Advance Leather Technology-Lpde6011

Ethiopian Institute of Textile and Fashion
Technology (EiTEX)
Bahir Dar University
Advance Leather Technology

Course code: Lpde6011
Study/Teaching Material Prepared by
Dr. Rajan Karthikeyan

Professor of Leather Technology,
Leather Engineering Dept, Faculty of Apparel,
Ethiopian Institute of Textile and Fashion Technology,

Bahir Dar University.
Course Outline
Chapter 1- Collagen and skin structure

Introduction, source of hide and skin, Hierarchy of collagen structure, Isoelectric point,
Collagen and water, Chemistry of collagen and Hydrothermal stability
Chapter 2- Skin and its components

Introduction, Skin features and components, non-structural components of skin, Variation in
skin structure due to species.
Chapter 3- Curing and preservation of hides and skin

Introduction, The Physical Chemistry of Raw Hide and Curing Process, Method of curing
and preservation, Drying, salting control, Temperature control, Biocides, Radiation curing
and Fresh stock
Chapter 4-Pre-tanning operation

Introduction to beam house operation, Soaking process, Rehydration, removal of salt,
cleaning pelt, removal of non-structural proteins, removal of dung and removal of hyaluronic
acid.
Conditions of soaking, Components of soaking solution, Defect happen during soaking, and it
remedy and greener approach of soaking process
Unhairing
Introduction and purposes of unhairing, Keratin and the structure of hair, Method of
unhairing, Hair burning, Hair saving, Variation in unhairing technology, Acid unhairing,
oxidative unhairing, reductive unhairing and Enzymes unhairing.
Liming
Introduction and purposes of liming, Removal of non-collagens components of the skin,
splitting the fiber structure at the level of fibril bundles, swell the pelt, hydrolysis of peptide
bonds etc. Variation in liming Chemical, pH and biochemical variation, Defects happen
during
liming, and it remedy.
Deliming
Advanced Leather Technology – Lpde6031 Page 2

Introduction and purposes of deliming, Deliming agent such as Water, acid, bases, ammonia
salt, alternatives buffer carbon dioxide, Melanin and Lime blast
Bating
Introduction and its purpose, Factor affecting and enzymes catalysis, Monitoring bating and
Enzyme assays
Pickling
Introduction and its purpose, processes condition, lyotropic swelling, sulfuric acid,
hydrochloric acid, formic acid, pickle formulation and implication for chrome tanning.
Chapter 5 -Tanning
Introduction and chemistry of tanning, Block and groups of periodic tables, Different types
tanning method, Mineral tanning Chrome (preparation of chrome salt, chromium chemistry,
reaction, basification, masking, role of sulfate, ethanolamine, solvent and counterion in the
chrome tanning mechanism. zero float processing, non-aqueous float and modifying
substrate. Titanium, zirconium, iron, and mixed mineral tannages, vegetable table tanning and
Combination tanning, other tannages (Oil tannages, sulfonyl chloride, syntans, resin and
polymeric tanning, aldehydes, and aldehydes etc). Miscellaneous tannages (Epoxy tanning,
isocyanates tannages, multi-functional reagents.) and Zeolites tanning method.
Chapter 6 -Post tanning

Definition, relation between tanning and post tanning, principle of post tanning, compact
processing and dynamic mechanical and thermal analysis, dyeing, dyeing substrates and
alternative coloring method, fat liquoring and its chemistry, water resistance and drying.
Chapter 7-Finishing
Definition, classification, material, and principle of finishing and novel finishing technics.
Chapter 8- Cleaner option and future of leather processing

Introduction eco-leather, general principles of cleaner production, cleaner option each stage
of leather processing and other relate subjects’ biotechnology, microbiology, and role
artificial intelligence in leather industry.

Basic Raw Materials of the Leather Industry:
Hides and skins from domesticated animals of bovine and ovine origin are the basic raw
materials for the tanning industry. Hides and skins are obtained as a by-product from the
slaughterhouse or meat industry.
Hide: Outer covering of a large animal such as a cow or buffalo separated from the body
with or without hair, whether green or dry condition.
Skin: Outer covering of animals such as sheep, goat and calf separated from the body, with or
without hair, whether green or dry condition.
Origin of Hides and Skins used by the Leather Industry:
Every year, the global leather industry slaughters more than a billion animals and tans their
skins and hides. The important animal species used for the production of hides and skins are
of cattle, calf, sheep, lambs, goats, pigs, camel and horses which are slaughtered for meat.
Other species are hunted and killed specifically for their skins, including zebras, bison, water
buffaloes, boars, kangaroos, elephants, eels, sharks, dolphins, seals, walruses, frogs, turtles,
crocodiles, lizards, and snakes.
Parts of Hide/Skin
Different parts of the skin have different names:
1 - The Butt - is the thickest and strongest part of the animal and normally provides the best
quality leather
2 - The Neck - is thick and strong but provides a poorer cut due to creases and growth marks
3 - The Shoulder - is thinner and weaker than the butt or neck
4 - The Backbone - tends to be thinner than the butt area
5 - The Belly - is thin and has a less dense structure
6 - The Flanks - are the thinnest and weakest part of the skin
7 - The Shanks and 8 - Tail end

Principal Processes Involved in Leather Manufacture
(a) Before tannage
 Flaying- removal of the skin from the animal.
 Curing – to preserve skins during transport or storage.
 Soaking – to restore “cured” hides and skins to a natural raw condition.
 Liming – to loosen hair, fat, flesh, etc., and “plump up” the skin ready for tanning.
 Unhairing – to remove the hair.
 Fleshing – to cut away unwanted fat and flesh.
 Deliming – to neutralize the alkali from liming
 Bating – to make the skin softer and cleaner.
 Pickling – to bring the skin to the right acidity for tannage. If the skins are pickled, they
may be preserved at this stage and in some cases degreased.

(b) Tannage
The hides and skins are now tanned by using any suitable method using either vegetable tans
or chrome or alum or oil, etc.
(c) After Tannage

(Note: - The sequence of processes varies considerably for different leathers and the
following is only a rough guide.)
Heavy leathers, e.g. Sole (or bottom) Leathers

 Washing or Scouring – to remove surplus tan.
 Setting Out – to remove wrinkles and flatten the leather.
 Oiling- to make the grain flexible and of good colour.
 Stuffing- to impregnate with oil and fat for waterproof or mechanical leathers.
 Drying.
 Rolling – to compress the leather and make it firm and flat.
Light leathers, e.g. Shoe Upper Leathers

 Shaving or Splitting – to achieve uniform thickness.
 Washing – to free from surplus chrome salts.
 Neutralising – to adjust acidity.
 Dyeing – to obtain the required colour.
 Fatliquoring – a method of applying oil to achieve softness or “handle”.
 Setting Out – to remove creases and surplus moisture.
 Drying.
 Staking – to flex and soften the skin.
 Finishing or Seasoning – to improve appearance.
 Glazing – high pressure polishing; or
 Plating – in a hydraulic press to give a smooth, flat surface; or
 Embossing – in a press to produce a fancy design.

Chemical Composition and Structure of Hides and Skins
The general chemical composition and physical structure of skin varies from animal to
animal. The freshly flayed skins and hides typically have on the weight basis about 65% of
water and 30-33% of protein matter and the rest being contributed by fats, carbohydrates and
minerals. The proteins present can be broadly classified into fibrous and non-fibrous proteins.
The most important of the fibrous protein present in skins and hides is collagen, which is the
true leather making protein present in the skin. Besides collagen, other fibrous proteins like
elastin and reticulin are present in small quantities. Hair and wool present in hides and skins
are made up of fibrous protein, keratin. The non-fibrous proteins include albumins, globulins,
mucins and mucoids.
The skin has four distinct layers histologically and they are
 Epidermis
 Grain layer or Corium minor
 Corium major and
 Adipose or Flesh layers.
The epidermis is composed of four strata of keratinous cells and it is removed during leather
processing. The grain layer consists of fine collagen fibers and also contains major skin
components including hair and related appendages, sweat and fat glands and erector-pili
muscles. This layer is also known as thermostat layer or corium minor. The aesthetic value of
leather comes from the grain layer. Epidermis is generally divided into
 Stratum corneum
 Stratum lucidum
 Stratum granulosum
 Stratum germinatum
Corium major is the main portion of the skin. It comprises a three dimensional network of
collagen fiber bundles. The tightness of the weave and the average angle of weave define the
properties of the skin or the leather made from it. The interweaving of collagen fibres in
corium layer gives strength and resiliency to skin and leather made from it.
Flesh or adipose layer is not really a part of the skin histologically. When hides and skins are
removed from the animal, varying amounts of flesh adhere to different areas of the skin
depending on the skill of the flayer. It is composed of fatty tissue, blood vessels, nerve and
muscle tissue.

Histological Structure of a Cow Hide
Epidermis of Cow:
 It covers approximately 0.6 to 1.8% of the total thickness of the skin.
 It generally does not contain any papillation, which accounts for roughness of grain,
but rarely found in heavy hides.
 The average hairs per square inch account to 13,000 and pigment is found in
epidermis.
 The hair follicles are rooted from 0.4 to 1.5 mm and the longer hairs are generally
more pigmented.
 The sweat glands are comparatively small than that of a calf skin but a common factor
and they are more concentrated in the neck area.
 Also a row of erectorpili muscles can be seen and since the number of hairs are high
all the epidermal appendages such as fat and sweat glands are also high in number.
Grain Layer of Cow:

 It is not of uniform thickness and covers approximately 8 to 35% of the total
thickness.
 Comparatively more amount of elastin are found in cow hides than in calf skins. They
are mostly noticed near the grain membrane.
 The collagen fibres of the grain layer does not usually merge into the corium and
hence causes a line of separation which causes pipeness in heavy hides.
 Also poor merging of grain to corium mostly noticed in fallen hides.
Corium Major of Cow:

 It covers approximately 62 to 85% of the total thickness of the hide or skin.
 The collagen fibre bundles are quite big and are compactly woven.
 The angle weave varies between 45o and 80o and they are much less in the neck and
belly which makes them less compact.
 More reticulin is present in cow hide than calf skin but when compared to buffalo
hides, it is denser.
 Fibre bundles are more thinner in fallen hides.

Flesh Layer of Cow:
 It covers approximately 2 to 5% thickness of the entire layer of the skin.
Histological Structure of a Buffalo Hide

Buffalo hides are thicker than most cattle hides of the equal weight, but the thickness varies
from 3.35 to 6.89mm (excluding the flesh layer). The hides of the female buffalo skins are
usually thicker than those of male buffaloes of the equal weight.
Epidermis of Buffalo Hide:
 It accounts for 1.2 to 2.4% of the entire thickness of the hide. It is made up of
epithelial cells.
 Two types of hairs viz, long or coarse, and short or fine are found in buffalo hides.
The coarse hairs are rooted deeper a little below the junction of the grain and corium.
 The coarse hairs are lesser in number

 The hair follicles in buffalo are straight and deep down 0.3 to 2.3 mm below the
surface.
 The cells of the stratum germinatum contains pigment granules constituting of

melamin and the epidermis only is highly pigmented.
 The epidermis of the buffalo hides are highly papillated contributing to the roughness
of the grain surface and the papillation is more in shank and belly.
 The average number of hairs are 900 to 1200 per square inch and are highly scattered
altogether giving rustic grain pattern.
Grain Layer of Buffalo Hide:

 It is composed mainly of connective tissue fibres.
 It covers approximately 6 to 24% of the total thickness of the hide.
 In the grain layer, the collagenous fibres are quite small and fine and are very
compactly woven without any apparent orderly arrangement.
 Apart from collagen fibres a considerable amount of elastin fibres are present in this
layer, between the hair follicles and erectorpili muscles.
 Elastin is an important protein and provides additional strength.
 In the buffalo hides the cells of the fat gland are not enclosed by a common factor and
just looks like a flower.
 The sweat glands in the buffalo hide are less numerous and less developed.
Corium Major of Buffalo Hide:
 It is also called the reticular layer of its network like appearance.

 It covers approximately 75 to 90% of the total thickness of the hide. It is relatively
thicker in buffalo.
 The fibre bundles in the corium are relatively much larger.
 In the buffalo hides, the collagen fibre bundles of the corium are neither compactly
woven nor do they run at a very high angle to the grain surface.
 It consists of reticular tissue running in all the directions and forms a sheath. More
amount of reticulin is found in neck and belly.

 The buffalo hides are less greasy than all other cattle hides.
 The most noticeable feature of the Indian buffalo hide is the thinner back-bone region.
Flesh Layer of Buffalo Hide:
 It approximately covers 3 to 5 % of the total thickness of the hide or skin.
 It contains very much less amount of fat as considered to other skins.
 Apart from fat cells it contains a twitch muscle (voluntary type) to drive off flies.
 From the quality and thickness and the histological characters, the buffalo hides may
be the best suited for the manufacture of harness leathers.
Histological Structure of Goat Skin:
Although goat skins are available in various parts of the world, Indian goat skins are usually
considered the best among them. The normal size of the skin varies from 23 x 12 inches and
33 x 18 inches. Skins of sizes below the former and above the latter are called "kids" and
"heavies" respectively. In many aspects the structure of a goat skins can be considered in
between a cow calf and a sheep skin.
Epidermis of Goat Skin:
 The epidermis of a goat skin covers approximately 1 to 2.6 % of the total thickness of
the skin.
 The average number of hairs varies from 8000 to 18,000 hairs per square inch. Two
types of hair are present (coarse and fine hairs).
 Like calf, the goat has straight hair follicles and hence straight hairs. The hair follicles
are quite deeply rooted.
 The glands and fat cells are very much less in number in goat skins. The erector pili
muscle is well developed and long in goat skin.
Grain Layer of Goat Skin:
 The grain layer of the goat skin usually occupies approximately 24 to 54 % of the
total thickness of the skin.

