recent Advances in the Use of Surfactants

in Cutting Fluids
The investigation by Zimmerman et  al. [84] focused on the design of a mixed
anionic–nonionic emulsifier system for both petroleum and bio-based MWFs to pro-
vide improved lifetime and stability under hard water conditions. Experimental con-
ditions were designed to evaluate the effect of emulsifier structure (branching in the
chain and head group), molar ratios of anionic to nonionic surfactant, and surfactant
concentration. Results from an investigation of 2500 formulations indicate that the
use of gemini anionic surfactants provided improved hard water stability for both
mineral oil- and vegetable oil-based formulations, even in the absence of a chelat-
ing agent. The results also suggest that a total surfactant concentration of >50% was
necessary to attain particle size stability in hard water. These results were used to
Q4 design MWF formulations with fewer components that had improved over a lifetime
with hard water.
One of the problems in steel fabrication is that the oil in O/W emulsion is strongly
repelled by the steel. The oil does not wet the steel and steel/steel friction is high.
Kumar and Biswas [85] studied the dispersion of oil in cutting fluids with anionic
Q5 surfactants. The measured force of interaction was between a silica colloid (AFM)
probe carrying the oil film and steel substrate in water. They reported that for oil-
Q6 insoluble surfactants, the interaction times was short and the strong entropic repul-
sion (without the surfactant) was replaced by a strong attraction. The steel-on-steel
sliding friction in this case was low compared to the case where the surfactant was
soluble in the oil.
Nakagawa et al. [86] prepared a series of esters from the reaction of acid chlorides
with polymeric nonionic surface-active agents (copolymer of propylene oxide and
ethylene oxide) (Figure 11.3). The materials were screened for antirust and other
properties of importance in water-based cutting fluids. An aqueous emulsion of
triethanolamine and oleic acid ester of the polymeric nonionic surfactant showed

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 Use of Surfactants in Metal Cutting Fluids Formation 273

O
RCO (C2H4O)n (C3H6O)m (C2H4O)n H
RCOCl

HO (C2H4O)n (C3H6O)m (C2H4O)n H

RX

RO (C2H4O)n (C3H6O)m (C2H4O)n H

Figure 11.3  Propylene oxide and ethylene oxide polymeric nonionic surfactants. (Adapted
from H. Nakagawa et al., J. Surfactants Deter., 1, 207–211, 1998.)

excellent antirust property when used as a water-based cutting fluid. The emul-
sion of triethanolamine and monononyl ether of the surfactant also showed antirust
properties.
Weiqiang et al. [87] used three novel ashless triazine dithiocarbamate derivatives
as additives for cutting fluid formulations containing rapeseed oil. The formulations
showed excellent load-carrying capacity, good corrosion inhibition performance,
and high thermal stability. They claim that the synthetic additives reacted with the
counterface metal and generated a surface protective film consisting of sulfates, FeS,
and adsorbed compounds containing nitrogen [88].
Pottirayil et al. [87] investigated the effect of the hydrophilic/lipophilic balance
(HLB) of surfactants used as emulsifiers on the lubricity of emulsions used in cutting
operations. The surfactants investigated were polyethyleneglycol-460-monooleate,
SPAN-80, polyethyleneglycol-860-monooleate, and TWEEN-20 (Figure 11.4). A
better lubricity was observed with surfactants of lower HLB. The coefficient of fric-
tion corresponding of emulsifier with lower HLB was significantly lower. The emul-
sion dispersed with a lower HLB surfactant was found to generate a more robust
tribofilm consisting of organic oxides, than that generated by a high HLB surfactant.
The suggested mechanism was that, at concentrations close to the critical micelle
concentration, the surfactants with low HLB self-assembled into a bilayer structure
where hydrophobic tails of the layers trapped a thin film of oil and underwent easy
shear under traction. In the process, the trapped oil was released easily to the tribo-
logical interface. With the high HLB surfactant, the micelle has a closed spherical
morphology, which must be deformed and broken to release the encapsulated oil.
The energy required to do so was higher than in the case where the micelle is a
bilayer in the low HLB surfactants.
Cambiella et al. [89] studied anionic, nonionic, and cationic surfactants for the
formulation of MWFs. They investigated the effect of the surfactant type and con-
centration on emulsion properties such as surface and interfacial tension, contact
angle, oil droplet size distribution, electrophoretic mobility, wetting ability, and
creaming. The emulsifier concentration was found to play a key role in the interfacial
properties. The results showed that different emulsifiers displayed different proper-
ties and that no general rules can be proposed for the formulation of O/W emulsion

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 274 Surfactants in Tribology

(a) O O
OH
O
HO OH

(b) O
O
CH3(CH2)6CH2 CH2(CH2)5CH2 O H
n

(c) O
O
CH3(CH2)6CH2 CH2(CH2)5CH2 O H
n

(d)

HO O n = a + b + c + d = 20
a O OH
b
O
O O c O
O OH
d

Figure 11.4  Structures of surfactants with different HLB investigated by Pottirayil et al.
[87] for effect on lubricity: (a) SPAN-80 (HLB = 4.3); (b) polyethylene glycol-460 monooleate
(HLB = 10.1, n = 10.45); (c) polyethylene glycol-860 monooleate (HLB = 14.7, n = 19.55); (d)
TWEEN-20 (HLB = 16.7).

MWFs. The result indicates that the lubricating behavior seems to be controlled by
the interactions of the oil droplets with metal surfaces.
Chio et  al. [74] reported a new additive for cutting fluid formulation, namely,
DBP. DBP showed excellent antiwear performance compared to tricresyl phosphate
(TCP), as a conventional additive under high-speed and high-temperature condi-
tions. The structure of DBP and TCP are composed in Figure 11.5.

11.4 Conclusion
MWFs play a significant and important role in the prospecting and fabrication of
metals. There are several types of MWFs according to the type of oil and water
phases. These types include petroleum oil-based fluids, chemical fluids, and bio-
based fluids. Commercial MWFs are considered a source of environmental pollu-
tion. This is due to the use of mineral and synthetic oils during formulations. The
current trend is to optimize the MWF formulation by using environmentally accept-
able surfactants and other ingredients.

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 Use of Surfactants in Metal Cutting Fluids Formation 275

O
O P OH
O

(DBP)

O P O
O

(TCP)

Figure 11.5  Structures of dibutyl-3,5-di-t-butyl-4-hydroxybenzyl phosphonate (DBP)

and tricresyl phosphate (TCP).

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