 In the grain layer, the collagen fibre bundles are compactly woven. Because of lesser
number of cellular components and fat glands, the goat skin is comparatively compact
than sheep skin.
 In the goat skins there is more elastin and its covers approximately 2/3 rd of the entire
layer of the grain. The presence of larger amount of elastin tissue in perhaps one of
the reasons why greater efforts are needed to open up the grain structure during
pretanning process.
 In good quality goat skins corium and grain layer merges uniformly.
Corium Layer of Goat Skin:
 The corium proper of the goat skin occupies approximately 45 to 75 % of the total
thickness of the skin.
 The collagen fibres present in this layer are firmer and fuller than the corresponding
ones in the sheep skins. It is nearly equal to that of a cow calf hide.
 In goat skins a very low angle of weave is present.
 Fat cells and fat droplets are rarely found in the corium proper of goat skin.
 A considerable amount of reticular tissue is present in goat skin.
Flesh Layer of Goat Skin:
 It roughly covers 1 to 2 % of the total thickness of the skin.

 A considerable amount of elastin tissue is present in the layer.
 Natural fats and fat cells are present in this layer.
Histological Structure of Sheep Skin
The sheep is bred mainly for its wool and meat, and the skin is usually a by-product. In
general, the longer the wool, the thinner will be the skin. The place of origin has a greater
influence on the nature of the skin. In size, sheep skins are almost equal to goat skins but in
texture and strength they are less compact and weaker.
Epidermis of Sheep Skin:
 The epidermis of the sheep skin roughly occupies 0.8 to 2.5 % of the total thickness of
the skin.
 The hair follicles are curved and hence the curliners nature of the wool. The wool is
deep rooted into the skin.
 The sweat glands in the sheep skins are well developed and present in great numbers
making the junction of corium and grain weak.
Grain Layer of Sheep Skin:
 The grain layer of the goat skin covers approximately 44 to 74 % of the total thickness
of the skin.
 The collagen fibre bundles in the grain layer are less compactly woven comparably.
 The presence of numerous sweat glands and fat cells make the leather spongy.
 They have a considerable amount of natural fat along the spine line.
 A continuous layer of fat is present at the junction of grain and corium, the removal of
which makes the leather weak during the pretanning.
 In good quality sheep skins grain uniformly merges into the corium.
Corium Layer of Sheep Skin:
 The corium proper of sheep skin occupies approximately 24 to 55 % of the total

thickness of the skin.
 The collagen fibre bundles are extremely thin and are not closely interwoven and
tends to run parallel to the grain surface which accounts for the looseness of the
structure.
 A considerable amount of natural fat is present in this layer spreaded throughout.
 A skin containing too many fat cells will yield only a spongy leather.
Flesh Layer of Sheep Skin:
 The flesh layer approximately covers 1 to 2 % of the total thickness of the skin.
 This layer consists layers of tightly packed fat cells.

Hair Sheep Skin:
From the histological characters it appears that hair sheep skin occupies a position between
goat skin and wool sheep skin and passes certain special qualities viz.
 Firmness with a smooth strong grain.
 Low angulation of fibre bundles with fairly compact weave.
 Full fibres with good tensile strength.
Collagen
Collagen is an insoluble fibrous protein which plays a major structural role in extracellular
and connective tissues, and is the single most abundant protein in the animal kingdom. The
name, collagen, is derived from the Greek “kolla” (glue) and “genes” (born of), and describes
its link to gelatin, as gelatine was used as glue and is produced when collagen is boiled for
extended periods of time. The protein consists of two identical α1 chains and one α2 chain,
each with a left-handed helical conformation. The three chains together form a right-handed
triple helix known as tropocollagen. Tropocollagen molecules spontaneously assemble into
fibrils: long, rod-like structures of quarter-staggered molecules with characteristically high
tensile strength and high enzymatic resistance. These fibrils then arrange together to create
collagen fibers and fiber bundles that make up the extracellular matrix of many organs.
Collagen is a major component of the extracellular matrix, providing mechanical and
supportive functions in a wide range of body tissues.
Properties of CollagenP
The collagen is clearly distinguished from all other proteins by a number of well-defined
histological, physical and chemical properties.
Principal Diagnostic Characteristics of Collagen

– Its unusual amino acid composition.
– Its mechanical properties like low extensibility and shrinkage by warming.
– Its ability to swell in acids and alkalis.

– Its chemical inertness in the native state to common proteolytic enzymes.
– Its conversion to gelatin on prolonged heating with water or alkali.
(i) Shrinkage Temperature and Stabilizing Cross Linkages

When a fibre of collagen heated in the presence of water, at a certain temperature, it contracts
to about one third its original strength. The reason for this shrinkage is that a linear polymer
immersed in fluid medium, in the absence of any stabilizing cross links assumes it’s most
parabolic shape, namely random coil i.e., molecules lose their structure and the peptide
chains, which were previously held out straight, assumes a random configuration. When
shrinkage takes place, it is thought that the hydrothermal agitation at this temperature is
sufficient to overcome the forces (chiefly hydrogen bonds) which hold together the
polypeptide chains. In amino acid analysis, these shrinkage temperature have been correlated
with the Hypro content of the collagen. The lower the amount of hypro, the lower the value
of shrinkage temperature.
Possible Inter Chain Linkages in Collagen

– Electrovalent salt linkage between charged amino and carboxyl group.
– Ester linkage between hydroxyl and carboxyl groups.
– Keto imide linkage between amino and carboxyl groups.
– Amide cross linkage between amide and carboxyl groups.
– Hydrogen bonds.
The hydrogen bond is the most important stabilizing link in collagen. The hydrogen bonds
arise through the coordination of peptides on adjacent chains. But the presence of the imino
acids (Proline and Hypro) in collagen leads to a frequent interruption of the normal sequence
of the –CO–NH– backbone with –CO–N= links. This reduces number of hydrogen bonds.
But the interchain hydrogen bonds are formed in collagen between the hydroxyl groups of
hypro and carboxyl of an adjacent peptide as shown in the Figure 17. The hydrogen bonds are
relatively weak compared with the covalent type of linkage. But the collagen stability does
not lie so much on the own strength of hydrogen bond but the large number of hydrogen
bonds formed.

Thus the molecular stability of collagen arises from the interplay of a wide range of forces
such as covalent, electrovalent, hydrogen and hydrophobic bonding. The stability formed by
carbohydrates and muco-polysaccharides to collagen is also considerable.
Figure 17. Model of Hydrogen Bonding in Collagen

Figure 18. Schematic of Intramolecular and Intermolecular Covalent Crosslinks in
Collagen
(ii) Isoelectric Point
Electrostatic attraction is one of the important forces, where the triple helix is held together
and it is represented below:
P-CO2 – …. +H3N-P
These are the so-called ‘salt links’, formed by electrostatic reaction between acidic and basic
sidechains of the protein, which together determine the isoelectric point of collagen. The IEP
is an important parameter, because it controls the charge on the protein at any given pH: since
the reactions in leather making are usually dependent on charge, they are in turn dependent
on the IEP and the way the value of the IEP varies during processing. The isoelectric point
is defined in several ways, but the most fundamental definition is that it refers to the point on
the pH scale at which the net charge on the protein is zero, illustrated as follows:
Because the charge on the protein can be adjusted with acid or alkali, to make the protein
positively or negatively charged, respectively, there must be a point on the pH scale when the
net charge passes through zero. Therefore, the IEP depends on the relative availability of

groups that can participate in reactions with acid and alkali, the carboxyl and amino groups
(see Figure 19).
Figure 19. Generalization of Charges on Collagen
At the isoelectric point, the following phenomena occur, each of which might be used as the
definition, as a whole or in part.
– net charge is zero
– content of intramolecular salt links is maximised
– swelling is at a minimum
– shrinkage temperature (and other aspects of hydrothermal stability) is maximum
There are two points relating to isoelectric point and its relevance to leather making that are
very important and worth emphasising:
 IEP is a point on the pH scale, so it does not change with changing pH of the system. The
IEP of collagen is the same whether is in the alkaline, limed state or in the acidic, pickled
state. The importance of this point is that the isoelectric point can only be changed if there
is a chemical change that alters the availability of active groups; this can occur in the
beamhouse processes, in the tanning processes and in the post tanning processes.
 The charge on collagen is determined by the relative values of the IEP and the pH. If the
pH is higher than the IEP, the collagen is negatively charged, and if the pH is lower than
the IEP, the collagen is positively charged. Moreover, the further the pH is from the IEP,
the greater is the charge, although it is limited by the availability of amino and carboxyl
groups. The importance of this concept relates to the application of charged reagents,
particularly post tanning reagents and their interaction with the charged leather substrate.

It can be assumed that at the starting point of processing for collagen, prior to raw pelt going
into liming (alkaline treatment for unhairing and modification of the skin’s fibre structure),
the IEP is at physiological pH, about 7.4.
Table 3. Representative pI Values of Collagen and Leather
Structure of Collagen
It is a feature of the properties of collagen that it has ‘layers’ of structure, collectively known
as the ‘hierarchy’ of collagen structure, which combine to allow the formation of fibres.
These can be divided as follows: (see Figure 21 & 22)
– Primary Structure
– Secondary Structure
– Tertiary Structure
– Quaternary Structure

Primary Structure of Collagen
Primary structure denotes the complete amino acid sequence in a protein. Collagen is usually
characterised by high content of glycine, proline and hydroxyl proline. This also consists
hydroxyl lysine and low amount of aromatic and sulphur containing amino acids.
Glycine is the smallest of the amino acids and the high proportion of this small amino acid
allows the polypeptide chains to come close to one another and form a structure of high
mechanical strength.
Hydroxy proline is present only in collagen and so the estimation of this amino acid may give
the presence of collagen in a skin. On the other hand cysteine and tryptophane are not present
in collagen. But tryptophane is present in all other skin proteins. This also helps in detection
of collagen.
The amino acid sequence is a tripeptide repeat (Gly-X-Y)n (n ranges from 100 to 400).
Therefore, one-third of the amino acid residues in collagen are Glycine. Furthermore, X is
often proline and Y is often hydroxyproline: 12% of the triplets are -Gly-Pro-Hypro-, 44%
are -Gly-Pro-Y- or Gly-X-Hypro- and 44% are -Gly-X-Y- where X and Y are not defined. In
this way, the helical shape of the molecule is determined.
Thus collagen can be defined as “Three repeating tri-peptides each coiled in a left-handed
polyproline helix interacting to form a right-handed super-triple helix and containing
hydroxyproline and hydroxyl lysine”.
The amino acid content of collagen and other proteins associated with skin are compared in
the Table 4:
Table 4: Amino acid contents of Collagen and skin proteins: residues per 1000
Collagen type I Collagen type III

Type Amino acid Elastin Keratin
Glycine 330 309 355 81
Alanine 110 97 178 50
Non Valine 22 27 175 51
polar
Leucine 26 36 59 69
Isoleucine 12 18 19 28
Hydroxy Serine 34 43 4 102

Threonine 18 22 4 65
Tyrosine 5 3 12 42
Aspartic acid+ 47 53 60
asparagine 2
Carboxy
Glutamic 73 76 12 121
acid+glutamine
Lysine 38 22 5 23
Hydroxylysine 6 12 0 0
Basic Arginine 48 45 5 72
Histidine 4 6 0 7
Tryptophan 0 0 0 12
Proline 126 97 125 75

Imino
Hydroxyproline 93 108 23 0
Cystine 0 0 1 112
Sulfur
Methionine 4 8 0 5
Phenylalanine 14 18 22 25
Aromatic
Tyrosine 5 3 12 42
(a) (b) (c) (d)

(a) (b) (c) (d)
Figure 21. Schematic Representation of Collagen Structure
(a) Primary Structure: Sequence of Amino Acids forming Polypeptide Chains
(b) Secondary Structure: Coiling or Folding of its Polypeptide Chain
(c) Tertiary Structure: Three Dimensional Shape of the Polypeptide
(d) Quaternary Structure: Final Three Dimensional Rope like Structure formed by
Several Polypeptide Chains

Figure 22. Schematic Representation of Collagen Structure
Secondary Structure of Collagen

The secondary structure of collagen refers to the local configuration of polypeptide chains,
which is dominated to a large extent by the stereo chemical features of the constituent amino
acid residues. The stereo chemical features gives the bond length and bond angle of the chain
backbone. Each of the frequently occurring imino acid residue is capable of turning the
peptide chain by 90o and when the two imino acid residues occur together 180 o turn is
expected. The pitch of the helix is 8.7 A o. This is a left handed coil with 3.3 amino acid
residues per turn.
In polypeptide the option of rotation around skeletal bonds is usually decided in favour of
formation of large numbers of peptide backbone hydrogen bonds to acquire stability, either
intra molecularly (within the same molecule e.g., one helical turn can bind with the next
helical turn by H-bonding offers stability to α-helix) or inter molecularly (e.g.,β-structure,
parallel or anti parallel formation, when two adjacent polypeptide chains occupying the same
plane can join together by H-bonding (see Figure 23).
α-helix Parallel β- Sheet Antiparallel β- Sheet

(Intra Molecular H-bond) (Inter molecular H-bond)
Figure 23: Secondary Structure of Collagen
In collagen, the abundance of proline and hydroxyl proline residues prevent the formation of
α helical chain segments, instead, long sequences of individual chains of collagen of left
handed version is produced. The occurrence of glycine residue at almost every third position
appears to have sterically permissible H-bonding.
There are number of bond energies contribute to the stability of collagen, either weak or
strong and intermolecular or intra molecular in nature. The stabilising forces that are present
in collagen molecule are
Ñ Hydrogen bonds
Ñ Hydrophobic bonds
Ñ Ionic bonds
Ñ Stability due to resonance
Ñ Covalent bonds

Peptide backbone H-bond
Tertiary Structure of Collagen
Tertiary structure of collagen normally refers to large scale folding, helicity, and other
convoluted forms assumed in space by the totality of the polymeric chains, which constitute
the fundamental molecular unit. In collagen, the fundamental molecular unit is called
Tropocollagen (TC) molecule, a right handed super coiled molecule, made out of three left
handed strands of α-helices (see Figure 24).
The dimension of Tropocollagen molecules are about 3000A o long and 15Ao in diameter with
a molecular weight, which shows some variations according to the species and method of
extraction, but was found to be very close to 300,000. Each of the three polypeptide chain
known as α-chains, which constitute the tropocolloagen, extends the entire length of the
molecule. An α- helix has a molecular weight of about 100,000 and contains therefore,
roughly 1,000 amino acid residues. Amongst these three α-helices, two has almost identical
amino acid composition are called as α1chains. The third one has somewhat different amino
acid composition called as α-2 chains.
The fundamental tropocollagen molecule is essentially made up of three polypeptide chains,

each coiled itself singly in the anti-clock wise direction to form left handed helices. In each
turn of the left handed helix there are on an average 3.3 amino acid residues and the
projection of each amino acid residue on the axis of the single helix is 3Ao.
Three such helices in the tropocollagen molecule jointly coils again in the clockwise direction
with a rotation of 36o per amino acid residue to form a giant super helix. The super helix
formed from three individual α- helices is a right handed helix. A super helix has therefore a
coiled coil structure. The final projection of each AA residue on the axis of the super helix is
further reduced to 2.86 Ao from 3Ao. In each turn of the major helix, there are nearly 30
amino acid residues and the projection of each turn to the super helical axis is about 85.8A.
Figure 24. The Triple Helix
Quaternary Structure of Collagen
The quaternary structure constitutes the aggregation, organization and packing of the
Tropocollagen molecules to form a three dimensional fibril structure. This structure is
important because it imparts the routine all the unique physical and functional properties.
This structure is of macro molecular level while primary, secondary and tertiary are micro
molecular level. The quaternary structure mainly depends on electron microscopy.
In electron microscope, the native collagen has a standard structure. The bands are
approximately 67 nm apart. 5 “rows” of molecules with staggered stacking leads to together
make the D-period. The value of D is obtained by dividing the staggered array of molecules
into five units of equal length. The composition of the five sequences shifted by the distance
D is shown schematically in the Figure 25.
Figure 25. The Penta Molecular Lateral Structure - Schematic diagram showing repeating
distance D = 67nm and Head to tail cross linking. TC molecules are staggered at quarter of its
length (very similar to the brick work in civilian construction).

Figure 26. Axial Structure of D-periodic Collagen Fibrils
The above figure is the schematic representation of the TC molecule in an array within
collagen fibrils. A micro fibril consists of five strands of TC molecules, displaced against
each other from one row to next row. The staggered distance D causes the segments a, b, c, d
and e to be immediate neighbours. Head-to-tail cross links permitted by the sequence of α-1
chains are known.
Thus the TC molecules are arranged in such a way that one molecule over laps the other by
quarter of its original length. This will enable a strong interaction between the TC molecules.
The lysine and hydroxyl lysine residues are present in the polypeptide chains are responsible
for bond formation. Thus covalent cross links between collagen molecules within the fibrils
are made. This is very much necessary for the tensile strength.

The quarter staggered macro molecular level is followed by supra molecular level (see Figure
27). The supra molecules are packed closely and are held by definite intermolecular bonds.
Such bonds are usually classified as:
Side-to-side
Connecting overlapping molecules shifted by 1/4th of their length (quarter staggering). These
bonds are easily cleaved by pepsin.
Head-to-tail
In which two different molecular ends participate in bond making. This bond is fairly
resistant to pepsin and lies in the molecular overlapping range.
Tail to- tail
Connecting two TC molecules by their (identical or similar) ends, located at their last
residues and are to some extent pepsin selective.
Within the micro fibril only head-to-tail bonds are possible. Between fibrils side-to-side and
head-to-tail bonds can occur. Probably, N-terminal non-helical region is involved in the
formation of head-to-tail bonds, whereas the larger C-terminal non-helical regions are
supposed to establish inter fibrillary bonds.
The region due to the aggregation of molecules into fibrils, will always be surrounded by
clusters of hydrophobic residue, present at the different molecules, since, they themselves are
hydrophobic. Moreover the variety of forces of different strengths, which hold together atoms
within the same chain or different chains, account for the fact that, TC molecules aggregate to
form complex crystallites of several kinds including, native, segment long spacing (SLS) and
fibrous long spacing (FLS) crystallites.

Figure 27. Quaternary Structure of Collagen

Preservation/Curing of Hides and Skins
Curing or preservation is a term used to protect the hide or skin temporally against
putrefaction damage. Hides and skins can be processed within hours of slaughter if the
tanneries are situated close to slaughterhouses, as it happens in some western countries. But
in most cases, the hides and skins have to be protected against bacterial damage during the
period between flaying and the commencement of leather processing. The process or the
treatment followed for the prevention of putrefaction is termed preservation or curing.
Putrefaction is caused by the digestive action on the skin of micro-organisms called bacteria.
Putrefaction only occurs in the presence of free water and the presence of dissolved
substances like high quantities of salts, acids or alkalis, bactericides or other toxic chemicals
may inhibit the bacterial action. Thus a perfectly cured stock can be stored for a considerable
period of time and can be transported from one place to the other until it is actually subjected
to processing by the tanners.
An ideal curing procedure must not change the condition of the stock to such an extent that
they cannot be brought back to their original fresh condition by simple processes like
washing and soaking. The fiber structure should not be damaged physically or chemically or
the inter-fibrillary proteins should not undergo any permanent change.
Principle Involved in the Preservation

The strategy for the prevention of putrefaction should take into consideration the factors that
contribute to the accelerated growth of bacteria and to device methods for controlling these
factors. The fundamental requirements of most bacteria are:
 Suitable pH
 Suitable temperature
 Food
 Sufficient water/moisture
pH
pH is an important factor to be considered for the degradation of the skins and hides. The
reason is that the bacteria or enzyme is active at neutral pH or slightly alkaline conditions.
The rate of growth of damaging bacteria is most rapid around the pH of a fresh hide. It
decreases at extremely high and low values. Treating hides and skins with acid or alkali
would certainly reduce or eliminate bacterial activity. However, the effect of the treatment

with acid or alkali would cause unacceptable damage to the quality of leather made from the
hide or skin. These considerations and the complexity of the procedure mean that pH control
is not a suitable way of preserving the fresh hides and skins.
Temperature
Bacterial growth is closely related to temperature. The growth is rapid in those conditions
presented by a fresh hide or skin at about 37oC, which is the body temperature of the animal.
It is necessary that the skin being preserved should be stored below 30 oC. Most of the
bacteria show considerable activity above 15oC. At very high temperature, bacteria would be
killed. Subjecting hides and skins to high temperature would indeed stop bacterial growth but
such treatment would cause irreversible changes in the substances that make leather.
Reduced temperatures below 5oC have little adverse effect on hides and skins and provide
some scope for preservation. The growth of bacteria slows down or ceases at sufficiently low
temperatures. But the chilling and freezing have been considered more expensive processes
compared to salt based method.
Food
Unfortunately hide or skin, being a proteinous substrate, is an excellent food for bacteria; so
nothing can be done to deprive bacteria of food except inhibiting their growth through the
control of other factors. However, the growth of bacteria increases if additional food in the
form of blood is available.
Moisture
Moisture content of the raw hide or skin is an important factor responsible for the growth of
the bacteria. The moisture content of fresh hides and skins, which is about 65%, is quite
adequate to support bacterial growth. However, if the water content is reduced by methods
such as drying and salting, the bacterial activity decreases and eventually stops when the
moisture content is less than about 35%. At this level of moisture, mould growth may still
continue particularly on fatty hides and skins. The moisture content should therefore be
reduced to less than 20% to provide complete preservation in the absence of any bactericide
or bacteriostatic agent. If the level of water is reduced to 10% or less, two problems become
apparent. First, such over-dried hides and skins become brittle and may crack during
handling. Secondly, and more important, low moisture content materials rehydrate only

slowly and perhaps incompletely during the course of soaking and subsequent tanning
operations.
The preservative action of salt is most often described in terms of its osmotic effect but a
better explanation involves availability of water or A W, which is the vapor pressure of the test
material divided by the vapor pressure of pure water. The A w of pure water is 1 and that of
hides and skins is about 0.99. Most bacteria grow best in an A w close to that of pure water but
will tolerate an Aw of 0.7. During the course of preservation procedures like salting, the high
Aw of fresh hides or skins is reduced by dissolving large quantities of a soluble chemical into
the moisture inside the material being preserved. The microorganisms must compete with
solute molecules for the water they require for the growth.
Therefore, drying makes water unavailable to bacteria physically (by eliminating some of it)
and chemically (by causing an increase in the concentration of soluble materials and hence a
decrease in the Aw). Salting makes the water unavailable to the bacteria physically (by
eliminating some of it by osmotic effect i.e. dehydrating) and chemically (tying it up in
concentrated solutions).
As discussed earlier, the moisture content of the raw hides and skins is a very important
factor that controls the bacterial activity in them. Bacteria do not grow unless there is critical
moisture content in the material. The principle of abstraction of water below this critical level
is adopted in the popular curing methods viz.; salting and drying.
Classification of Curing
Curing is broadly divided into short term preservation and long term preservation (see Flow
Chart 1).
Long Term Preservation Methods

There are two important methods of curing which work on the principle of dehydrating the
skins. They are (1) simple drying and (2) salting.
Curing by Drying
Simplest and cheapest method of curing hides and skins is by drying them by evaporation
directly under the sun. This method is prevalent in some tropical countries like certain parts
of India and Africa. This method can be achieved in two ways: on the ground or in frames or
over wires off the ground.
Preservation Methods
Long Term Preservation Short Term Preservation
Salting Drying
Chilling Freeze Drying Irradiation Chemical
Wet Salting Dry Salting Brine Curing
Flint Drying Drying by Pegging Frame Drying
Flow Chart 1. Classification of Curing Methods
Flint drying
Hides and skins are spread out on the ground or on the branch of a tree and are allowed to dry
out in the hot sun. As a result, the hides and skins shrink and crumple up and are known as
crumpled hides. As these hides are exposed to the hot mid-day sun, they dry out quickly
forming a hard and impermeable crust on the surface, through which the moisture from the
inner layer of the hides cannot come out. This leaves the inner layer wet, which may be
attacked by bacteria, under suitable conditions, thus causing blisters when these stock is
converted into leather. These are called sun ‘blisters’. This type of hides is of inferior
quality. Pre-treatment with bactericides has been attempted to prevent this.
Drying by pegging
It consists in stretching out the hide, flesh side up weighing it down with stones or pegging
the edges with sticks to the ground (see Figure 1). Because of the lack of air circulation from
beneath, moisture and heat are retained in the hair side touching the ground, making it an

extremely attractive medium for destructive bacteria. It produces dried material of the most
appalling quality, and consequently of the poorest value to the producer.
Figure 1. Drying by Pegging
Frame Drying
In this process, the hides are stretched and dried by tying them with strings to a rectangular
bamboo or wooden frame. The framed hides are then dried out in the mild sun in an open
yard, where a good current of air is flowing. The best option is to frame-dry under a shed.
While frame-drying in the open is cheaper, it is better to use a shed where suitable cross-
ventilation occurs. Shed drying also allows for close supervision as well as protection from
theft and control of damage from vermin. Drying sheds can have regular frames made of
wood or metal pipes that are permanently fixed. Large frames meant for hides, 3m × 3m, can
be adapted for skins by partitioning allowing four skins to be stretched as shown in Figure 2.

Figure 2. Frame Drying Method
Although the dried hides are practically immune to bacterial action, they are liable to be
attacked and severely damaged by insects like beetles when kept in storage. Hence, such
hides used to be dipped in a solution of sodium arsenate for about a minute and then dried
again. Some of the other insecticides used include D.D.T., γ-hexachlorohexane and dieldrin.
Curing by Salting
There are three methods of salt curing methods practiced, namely (1) wet salting (2) dry
salting and (3) brining.
Wet Salting
This is the common practice followed in many countries. Hides after flaying are salted on the
flesh side. Salt is generally applied in two instalments. A number of such treated hides are
kept in a pile for about 10 days or more (see Figure 3). A wet salted hide having moisture
content of about 40-50% may not give problem in soaking, the first operation in leather
making the moisture content of skins and hide is restored to its original moisture of about
65%.
Since sea salt often contains sulfates and chlorides of calcium and magnesium as impurities
and hence, the salted skins are affected by salt stains. Salts of marine origin are also mostly
contaminated with a large number of halophilic bacteria, which are responsible for the
development of “red-heat” on salted hide or skin. To improve the salt cure and also to prevent
the growth of halophilic bacteria, the use of antiseptics like sodium pentachloro phenate in
admixture with salt has been advocated. However, the use of sodium pentachloro phenate has

been discontinued world over as a biocide for toxicological reasons. Use of 2-4% soda ash
and 1% naphthalene has also been suggested. Boric acid is used along with salt in countries
like Australia.
The grain size of the salt is said to have a great influence on the quality of cure. Normally 40-
50% of salt is required on the green weight of the hide or skin for complete curing, but there
is a tendency to use more salt for curing in most cases.
Dry Salting
In this process, the hides and skins are first treated with powdered salt or brine and dried.
The object of this method is to combine the advantages of both the wet salting and dry-cure
techniques. Hides and skins are either brined or coated with brine or salted with powdered
salt and then dried by nailing on boards or suspending loosely in frames. Such cured hides
can be stored for longer duration and are lighter in weight. A mixture of clean salt containing
5 parts of anhydrous sodium sulphate and 1 part of sodium chloride has also been
recommended for dry salting. Khari salt (an earthly material) containing mostly sulphates
with a small amount of chlorides is less hygroscopic and therefore preferred for dry salting
purposes over common salt.
Figure 3. Wet Salted Cow Hide

Brine curing
This method is mostly followed in South America and the brine cured hides are called
‘Frigorifico’ hides. The washed hides are put in a concentrated brine solution of about 22-24 o
Be for a period of 12-24 h, making sure that the hides are submerged in the brine solution.
They are removed from the brine and allowed to drain. Clean fresh salt is now applied on the
flesh side of each hide and the hides are piled and left in that condition for 30 days. It has
been claimed that by brining, the cured hides obtained are standard cured stock that produce
heavier leathers of high quality. The quality of brine cured hides against packers hides has
been assessed. The brine cured hides are free from salt stains and can be preserved for a
longer period.
Alternately, in a large commercial slaughterhouse, the hides are taken from the killing floor
and sent through a large tumble washer that cleans off surface dirt and manure. Next, the
hides passed through a fleshing machine in order to remove the remaining fat and meat. The
cleaned hides are then loaded into a vat of brine (see Figure 4).
Figure 4. Modernised Brine Curing System

Curing by pickling
This method is mainly used for dewooled sheepskins exported from Australia and New
Zealand. Pickling preserves skins partly by dehydration and partly because of the low pH

obtained in the system. Generally sulphuric acid and common salt are used for pickling skins
for preservation. Either excess or insufficiency of acid or salt is harmful. It has been
suggested that pickle liquor should contain 12-15% (w/v) of common salt and 1.5-2.0%
concentrated sulfuric acid. Fungicides are also used to prevent fungal growth.
Short Term Preservation Methods

Preservation by Irradiation
Attempts have been made in the United States of America (USA) to achieve hide sterilization
by irradiation with gamma rays and electron beams. For hide processing, for reasons of
efficacy, safety, versatility, speed and cost, electron beams were reported to be superior to
gamma rays. A microprocessor controls the electron beam dose parameters of the exposure,
monitoring them every one hundred milliseconds and documenting them continuously. The
“dose” or measure of energy absorbed by the treated product is reproducible to within a
fraction of a percent. Once the system parameters are established for a given product, the
computerized control systems ensure that the process can be repeated without deviation. The
advantages of the system are the decreased salinity of effluents and there is no toxic effect.
The disadvantages are: (i) the need for very expensive equipment, (ii) the need for full
protection of the workers operating the equipment, (iii) possible reduction in tensile strength
of the leather, (iv) the need for covering each hide with plastic bags to prevent
recontamination with microorganism during storage and (v) high cost of treatment.
Curing by Silica Gel
In place of the salt which functions as a curing agent mainly because of its ability to
dehydrate the hide/skin below critical moisture content apart from its bacteriostatic property,
a dehydrant silica gel has been used to preserve the raw hide/skin alone or with reduced offer
level (5%) or in combination with a preservative. The efficacy of the systems were analyzed
by the moisture content, total extractable nitrogen content, bacterial count and pollution load
generated during leather processing. The results showed that the leather obtained was
comparable in properties with a potential to reduce pollution load in terms of TDS by 70-75%
and chlorides by 80-85% compared to salt curing system.
Chilling and Freezing
Chilling and freezing are practiced universally for preservation of meat but only in Western
countries and Australia, industrial application of cooling system for hides and skins is being
practiced to a limited extent. It is reported that hide freezing has been a common practice in
colder regions of erstwhile Soviet Union. A pre-treatment with a biocide followed by chilling
has been studied for the storage of ostrich skins in Africa and have also experimented with
curing using cold storage.
In Australia, studies were conducted for freeze curing of hides for long term storage and it
was estimated that cost savings to the tune of 30% in comparison with salt curing was
possible. Now it is commercial practice in Australia to use chilling as a method of short term
preservation for hides for certain situations. A temperature between 2 and 5 o C is employed
and the results are reported to be satisfactory. However, preservation time is limited and
Table 1 summarizes the dependence of preservation time on the storage temperature.
Table 1. Dependence of Preservation Time on Chilling Temperature
Preservation temperature oC Preservation time

0 3 weeks
5 2 weeks
10 5 days
15 2 days
20 1 day

PRETANNING PROCESSES
Soaking
In the manufacture of leather from raw hides and skins, soaking is the first and a very
important operation, as succeeding operations and the final quality of leathers depend on
proper soaking of the raw stock. In this operation, the hides/skins are brought back to the
original soft and pliable condition using soaking aids and bactericides. This operation is
generally carried out in pits / drums depending in the raw stock, using the required quantity
of water.
Objectives of Soaking

 Rehydration (wetting) of the hide/skin.
 Removal of salt used for preservation.
 Removal of dirt, blood and dung.
 Removal of unstructured or non- fibrous proteins such as albumins and globulins.
 Attack on epidermal structures.
 Optimum preparation of the skin for the subsequent process.
Soaking Method of Wet salted Hides:

Soaking method depends on the type of raw material. Specifically, it depends on the type of
curing of raw stock. Thus, fresh hides/skins require only a few changes of water, preferably
cold water, to remove blood, dirt, etc. Wet salted stocks have to be soaked for longer period
(6-15h), depending on the degree of dehydration. In case of prolonged soaking, suitable
preservatives are to be used. To reduce the time of soaking, wetting agents are used. It is
important to remove surface salt, dirt and blood etc. by a pre wash or dirt soak of 30-60 min.
Dirt soak is most effective when it starts with floating process rather than continuous washing
process to avoid the danger of fibre breakage due to mechanical action when the raw material
is partially dried. (i.e raw material with very less moisture content, see Figure 5). Soaking at
pH 9.5-10.0 using sodium carbonate or sodium hydroxide speeds the soaking effect as the
protein fibre absorbs water more readily at a higher pH. It is important the soaking pH should
not exceed above 10 because the hair root will be immunized.
Completion of soaking is tested by folding the skins/hides flesh side out, and feeling for
uniform softness and flexibility.

Figure 5: Raw Material for Soaking
Figure 6: Uneven Tanning Results from Improper Soaking

Typical Recipe/Process for Soaking of Wet salted Hide/Skin: (Drum Method)
Raw Material:
Wet salted cow hide / goat or sheep skin
Dirt Soak
Soak the hide/skin in 200 to 300% water at 20-25oC for 30 min.
Then run the drum for 30 min and drain the water.
Next, the skins are subjected to two washings with plain water to bring down the Be > o1
Main Soak
Add 200% water at 20-25oC

0.25% Non ionic wetting agent
0.2 % Preservative
0.5% Sodium Carbonate
Run the drum for 30 min. Check the pH 9.5. If necessary add additional sodium carbonate.
Then the drum is run for 5 min / hour for overnight.
Next day, check the completion of soaking and the soaked skins are taken for Liming.
Soaking Method for Dry salted or Dried Hides/ Skins:

Dry salted and dried hides and skins have a low moisture content of 10-15%. For soaking dry
salted stock, soaking aids and preservatives are to be necessarily used. Additives like sodium
sulphide, caustic soda, soda ash may be required for proper rehydration. Enzymatic soaking
aids have been found to be very useful to reduce the time of soaking. Dried hides require
soaking for a period longer than that for dry salted stock, along with suitable wetting agents
and preservatives. The soaking time is dependent on the condition of the goods and will be
from 24-48 hours.
For soaking of dried hides or skins, a static soak should be prepared in a pit or paddle (see
Figure 7 & 8). Sufficient float must be used to fully cover the skins and pre-mixed with
sodium carbonate to pH 9.5-10.0 with suitable wetting agents and preservatives. In the case
of processes conducted in drums (see Figure 9) or paddles the vessel may be turned 1or 2
revolutions each hour. Both for dry salted and dried hides/skins; an intermediate breaking
over the beam, i.e., green-fleshing will facilitate easy soaking.

Figure 7: Soaking Pit
Figure 8: Soaking Paddle

Figure 9: Soaking Drum
Liming
In liming process, the hides and skins are treated with lime [Ca(OH) 2] and sodium sulphide
(Na2S) and/or sodium hydrosulphide in the presence of soft water at a temperature between
18 and 250C in pit/paddle/drum. This is done depending upon the soaked material and final
end-product. During this process, hair and flesh is loosened and removed by hand/machine to
make the material free from any hair and loose flesh presenting a clean surface.
Objectives of Liming:
 Primary objective is to loosen and removal of epidermis layer i.e, hair, wool etc.
 Saponification of the fat and removal of adipose or flesh layer during fleshing
operation.
 Uniformly open up the fibre structure by alkali swelling. Uptake of water push the
structure apart i.e splitting effect.
 Splitting of fibre structure at the level of fibril bundles. Fibre splitting allows better
penetration of tanning and post tanning auxiliaries.
 Removal of unwanted proteins such as sweat glands, blood vessels, lymph and nerve
tissues.
 Complete removal of interfibrillar non-fibrous or globular proteins such as albumins
and globulins
 Modification of collagen reaction groups.

Swelling Effect in Liming:
Pelt can be swollen by two mechanisms
Ñ Osmotic Swelling
Osmotic swelling is caused by the imbalance between the ionic concentration outside the pelt
and inside the pelt. Normal liming operation takes place between pH 12-13. When the hide is
introduced into the lime, the grain and flesh surfaces of the skins are subject to solutions at
pH approximately 12.5, while the centre of the skin (cross section) is still neutral pH. As a
result swelling occurs.
Ñ Lyotrophic Swelling:
This swelling is caused by the disruption of the structure by the action of lime and other
alkali that can insert into the hydrogen bonding of protein chains. The lyotrophic effect
results in the opening up of collagen structure. This phenomenon is both physical and
chemical. The longer the liming, the more opening or fibre bundle splitting may take place in
the skin. The swelling of the protein results in a much greater increase in the diameter of the
fibre than its length and results in plumping of the stock. Plumping adds thickness to the final
leather, improves softness, etc.
When the degree of swelling is more, i.e. strong liming outcome, the final leather would be
 softer
 smooth grain and stretch
 Increased area yield.
When the degree of swelling is less, i.e less liming outcome, the final leather would be
 grain is finer and tighter

 tinny with insufficient softness
 less fullness
 prominence of neck folds.
Key points to be remembered during liming
 The liming pH determines the degree of swelling; it should be 12.5-13.0.

 Sodium cation gives more swelling than calcium.
 Lime swelling can be affected by the presence of salt (after soaking the wash water
Be should be at 0 or > o1)
 The temperature of liming bath should be 25-28oC.

Alkali Immunization or Immunization of Keratin:
Removal of hair from the skin is accomplished by the combination of reducing agents
(sodium sulphide) and lime by the reduction of disulphide linkage of cystine amino acid of
keratin. But the hydrolysis of cystine linkage or breakage of disulphide bond of cystine (cys-
S-S-cys) is greatly decreased by the application of excess alkali prior to the application of the
sulphide. If an excess alkali or lime comes in contact with the hair in the follicle prior to the
reaction of reducing agents, the action of the reducing agents is greatly limited. This
phenomenon has been known as immunization of keratin.
Liming Methods
Liming method depends upon the raw stock as well as the final leather required to be
produced. In case of goat or sheep skins where the wool of hair has some value, a paint
liming system is to be adopted. In the case of cattle hide, hair pulping method is used in
paddle/drum. Short liming is necessary to get tighter leather and less looseness in leather. For
soft leather where good opening up of structure is required, a slightly longer liming is
adopted to increase the swelling and splitting of fibres. Reliming with the addition of soda
ash/caustic soda is done to adjust the desired degree of plumping.
Paint Unhairing and Reliming Method for Goat and Sheep Skins
The soaked skins after weighing are painted with a paste consisting of 5-7% lime, 2-2.5%
sodium sulphide, 10% water and/or 0.2% wetting agent. The paint is applied on the flesh side
of the skin and they are kept in pile flesh to flesh covered well with wet gunny cloth for 3-5
hours or sometimes overnight depending upon when the soaked skins arrived in the lime
yard. They are then unhaired and relimed in a pit or paddle or drum.
In the case of drum, the unhaired skins are further processed using 2% lime and 1.5% sodium
sulphide in the presence of 100-150% water for 18 hours. The drum is run for 5-10 minutes
for every one hour. However the R.P.M of the paddle/drum has to be controlled to avoid too
much of beating action. Normally R.P.M. will be 2-3.
In the case of paddle the unhaired skins are processed using 10% lime and 1-1.5% sodium
sulphide for 2 days with occasional running of the paddle for 15’ every 2 hrs. In case of pit
reliming, they are handled 2-3 times every day for 2 days.
Drum Liming (Hair burning or pulping method)
Mostly hair burning method is followed for cow hides. In drum liming, the soaked skins are
put in the drum with suitable float. The required amount of lime and sodium sulphide is
added during the drumming of the skin. The drum is run intermittently and the duration is
determined by the type of raw stock and type of final leather. Here the hair is pulped out
(removed in the drum itself) and the material is sent for fleshing.
Lime Blast:
Lime blast means deposition of insoluble calcium compounds on the skin. Normally occurs
when the limed hides are carelessly exposed in the open air for too long or inadequately
covered by the liming liquor.
Ca(OH)2 + CO2 CaCO3 + H2O
Fleshing
This operation is done mainly to remove the adhering flesh in the hides and skins. This is
done by subjecting the limed pelts to the fleshing machine and mechanically removing the
unwanted flesh.
On removal of the flesh, the tanning auxiliaries will be able to penetrate the cross section of
the skins at ease in their subsequent tanning operations.
Enzymes in Dehairing
Enzymatic dehairing is an environmentally friendly alternative to the conventional chemical

process.
Mechanism
1) The enzymes digest the basal cells of the hair bulb and the cells of malphigian layer.
2) This is followed by loosening of hair with an attack on the outermost sheath.
3) Subsequent swelling and breakdown of the inner root sheath and parts of the hair that
are not keratinized.
Advantages
1) Complete elimination of sodium sulphide.

2) Recovery of hair in good quality and strength which is of value.
3) Creation of (good) conductive atmosphere for the workers.
4) Enzymatically dehaired leathers have better strength and greater surface area.
5) Elimination of bating process.
6) Time factor- lime sulfide process takes about 16 hrs, whereas enzymatic dehairing is
completed between 8 to 12h.
Methods of Application
There methods of application enzymes in dehairing process
1) Paint method
2) Dip method and
3) Spray method
Paint Method
Enzyme is mixed with an inert material or surfactant like kaolin and made into a paste. The
pH is adjusted and applied on the flesh side of hides and skins, piled flesh to flesh and
covered with trays or polythene sheets and kept for dehairing process. Lunacid (0.01%) is
added as a preservative. It prevents growth or deterioration of the hides and skins.
Dip method
The hides and skins are immersed in the enzyme solution at the required pH in a pit or tub.
The disadvantage of this method is the dilution of enzyme solution. Through, distribution of
enzymes is uniform, the dehairing at the backbone of neck is not up to the mark (or) will not
be that good. So spraying technique is carried out.
Spray method
The advantages of the spray method over paint and dip methods are
1) Concentrated solutions can be sprayed

2) When the enzyme is applied with force on the flesh side, entry (or) penetration
becomes easier.
3) Backbone and neck can be sprayed with more enzymes, by making the process
quicker.
4) No effluent arises from this method.

5) After dehairing, hair will be free from the adhering skin tissues.
Deliming
The process of removing the Lime present in the pelt is called Deliming. The lime may be
present as deposition as well as in the combined form with the collagen. The loosely held
lime gets washed off during the wash with water. However, the combined limed needs to be
treated with the salts of weak acids such as Sodium bi-sulphite, Ammonium sulphate or
chloride. Deliming is partial or complete according to the types of leather finally produced.
For example Sole Leather and belting leather needs partial deliming, while the softer version
requires total deliming. Inadequate deliming may give rise to an increase of basicity during
chrome tannage and cause wrinkled grain, hardness, loose grain or cracky grain.
Objectives:
Ñ Removal of Lime
Ñ Lowering the pH from 12.5 to 8.0, suitable for bating
Ñ Depleting the pelt, particularly reversing the swelling.
Method of Deliming:
After washing the pelt, deliming is done in the drum with 100% water at 30-35℃ and 1.0 -
3% addition of ammonium sulfate or ammonium chloride for 30-120 min. As deliming
proceeds, calcium is solubilized in ammonium sulfate or ammonium chloride. The lime is
gradually removed from the skin by diffusion. The natural buffering pH of ammonium sulfate
is about 5. In the presence of the calcium hydroxide and ammonium salts the solution pH is
buffered between 7 and 8. This is also the pH range of maximum enzymatic action during
bating.
Ammonium chloride is used for softer leathers and ammonium sulphate is used for firmer
leathers. The use of sodium bisulphite is to get white pelt at a later stage. Technologically
there is difference in the reaction of ammonium sulphate and chloride with calcium ions. In
the presence of sulphate, calcium ions forms sparingly soluble calcium sulphate which may
precipitates in between the fibre bundles and needs more washing after deliming. In the case
of ammonium chloride this danger does not exist, because chloride ion does not form an
insoluble salt with calcium.

Ca (OH)2 + (NH4)2 SO4 CaSO4 + NH3 +H2O
Ca (OH)2 + 2NH4 Cl CaCl2 + 2NH3 + 2H2O
Completion of Deliming
The completion of deliming is checked by cutting a small piece from the thickest portion of
the pelt and adding a few drops of phenolphthalein in the cut section. If the pink colour is not
seen in the cut section, it is considered that the goods are delimed completely. Partial
deliming is indicated by the red colour becoming less intensive.
Bating
The bating process is mostly performed in the deliming bath and is a enzymatic treatment
with alkaline proteases from plant, animal, bacteria or fungal source. It effects a further
opening up of the collagen fibres, depleting of the skin material, loosening of scud. After the
bating operation, the skins are much more softer and well opened up.
Objectives:
 Loosening and removal of scud, short hair and pigments.
 Partial or balanced break down of Elastin protein.
 Improving the elasticity and smoothness of the grain
 To prepare a clean and white pelt
Method of Bating:
Bating process is normally carried out in the deliming bath after the required pH is achieved.
1-3% bating enzyme is used and the drum is run for 45-90 minutes. Over-bating will lead to
the dissolution of hide substance and will lead to an empty leather with grain damage and loss
of strength. Under-bating will not give the desired smooth grain on the pelt, affecting the
smoothness, cleanliness and clarity of the grain pattern expected on the final leather. Scud
removal will not be proper.
Completion of Bating:

Thumb test for hides/ skins: The impression or pressure of the thumb should remain on the
grain surface for some time.
Air Permeability method for skins: Especially in the case of skins the permeability to air is
tested by pleating the skin like a bag and pressing the trapped air through the skin. The degree
of porosity is a measure of the attained bating intensity.
Bating of Wet blues
If wet blues are produced under poor beamhouse process, a significant amount of elastin can
be left in the grain. Proteases, which have a pronounced elastolytic effect, can remove or
degrade these fibres and thus improve the relaxation of the wet blue. This process have an
application pH ranges from 3-7, so depending on the final leather requirements they can be
applied during or before the neutralisation process for two hours or even overnight. An
improvement of area, a better cleanliness and more uniform dyeing can be achieved, those
proteases with a high elastase and collagenase ratio showing the most pronounced effect
regarding grain relaxation.
There is a risk of a looser grain break and reducing the grain strength, but these risks can be
minimized by controlling running time, pH and dosage and using appropriate retanning and
fatliquoring agents.
Pickling
The purpose of pickling is to acidify the pelts to a certain pH prior to chrome tanning. In this
process the delimed and bated pelts are treated with acids and salt solutions. Pickling is an
essential operation for chrome tanning.
Method of Pickling
First, the required quantity of water is taken in the drum (80-100%) and then specified
amount of common salt (8-10%) is added to the drum. The goods are run in the salt solution
for 10-15 minutes. The concentration of salt is checked using Baume meter adjusted to 6 - 7 o
Be. Then the calculated quantity of sulphuric acid (1%) is weighed correctly and diluted in
ten times of water and cooled for some time. The diluted acid (cooled) is added to the drum
in three or four instalments at an interval of 15 minutes. Finally, the drum is run for one hour
or till such time that the pH in the cross section of the pelt attains 2.8 to 3.0. Care should be

taken to see that acid swelling does not occur in the pelt. If salt is not correctly weighed and
used, there is a chance of acid swelling occurring in the pelt.
The completion of pickling is checked by testing the cross-section of the hide by means of
bromocresol green in order to determine the depth of penetration of the pickling.
Role of Salt in Pickling

The role of salts in pickling is to suppress the acid swelling through ionic strength effects.
The effect of salt in pickling process is dependent entirely on the total amount of water
present (pickle float). The amount of acid necessary depends partially upon the amount of
residual alkali in the skin which must be neutralised.
The salt added at the start of pickling do not combine to any real extent with the hide fiber
and therefore the ability of salt to avoid swelling in strong acid solutions is in direct relation
to its concentration and to its dissociation in ions. A 4% concentration of sodium chloride
serves to inhibit the swelling completely, but generally 6% is used in industrial practice at a
preventive measure.
The ability of a salt to prevent swelling at a given concentration also depends on the kind of
acid used. This is because the degree of swelling produced by weak organic acids depends on
their dissociation constant. For this reason, if using weak acids, it is often possible use lower
salt concentrations than require by strong acids. Anyhow, the inclusion of sodium chloride in
solution, the sodium and chloride ions being ionised, causes the chloride ion to pass from the
process bath into the collagen structure by osmotic effect.
Depickling
The main objective of depickling is to increase the pH or decrease the acidity of the pickled
stock. Occasionally, the tanner buying pickled pelts normally at pH around 2.0 will want to
adjust the pH to a higher value for vegetable tanning or chrome tanning. To do this the skins
should be covered with brine water containing the proper amount of salt. Then the pH can be
raised either by using 2-4% Sodium thiosulphate or mild alkalis.
Degreasing

Though part of the fat and natural grease is removed during the liming process by
saponification, degreasing operation is necessary for skins like wool sheep skins which
contain large amount of fats. Degreasing is an essential step in the production of glove and
clothing leather. The process may be carried out either after deliming or after pickling
normally with solvents in the presence of non-ionic emulsifier or by using enzymes.
The presence of natural grease in raw hides and skins, especially woolly sheep skins, results
in various defects, viz. fatty spues, uneven dyeing and finishing. During the degreasing
operation, the fat or grease is removed from the interfibrillary spaces of the skins to facilitate
the even penetration of tanning materials, fat liquors, and dyes, etc. Degreasing helps to
obtain soft and pliable leather for garment manufacture.
The degreasing is usually carried out without float and washing with water in the case of
delimed pelt and with saline water with pickled pelt is done to remove solubilised fat.
Enzymatic degreasing is suggested as a viable alternative to combat the pollution problems
caused by the use of solvents and detergents. Lipases which are projected as alternatives for
solvents and detergents, catalyze the breakdown of fats and can be obtained from animal,
microbial and plant sources.

TANNING
What is Tanning?
Raw hide/skin Leather
Tanning
{Putrescible} {Non-Putrescible}
Definition of Tanning
Tanning is the conversion of putrescible organic material (animal skin) into a stable material
(leather) that resists putrefaction by spoilage of bacteria.
Objectives of Tanning
 The main objective is converting the putrescible protein into non-putrescible.

 To increase the hydrothermal stability of collagen.
 To stabilize the skin collagen against proteases.
 To form the new cross links.
 In order to achieve the additional dimensional and matrix stability.
 To add the mechanical stability of the matrix.
Vegetable Tannins Cr85%
Tannins are common in fruits (e.g. grapes), in tea, in chocolate, in legume trees (Acacia spp.,
Sesbania spp. ...), in grasses (sorghum, corn) etc. They are responsible for the astringent taste
we experience when we consume wine or unripe fruits, and for the enchanting colors seen in
flowers and in autumn leaves. Vegetable tanning materials occur in nearly all forms of plant

life. They are used commercially where the amount of tan is high and large quantities can be
extracted economically.
Definition of Vegetable Tannins
Defined as plant polyphenolics in the molecular weight range of 500 – 3000 Daltons. Tannins
are naturally occurring plant polyphenols. One of the most satisfactory definition of tannins
was given by Horvath in 1981.
"Any phenolic compound of sufficiently high molecular weight containing sufficient

hydroxyls and other suitable groups (i.e. carboxyls) to form effectively strong complexes
with protein and other macromolecules.
Classification of Vegetable Tannins
Tannins are classified into two main types.

i. Hydrolysable Tannins or Pyrogallol Tannins
ii. Condensed Tannins or Catechol Tannins
Hydrolysable tannins are further classified into Gallo tannins and Ellagi tannins.
Hydrolysable Tannins
Hydrolysable tannins undergo hydrolysis rapidly at raised temperatures, particularly above
60oC to form sludge or bloom and at lower temperatures by microbial or enzyme attack if
present. Hydrolysable tannins are further divided into two namely: Gallo tannins and Ellagi
tannins.
Gallo tannins are those which yield gallic acid and glucose on hydrolysis. Examples are
Sumac, Tara, Dhawa.
Ellagi tannins, on the other hand, produce ellagic acid in addition to gallic acid and glucose
on hydrolysis. Examples are myrobalan, divi-divi, oak, chesnut.
Condensed Tannins
Condensed tannins which are not prone to hydrolysis but are liable to oxidation and
polymerization to form insoluble products called tannin reds or phlobaphenes. Condensed
tannins contain proanthocyanidins composed of flavanoids.

(Hydrolysable Tannins)
Flavone (Condensed Tannin)

Difference between Hydrolysable and Condensed Tannins
Hydrolysable Condensed
Tannins undergo hydrolysis reaction Not hydrolysable
Produce sludge/bloom tannin reds Yields phlobaphenes
or
Less astringent Highly astringent
Well buffered Poorly buffered
Small molecules Large molecules
Loss of tannin on storage more Loss of tannin on storage is less
Leather is lighter in color Leather tends to dark red on
exposure
to light
When react with iron salts it forms When react with iron salts it
Bluish salts form Greenish black compound
Table: Parts of plants used as sources of tannins.
Bark Wood Fruit Leaves Root

Wattle Quebracho Myrobalans Sumac Canaigre
Oak Oak Valonia Dhawa Badan
Chesnut Chesnut Divi-divi Gambier Taran
Mangrove Burma cutch Algarobilla Mangue Potentilla
Eucalypts Eucalypts Tara Palmetto
Spruce Urunday Teri
Hemlock Tizera Sant
Babul Pomegranate
Konnam
Avaram
Arjun
Principles involved in Vegetable Tanning

The factors which affect the vegetable tanning process are
 Concentration of Tan liquor
 Acidity or pH
 Temperature
 Particle size
 Neutral salt content
 Concentration of Tan liquor
The diffusion of the tannin is carried out through the grain surface and the flesh side, and it
ends at the corium. The diffusion speed depends greatly in the difference between internal
(water retained in between the fibres) and external liquid concentration. Use of astringent
tans, which refers to concentrated solution at the initial stages of tanning prevents the
diffusion of tannins.
 Acidity or pH
In order to aid penetration of tannins, the iso electric point of collagen should be at 4-5 at the
initial stages of tanning. Tanning generally finishes at pH 3.3-3.5 for better fixation. Tanning
also not carried out at low pH results in a slow rate of tannin penetration and also results in
case-hardening where the outer layers are over tanned where the center layer remains raw.
 Temperature
As the tan liquor temperature fall below 21 oC, the rate of tanning rapidly decreases, and flat
leather usually results. When the temperature raises above 28 0C, the rate of tanning usually
increases, but undesirable leather qualities may result.
 Particle Size 500 -3000 daltons MW 30000
Salt precipitates tannins. The larger particles are precipitated by the lower salt concentrations
and that the smaller the particle, the higher the salt concentration required for salting out.
 Neutral salt content

The higher the salt concentration reduces the affinity of tannins with collagen. In lower
neutral salt concentration, hide swelling takes place and the peptide links of collagen are
more accessible to tannins but results in surface tanning without penetration.
Method of Vegetable Tanning –Pit Method

Vegetable tanning in pits, which is carried out practically only in a counter current way at the
present time, is a base of all conventional methods. In this manner, pelt comes in the most
diluted, exhausted solution of tanning matters at first. More concentrated solutions act on
pretanned pelt gradually. The density of the tanning solutions acting on pelt increases from
1°Bé to 5°Bé. Tanning time in pits usually varies from 2 weeks to 5 weeks. In this way
tanned pelt is then finished in drums in a bath with a density of 60-70°Bé. The total amount

of vegetable tanning agents used is usually 33-40% of tanning matters per pelt weight for sole
leather, 28-30% for technical leathers and 15-20% when tanning goatskins and sheepskins.
Principles to be borne in mind with counter current pit tanning
 The liquor to goods ratio should be kept as low as possible.

 The number of stages should be as high as possible.
 To maintain as high a tannin concentration at the hide surface as possible.
 It is beneficial to maintain the temperature of the system to around 20-25oC.
 Tannin extract should only be added to the strongest pit and the liquor may be
pumped from one pit to the next down the system.
Vegetable Tanning – Drum Method
Modern and rapid vegetable tanning methods generally involve the use of tanning drums that
reduce the time of tanning drastically. Process in drums requires the use of pretanning
syntans makes the penetration of vegetable tannins. Pretanning and tanning is carried out in
very short floats so that relatively high exhaustion tanning matters occurs and only very small
bath volumes are discharged. Once penetration is complete, water is simply added to the
drum which dilutes the salt solution and the tannin fixation takes places. A typical drum
tanning method is given in the following table.

% Chemical Name Time in Minute Remark
Raw material : Delimed Pelt

50 Water
8 Common Salt 7 Be 6-7
0.7 Formic acid (1:10 water) 3X10 + 30min pH4.5 -
5.0
5 Pretanning Syntan low mw 30
10 Wattle Powder condense 60
10 Wattle Powder condense 60
50 Water 30
5 Myrobalan Powder (hrodylsae 60
1.0 Formic acid (1:10 water) 90 pH 3.5
Processing of Leathers after Vegetable tanning to the Crust condition

Many vegetable tanned leathers are bought and sold in the crust condition. To prepare these
leathers the tanned goods either by pit or drum method are processed as follows.
Washing and Oiling

The tanned leathers are washed typically for 10-15 minutes in a drum at 30 oC. This should
only be sufficient to remove surplus tannin without causing any loss in yield. As part of the
preparation for drying, and to improve the crust leather, further offers are made which
include:
 Fatliquors, often sulfated fish oil (2-4%) to lubricate the fibre structure and to reduce
the evaporation rate in drying.
 Auxiliary type bleaching syntans (1-2%) to lighten and level the colour
 Fillers such as china clay (2-4%) to counteract any loss in weight, lighten the color
and enhance grain smoothness.
 Anti-mould (0.1-0.2%) to minimize the possibility of mould growth in drying.
Finally the leathers are horsed or piled and subjected to samm/sett, then offered for drying.
Mechanism of Reaction of Vegetable Tannins with Collagen

The main reaction between vegetable tannins and collagen is hydrogen bond formation
between the hydroxyl groups on the polyphenols and oxygen or nitrogen atoms on the
proteins. However acid/base reactions also occur to a lesser extent and more recently it has
been suggested that a hydrophobic interaction may also occur.

Chrome Tanning
Chrome tanning occupies an outstanding position in the tanning industry since its
introduction in 1884 by Knapp. Today around 85-90% of the tanning processes use
chromium tanning salts due to the versatility of the tanning system to produce different types
of leather with required properties for different end uses. The ability of Cr(III) to form poly-
nuclear complexes of intermediate size and stability confers such a unique tanning potential,
which results in leather with high degree of stability and shrinkage temperature(T s). Cationic
nature of the tanned leather imparts pronounced capacity for rich dyeing and affinity for
fatliquors to produce leather with excellent softness.
Polynuclear Complex of Chromium
What is Basic Chromium Sulphate (BCS) or Chrome Tanning Powder?
Chrome powder or BCS is green, readily soluble in cold water and consists of chromium
sulphate together with salts remarkably sodium sulphate. Tanning powder with 25% Cr 2O3
content are available with a range of basicities (25-50%), however chrome powder with 33%
basicity is most commonly used.

Basicity is a way of describing the reactivity towards collagen. A figure of 0% indicates zero
tanning power.
Cr2 (SO4)3 1% non-tanning
Cr2 (OH2) (SO4)3 33% tanning
Cr2 (OH4) (SO4) 66% too astringent
Cr2 (OH6) 100% insoluble and non-tanning
Chromium sulphate in solution has a strong attraction for hydroxyl ions (OH -) which
associate with the chromium molecule by replacing one or more sulphate ions (SO 4)2-. As the
pH increases during tanning more (OH-) is made available and it enters into the chromium
sulphate molecule and the molecule’s reactivity towards collagen increases. However when
the pH raises beyond 4.3 all the sulphate radicles are removed and chromium hydroxide is
formed. Chromium hydroxide is insoluble and no tanning power.
Low basicity chrome liquors have good penetration properties, but poor fixation. Higher
basicity liquors have high fixation but poor penetrating power. To achieve both penetration
and high fixation the basicity is raised during tanning in a process called basification – it
involves the addition of alkali.
Tanning procedure
Pickled skins (pH 2.8-3.0) are processed using 8% commercial BCS along with 50% pickle
water (brine solution of Be 6-7) for 90 min. Then 50% water is added and the drum is run for
30 min. To the running drum 1% sodium formate (mixed with 10% water) is added. After 30
min 1% sodium bicarbonate (mixed with 10% water) is added in 3 feeds at 10 min interval
and finally run for 60 min to bring the pH 3.8. A typical chrome tanning recipe is given
below.
Process Material % Duration pH

Pickling from Water 80
Delimed pelt
Salt 8 10 min
Formic acid 0.3 15 min

Sulphuric acid 1.0
4 feeds at 10 min interval. Finally run for 2 h. Check pH; leave overnight. Next 2.8-3.0
day, run for 30 min. Drain half the bath
Chrome tanning Pickle float 50
BCS 8 2h
Cationic fatliquor 0.5
Check penetration. Flood with 50% water
Basification Sodium formate 0.5 15 min

Sodium bicarbonate 1.25
4 feeds at 10 min interval. Finally run for 120 min. Check pH. Drain, wash and
pile for 2 days.
Boil Test
This is a test of the chrome tanned leather for resistance to boiling. The procedure is to cut a
thicker piece of the leather and note the area, by drawing around it on paper. The test piece is
then put into boiling water for 2 minute. The piece is recovered, quickly cooled in cold water
and the area is compared with the staring shape. The criterion is pass or fail. If there is no
visible change, the leather has passed but if any shrinkage can be seen, the leather has failed.
Mechanism of Chrome Tannage
The reaction sites of the chromium with collagen are the carboxyl groups of the collagen. The
cross-linking reaction between skin substance and the chrome tanning agent is shown as
schematic in the following figure. The cross linking is effected through coordinate covalent
bonds (complex bonds) with the COOH groups of the collagen.

Combination Tannages
The term combination refers to the use of more than one tanning agent. The properties of a
piece of leather produced by a particular tanning method are not always fully desirable to a
user. To improve the desirable properties and to eliminate completely the undesirable
properties, combination tannages must be used. In combination tanning systems, the skin is
first tanned with the method that provides the largest number of desirable properties for a
particular use. Then to compensate the unwanted properties and to provide other desirable
properties a second method of tanning is applied.
Chrome Retanned Leathers
Chrome retanned leathers are those first tanned with chrome salts and then retanned with
vegetable tannins. Emptiness, looseness, hardening due to re-wetting and drying are thus the
main undesirable properties of a pure chrome leather and they are reduced to a greater extent
by retanning with vegetable extracts. To achieve good embossing properties, retanning the
chrome leather with vegetable extracts is essential.
Semi Chrome Leathers
Semi chrome leathers are those first tanned with Vegetable tannins and later with chromium
into order to produce leathers with entirely different properties based on vegetable tanned
leathers.

Main Difference between Chrome and Vegetable tanned Leathers
S.No Chrome tanned leather Vegetable tanned leather

1 The leather is empty The leather is full
2 Slightly elastic Less elastic than chrome tanned
3 Less affected by acid atmosphere Affected by acid atmosphere
4 Difficult to wet back No difficult to wet back
5 Shrinks and becomes hard on re- Does not shrink or become hard like
wetting and drying chrome tanned leather on re-wetting and
drying
6 Absorbs fat slowly Absorbs fat quicker than chrome tanned
leathers
7 Stands the boil test Does not stands the boil test
8 Good embossing is difficult Embossing impressions are excellent and
permanent
9 Good tear resistance Less tear resistance than chrome tanned

POST TANNING PROCESSES
Introduction
The term “post tanning” refers to the wet processing steps that follow the primary tanning
process such as chrome, vegetable or other mineral tanning. The combination of post tanning
processes may not always be the same for all tannages. The choice of post tanning processes
depends on the primary tannage and the type of targeted article or final leather that the tanner
wants to produce. Some quality enhancements are carried out through post tanning
process/operations. Also, the kind of final leather is decided at this stage.
Objectives of Post Tanning

The main objectives of post tanning are mentioned below.
 To produce various types of crust/finished/final leather from wetblue.
 To modify the properties of wetblue with characteristic chemicals.
 To achieve properties such as fullness, grain tightness, softness, fat distribution,

desired shade through dyeing, fastness, grain tightness, elasticity, buffability,
smoothness etc as desired by the customer.
 To prepare good crust leather which is an input material for making full finished
leather article through mechanical operations viz. and setting, vacuuming, drying,
buffing, dry-drumming, embossing etc.
The general process sequence for post tanning activity is given below.

Process Sequence for Post Tanning
WETBLUE (SAMMED &

SHAVED)
WASHING
ACID WASH
RECHROMING
NEUTRALISATION
RETANNING
DYEING
FATLIQUORING
FIXING
PILING

Neutralization
Objectives
 To remove the acid liberated after chrome tanning and ageing.
 To increase the pH thereby the affinity is altered to facilitate better penetration of
syntans, dyes and fatliquors.
 To remove neutral salts and unfixed/soluble/free chromium present in the leather.
Neutralization or Deacidification
Chrome tanned and semi chrome leathers are piled up after basification. Even in overnight
piling, the pH drops, indicating the liberation of acid. The source of this acid may be i)
ionization of neutral carboxyl’s ii) ionization of positively charged amino (-NH 3+) groups and
iii) hydrolysis of chrome itself. But, what is more important is that this acid impairs fiber
strength and requires to be removed. When water with temporary hardness is available,
continuous washing definitely neutralizes the acid. Otherwise (i.e. when the water does not
have such temporary hardness), it is a tedious method to be given up in preference to
accelerated deacidification, using chemicals. Such deacidification with chemicals goes by the
name “Neutralization” in leather industry.
A Conditioning Process
The need for neutralization arises from another count also. The tanned goods have to be
invariably fatliquored, as lubrication is next only to tanning in leather manufacture. Majority
of leathers are to be dyed also. Both dyes and fatlliqours are mostly anionic. If these
negatively charged materials have to penetrate into collagenous fabric, then the collagen
should also bear a net negative charge, as a preponderance (majority) of positive charge on it
will attract the anionic materials and cause their fixation on the surface itself. Collagen
becomes anionic when H+ of the carboxyl and also of the positively charged amino (i.e. –
NH3+) groups are removed by treatment with an alkali. Addition of OH (i.e. alkali) entails pH
rise. The pH at which sufficient number of ionized carboxyl’s are present in the collagenous
lattice to disperse the anionic materials effectively is the point to which neutralization is to be
carried out. This pH is usually around 5, the actual pH being dependent upon the end product.
Neutralization, thus, is also a conditioning process comparable to pickling carried out
preparatory to mineral tanning.

Neutralization, as shown above, being a conditioning process necessary for dyeing and
fatliquoring, should be carried out, neither more nor less. That is, over-neutralization as well
as under neutralization are equally undesirable. The acid left in the leather in under-
neutralization interferes as pointed out above in retanning, dyeing, fatliquouring and storage.
The unevenness caused by the acid on the (molecular) size, charge and fixation of chrome is
responsible for this and the dye fixation is uneven, there is an excessive surface fixation and
no penetration. In respect of fatliquors also, uneven distribution, surface deposition takes
place.
Neutralization Agents, Characteristics and Requirements

The most important neutralizing agents are sodium formate, sodium bicarbonate, ammonium
bicarbonate, sodium carbonate, borax etc. Around 1-3% neutralizing agents based on the
shaved weight of wet blue is usually employed in the presence of 200% water. Washing
before and after neutralization is very important in order to remove the salts and free
chromium. The pH’s of 10% solution of different neutralization agents are given in the Table
2.
Table 2: Properties of Neutralizing Agents
S. No Alkali pH of pH of leather Remark

10%
solution
Surface Middl
e
1 Caustic soda 13.3 - - Danger of excessive neutralization
because of superficial action.
2 Soda ash 10.8 to 6.4 5.2 -do-
11.2
3 Bicarbonate 7.8 to 8.1 5.8 5.8 Good penetration. Excessive
neutralization only when large
amounts are used. Do not dissolve
above 350C, as above this, soda is
formed.
4 Ammonium 7.5 to 7.8 6.2 6.2 High penetration. Excessive
Bicarbonate neutralization cannot be excluded.
More expressive.
5 Borax 9.0 to 9.2 6.0 5.0 Only slow surface neutralization
and therefore fatliquor is close to
the surface. Good for skin garment
leather. On prolonged treatment,
the effect is equal to that of soda.
6 Sodium sulphite 7.8 to 8.0 - - Mild and uniform action. The SO 2
produced can bleach and make
white leather.
7 Hypo(Na2S2O3) 6.5 to 7.0 - - Poor agent. Requires to be used in
large amounts. Light colour due to
deposition of colloidal sulphur.
Smooth grain, light break and firm
leathers.
8 Sodium acetate 8.0 to 8.2 5.4 5.4 Highly penetrative. Excessive
neutralization possible.
9 Sodium formate 8.5 to 8.7 4.6 4.2 Rapid penetration. Mild action
even in large amounts.
Completion of Neutralization
The final neutralization pH for different types of leathers are given below
for upper leathers 4.8-5.0
for softy upper leather 5.0-5.2
for nappa leather 5.5
for glove leather 6.0
The following indicators can be used to check the completion of neutralization for ranges
below and above the mentioned values:
Bromocresol green pH 3.4 – 5.4 (yellow-blue)
Bromophenol blue pH 3.0 - 4.6 (yellow-blue)
Bromocresol purple pH 5.2 - 6.8 (yellow-purple-red)
Bromothymol blue pH 6.0 - 7.6 (yellow-blue)
Transition interval of bromocresol green indicator:

Yellow - pH 3.4 and below
Yellow- green - pH 4.0
Green - pH 4.5
Blue-green - pH 5.0
Blue - pH 5.4 and above

In order to check the completion of neutralization, a small piece of leather is cut from the butt
portion and few drops of bromocresol green indicator is added onto the cross-section. The
change of colour indicates the progressive depth of penetration of the neutralizing agent and
the pH value on the leather.
Common Problems in Neutralization

The most common problems occurs due to improper neutralization is illustrated in Figure 10.
Chrome Spots
 Caused by Precipitation of uncombined
chrome.
 Inadequate washing of the stock prior to

neutralization.
 Adding the neutralizing agent too rapidly.
 Sodium bicarbonate must be dissolved

completely in water in a ratio of 1:10 and
then given in feeds.
 Care must be taken that the temperature of

water must be below 380C
Pipiness in Cow Leather
 Caused due to surface

neutralization of strong alkali.
 Higher temperature of the float

used (>380C).
 Prolonged drumming time

Figure 10: Common Problems in Neutralization
Dyeing
Objectives
₋ The main objective of dyeing is to impart the colour as desired by the customer or
marketing and sales forecast.
₋ To plan the base colour before finishing for grain based finished articles.
₋ To get uniform shade in case suede and nubuck articles.
₋ To bring aesthetic look for final/finished leather.
Colour
Colour is a property of light. Colour can be broadly defined as the effect on the brain of an
observer when an object is viewed in the presence of a light source. A material looks
coloured to the human eye when it absorbs light in the visible wavelength range of 400-
700nm. Issac Newton first passed a beam of white light through a prism and saw it divide
into several colours, creating a spectrum of colours. The colours of the light wave spectrum
are red, orange, yellow, green, blue and violet (see Figure 11). In physics, mixing the colours
of the light wave together produces pure white light.

Figure 11: Electromagnetic Spectrum: Visible Light
How do we perceive colour?
 When white light falls on the substrate, a part of the light is absorbed and the
remaining part reflected. The light reflected and absorbed are said to be complimentary
to each other ( see Table 3).
 For e.g., a red coloured substance absorbs at around 490-500 nm (absorbed spectral
colour is blue-green) and the reflected spectral colour is red what we perceive. Hence,
blue-green and red are called complimentary colours.
 If all the light rays are absorbed, then we perceive black and when all part of the
light is reflected, then we see white.
Table 3: Complimentary Colours
Range of Absorbed spectral Reflected

wavelengths colour complimentary colour
in nm

400-435 Violet Yellow-green
435-480 Blue Yellow
480-490 Green-blue Orange
490-500 Blue-green Red
500-560 Green Purple
560-580 Yellow-green Violet
580-595 Yellow Blue
595-605 Orange Green-blue
605-700 Red Blue-green
Three Properties of Colour

 Hue is the basic name of a colour or the pure form of colour – there are six basic
hues: red, yellow, blue, green, orange, and violet.
 Intensity or saturation refers to the relative brightness or dullness of the colour – a

colour is at full intensity only when pure and unmixed.
 Value is the lightness or darkness of a hue.
Primary, Secondary, and Intermediate Colours

Primary Colours
Red, yellow, and blue are the primary colours. All other colours are derived from these three
hues.
Primary Colours Secondary Colours
Secondary Colours
Green, orange, and violet are the secondary colours. These are the three colours formed by
mixing two primary colours together.
Green is the middle mix of blue and yellow.
Orange is the middle mix of red and yellow.
Violet is the middle mix of blue and red.
Tertiary Colours
Tertiary Colours
These are the six colours formed by mixing a primary colour with a secondary colour.
Yellow-orange, red-orange, red-violet, blue-violet, blue-green, and yellow-green are the
tertiary colours. They are the midpoints between the primary and secondary hues.
Complementary colours
Complementary colours are hues that are opposite to one another. The basic complementary
pairs are
– Red and green
– Yellow and violet
– Blue and orange
Chromogens, Chromophores and Auxo-Chromes

The colour of a substance depends upon (i) nature of light and (ii) what happens when it
strikes the surface of the substance. A substance is coloured because of its ability to absorb or
subtract some components of white light. So the question, now, is what makes a substance
absorb light so that it appears coloured?
According to Otto Witt (1876), substances containing labile (i.e loose) electrons are capable
of light absorption. Such electrons in an inorganic substance are the ‘d’ electrons of
transitional metals like chromium and manganese. Almost all pigments are transitional metal
compounds. In the case of organic compounds, on the other hand, π-electron systems are
loose and can absorb light. These are multiple (i.e double or triple) bond systems. Such
multiple bond systems which can absorb light are known as “Chromphores” (Chromo
=colour; Phore= bearing). And chromphore containing compounds are known as
“Chromogens”.

Some chromophores are
Nitro Nitroso Azo Thio p-quinonoid
O–N=O –N=O –N=N– >C=S
In benzene, there are three (conjucated) double bonds and it absorbs light in the UV region
and hence colourless. However, when a nitro group is introduced, the resulting nitro-benzene
becomes pale yellow and the colour deepens with progressive nitration.
Colourless Pale Yellow Strong Yellow Deep Yellow
Similarly, azobenzene is coloured, even though benzene itself is colourless. Here, azobenzene
is the chromogen and the azo group –N=N- is the chromophore.
Benzene Azobenzene
Certain groups do not produce colours, themselves and yet intensify the colour of
chromogens. These auxiliary (i.e assisting) groups, which intensify colour, are known as
auxo-chromes. (auxo = to increase).
Pale Yellow chromogen Nitrophenol (deep yellow)

The absorption band of the chromogen may be shifted by the auxo-chromes either towards
the Red end or towards the Blue end of the spectrum. The ‘Red shift’ is known as
‘Bathochromic effect’ and the ‘Blue shift’ as ‘Hypsochromic effect’. Thus, auxo-chromes
shift the absorption band in the visible region and help colour formation. Majority of auxo-
chromes have got the bathochromic effect. Auxochromes are either acidic or basic:
Acidic: -OH, -SO3H, -COOH
Basic: -NH2, -NHR, -NR2
So they help in solubilisation and fixation of the dye onto the substrate. Auxo-chromes can
form H-bonds also with the substrate and this too helps in fixation. In fact, it is auxochrome
that coverts a chromogen into a dye.
Classification of Dyes
Dyes are classified in different ways
(i) According to the method of application
(ii) According to chemical constitution
(iii) According to source
(iv) According to end uses
(i) According to the method of Application

Based on their application in leather industry, the dyes are classified as follows.
 Acid dyes
 Direct dyes
 Basic dyes
 Pre-metalized or Metal complex dyes
 Reactive dyes
 Sulfur Dyes
Acid Dyes
Acid dyes are all sodium salts of dye-sulphonic acids and may be represented as d-SO 3- Na+ in
which‘d’ is the dye part. The dyes in which the dye part is in the anion are known as Anionic
dyes. Besides acid dyes, there are other dyes like direct, metal complex which are also
anionic.

The affinity and penetration characteristics of acid dyes for different kinds of leathers are as
follows
Affinity
Chrome leather > Chrome retan leather > Semichrome > Veg leather
Penetration
Properties of acid dyes

• Relatively small, typically hydrophilic molecules.
• Used for penetrating dyeing, producing level shades.
• Anionically charged, therefore high affinity for cationic leather.
• Fixed by acidification, due to the presence of sulfonate groups.
• They react predominantly through electrostatic reaction between their

sulfonate groups and the protonated amino groups of lysine.
• Secondary reaction is via hydrogen bonding through auxochrome groups.
• Some dyes may react with the bound chrome.
• Good fastness properties.
• Wide range of colours, offering bright deep shades.
Direct Dyes
Direct dyes are also anionic like acid dyes. The chief difference between the two lies in the
bigger molecular size of the former (Direct dye). The affinity of direct dyes for different
classes of leathers follows the same pattern as that of acid dyes. Only the affinity is a little
reduced. In fact, vegetable leathers have no affinity at all for direct dyes, though they have
some affinity for acid dyes. The bigger molecular size of direct dyes makes their penetration
poor and the dye is stopped on the surface itself.

Properties of direct dyes
• They are larger molecules than typical acid or basic dyes.
• Used for surface dyeing, with consequent likelihood of uneven colouring.
• Acid is not needed for fixation, because they are more reactive, due to the higher
number of reactive sites on the molecule and the hydrophobicity of the overall
structure.
• Fastness properties average to good.
• Usually dark colours.
• Have the same sort of structures as acid and basic dyes, although typically with
lower charge, resulting in lesser importance of electrostatic bonding.
• High molecular weight means more direct reaction, not requiring fixation by pH
adjustment.
• Relies more on hydrogen bonding from larger number of auxochromes per molecule,
similar to the relative astringencies of vegetable tanning agents, and more emphasis
on hydrophobic bonding.
• Direct dyes give mostly surface depth without much penetration due to their
bulkiness.

Basic Dyes
Basic dyes are all cationic dyes. The structures of basic dyes are essentially the same as
the acid dyes, except they carry a net positive charge from the cationically charged
amino substituents, even though they may also have anionic sites. Being cationic, their
affinity for chrome leather is negligible. But these dyes have good affinity for vegetable
tanned leather. Basic dyes are not readily soluble in pure water and hence are prepared as an
acidic solution. For this, the dye is made into a paste with an equal weight of 40% acetic acid
solution and then boiling water is poured to this paste, stirred well and filtered. The greatest
feature of basic dyes is their brilliance. The light-fastness and fastness to washing of basic
dyes are poor.
Diazo basic dye: Manchester Brown or Bismarck Brown.
Properties of basic dyes

• They produce strong, brilliant colours (red, orange, yellow, green, blue, indigo,
violet and black);
• They tend to be relatively hydrophobic, because they contain fewer solubilizing

groups than the acid dyes; consequently, they are often soluble in oils and non-
aqueous solvents.
• They tend to bronze, i.e. produce a metallic sheen. This is due to surface reaction,
when the dye molecules lie on top of one another, attracted by van der Waal’s
dispersion forces, allowing light to be reflected from the layered structure.
• Poor light fastness.
• High affinity for anionic leather, e.g. vegetable tanned, anionic retanned, acid dyed
leathers. The latter property is exploited in ‘sandwich dyeing’: acid dye, then basic
dye, possibly topped with more acid dye. The electrostatic attraction between the
charged species creates deep shades, with good rub fastness.
• Precipitated by hard water and anionic reagents;
• Applied by mixing with acetic acid, then diluting with hot water;
• They react electrostatically through their protonated amino groups and ionized
carboxyl groups on collagen;

Metal Complex Dyes
In order to improve the properties such as fastness to light, alkali, washing and bleeding a
metal atom is introduced into the dye structure. These dyes are known as pre-metallized or
metal complex dyes. There are two types of metal complex dyes: 1:1 and 2:1 metal complex
dyes. The wash fastness of 1:1 metal complex dye is less than that of 2:1 dye. Though the 1:1
class of metal complex dyes can be either amphoteric or anionic, the 2:1 classes are always
anionic.
1:1 Chromium premetallised dye, Acid Blue158 (CI 14880)

Properties of Metal complex dyes
Ñ They have lower anionic charge than the corresponding anionic uncomplexed dye.
Ñ Penetration and levelness of colouring are good;
Ñ They include pale, dull and pastel shades.
Ñ Fastness properties are good to very good;
Ñ They tend to be expensive, so are used for premium leathers, e.g. gloving, clothing,
suede, nubuck, aniline.
Ñ They may be formed from either mordant dyes or conventional acid dyes precomplexed
to a mordant metal ion, in the ratio of one dye molecule to one or two atom of metal.
Ñ Primary fixation mechanism is through reaction between the metal ion and
collagen carboxyl groups, which can vary in covalent character.
Ñ Secondary reactions may be electrostatic and hydrogen bonding, depending on

whether the dye is derived from mordant or acid dye precursor.

Reactive Dyes
Reactive dyes have a great potential to provide high fastness to wash including dry cleaning
and to give brighter shades. Generally dichlorotriazinyl, sulphatoethylsulphonyl and
trichloropyramidyl group of dyes are mostly used for leather. The leather may be dyed with
reactive dyes at pH 7.0 - 8.5 and at 30-50oC.
Properties of reactive dyes

• Reactive dyes are typically acid dyes that have been covalently bound to a reactive
group, capable of reacting covalently with collagen or leather.
• The principle behind this technology is that a covalently bound dye will be fast to
chemical removal.
• Useful in applications when the leather may be subjected to washing, dry cleaning or
perspiration damage, e.g. clothing and especially gloving leathers.
• Very good fastness to washing, dry cleaning, perspiration.
• Good light fastness.
• Limited range of colours: pale and medium shades.
• Expensive.
• Health hazard, due to their reactivity towards organic substrates.
Sulfur Dyes
Sulfur dyes are made by heating together aromatic compounds containing amino and hydroxy
groups with a source of sulphur.
Properties of sulfur dyes

• They are suitable only for leathers that can resist the high pH necessary for dye
reaction, e.g. aldehyde or oil tanned. Chromium(III) and vegetable tanned
leathers are severely damaged at pH 12–13: in each case the tanning is reversed.
• Good perspiration and wash fastness; insoluble in dry cleaning solvents.
• Generally dull shades, with a limited range of colours – a true red shade is not
available.
• They have little or no affinity for wool.
(ii) According to Chemical Constitution

Chemical classification based on the chemical structure of the colour forming chromophoric
groups of the dyes also is an important one from the manufacturing point of view. About 8
classes of chromophoric groups as shown below have been recognized. These have been
broadly classified into the 2 groups- Primary, Secondary.
Primary: Primary chromospheres are those which can give colour simply, single and include
the following:
 Nitroso ( –NO or = NOH)

 Nitro (–NO2 )
 Diazo (–N= N–)
 CNgp (either = C= N– or C = NH)
 CS gp (either >C= S or = C–SS–C )
Secondary: On the other hand, secondary chromospheres do not cause colour singly and yet
give colour on cumulation. And include the following once:
C=C and p-quinonoid and C=O
Thus, while ethylene and compounds of the type – (–CH= CH–) n – where ‘n’ is < 12 are
colourless, β–carotene, containing 11 double bonds, is orange coloured. Similarly, acetone
containing only one C=O is colourless and yet biacetyl, containing two C=O groups, is
orange.
(iii) According to the Source
According to source based classification, dyes are either natural or synthetic. All the early
dyes were natural ones from either vegetable or animal sources. Coloured substances from
fruits, flowers, leaves, roots, seeds, barks, wood and also galls of plants were extracted and
used. For making red leathers, the red dye extracted from shell- lac was extensively used in
the past.
Plant dyes were more popular in ancient times throughout the world, particularly in Europe.
One common feature of these plant dyes is that all these are mostly coloured vegetable
tanning materials. They were originally used in the form of barks, logs of wood, paste or
extract. But, nowadays, they are available as crystals and in powder form also. Haematine,
for example, is a dye extracted from logwood, once used as such for dyeing. Haematine is
even now in use for intense black.

Synthetic Dyes:
Synthetic dyes date from 1865 when William H. Perkin, an 18 years old English boy, made a
purple (a kind of violet) coloured dye from aniline by oxidation with acid dichromate and
named it as ‘aniline purple’. French liked the colour most and hence it was called ‘mauve’
(violet, in French). Since then, a large number of dyes had been invented before the dawn of
the 20th century. Since the parent material for all these synthetic dyes is aniline, the synthetic
dyes are known as aniline dyes also. In fact, leather- finishing with dyes only is known as
‘Aniline finishing’. As aniline is obtained from coal tar, the synthetic dyes are referred to as
‘coal-tar dyes’, as well.
(iv) Classification according to end- uses
Kinds of products being dyed are many, though their increase is not much. These are:
 Cotton, paper, jute (all carbohydrates)

 Wool and leather (all proteins)
 Synthetic fibres and plastics
 Food, drug and cosmetics
The purposes for which the dyes may be applied are also manifold as shown below:
 Photographic sensitisers
These, mostly xanthene, dyes extend sensitivity of the photographic plate to a wide range of
wave length, making them even panchromatic.
 Analytical indicators (eg., phenolphthalein, methyl orange etc.,)

 Fluorescent brighteners
Mordants
Leathers, after dyeing with the azo-hydroxy or azo methane dyes are treated with chrome.
Such (i.e chrome like) bonding substances are known as ‘mordants’. Wool dyes and acid dyes
can be fixed in this manner. These dyeings are resistant to washing, sweat and sunlight. But
nowadays mordanting is not practiced in the tannery because of the availability of pre-
metallised dyes.

Retanning
Fibre structure of hide or skin is not uniform throughout the entire area and it is most
common to fill the empty nature of chrome tanned leathers by retanning to improve the
required properties of leathers, which are intended for making footwear, garments, gloves,
furniture and automotive upholstery etc. Today several developments are taking place in the
field of retanning such as phenol formaldehyde and naphthalene formaldehyde condensates,
melamine, dicyandiamide and carbodiimide based syntans, polymers of various types, such as
acrylates, urethanes and melamine resins. Proteins and protein hydrolysates are finding
increasing amounts of applications as fillers in retanning operations. Retanning agents, which
afford full and yet tight leathers, are of importance.
Objectives
 To achieve strength properties for crust leather as per the desired end product.
 To fill the loose portions of the chrome tanned leather with vegetable or synthetic
tannins.
 To increase the cutting value or usable area after filling even at belly/flank area.
 To achieve less shrinking during drying and for easier drying.
 To achieve good tightness, buffability, embossing and finish properties.
 To improve the penetration of anionic type fatliquors, dyestuffs and finish adhesion.
 To improve certain specific properties like perspiration resistance, fastness to washing,
flammability etc.
Classification of Retanning Agents

 Phenolic syntans
– Replacement syntans
– Auxiliaries
– White-tanning agents and bleaching syntans
– Pretanning and retanning agents
 Polycondensation and polymerization compounds (Resins)
– Methylol urea
– Methylol melamine
– Methylol dicyandiamide
– Diisocyanate

– Acrylates
 Vegetable tanning materials
 Aldehyde tanning agents
– Formaldehyde
– Glutaraldehyde
– Dialdehyde starch
 Inorganic Retanning agents
– mineral based syntans (chrome, aluminium, zirconium salts)
 Protein fillers and their derivatives
Syntans
The term syntan refers to the range of synthetic tanning agents. There are two steps in the
synthesis of syntans: sulfonation and polymerisation. These steps can be conducted in either
order: these are the Nerodol and Novolak (Novolac) syntheses, typically leading to different
molecular constitutions and hence properties.
When Sulphonation step comes before polymerization:

 Sulphonate content is relatively high
 Increased solubility in water
 Reduced astringency
Nerodol synthesis: sulphonation then polymerization
When Sulphonation step comes after polymerization
 Sulphonate content is relatively less

 Less solubility in water
 More reactive towards the substrate
Novolak synthesis: polymerisation then sulphonation
Syntan Precursors
Crosslinkers for Precursors
Types of Syntans
Auxiliary Syntans
 These low molecular weight syntans are relatively unreactive (in a tanning sense).
 Solubilising higher molecular weight syntans or vegetable tannins, to allow more
uniform surface reaction and promoting.
 Dispersing dyes, to allow more level tannin fixation and colouring.
 Non-swelling acids fall into this category, since they rely on a mild tanning effect
after giving up their acid content to collagen in the pickling step.
 So-called ‘bleaching’ syntans may fall into this or the next group. When applied to
chrome tanned leather, the reaction is to strip some of the chrome from the leather and
hence reduce the colouring on the surface, a detanning effect.
Replacement type Syntans

 Replacement syntans are based on the condensation products of phenol and
naphthalene sulfonic acids with formaldehyde or urea.
 High molecular weight, astringent syntans are designed to replace vegetable
tannins and act as solo tanning agents.
 They can match the astringency of vegetable tannins and provide the same degree of
filling.
 It modifies the physical properties of leather with respect to its strength, softness,
fullness, weather resistance, dye penetration, levelness and brilliance of dye shades,
grain characteristics etc.
 A special class of replacement syntan based on polysulfones used for leathers which
require good light fastness properties.
Resin syntans
 Resin syntans are particularly used for filling those areas of the hide or skin where the
fiber Structure is loose. Resin syntans penetrate the skin structure easily and get
deposited in loose areas.
 Resin syntans give tighter fiber structure and finer grain break than vegetable tans.
 Composed of either acrylic resin or melamine or dicyanidiamide or urea or polymers.
 Resins are used as structure or property modifiers for leather: where they have value
in filling the fibre structure to tighten and even up the properties, particularly in loose
bellies.

Acrylic syntans
 Acrylic syntans are leather chemicals, which are polymeric in nature. They are homo-
polymers or co-polymers of acrylic acid, methacrylic acid and acrylonitrile in aqueous
solutions.
 Acrylic syntans are useful in retanning of chrome leather for making suede leather.
 Acrylic syntans help in achieving round, full, firm handle & good grain characteristics
with softness.
 Acrylic syntans are anionic in nature and can be used in combination with other
anionic syntans.
 Acrylic tanning agents are light fast in nature and can be used in light fast leathers.
 It tends to fill void spaces between grain and corium imparting grain tightness and
improved ‘break’ property. Break is an important property for upper leather as it
influences the durability of upper leather in use.
Other Types of Syntans
 Whitening syntans are used to produce leathers in white and pastel colour.
 Aluminum syntans improves grain tightness and buffability.
 Dye leveling syntans are used to get uniform colour on the surface.
 Pretanning syntans used before vegetable tanning helps in preventing excess
deposition of vegetable tannins on leather surface.
 Bleaching syntans removes stains of vegetable tannins.
Fatliquoring
Lubrication involves covering the surface of fibres with a thin film of oil and this oil is rather
tightly bound to the protein. Any excess oil, therefore, remains free or unbound in the
interstices of the fabric and will come out on pressing or flexing the leather, causing grease
problem.
Objectives
 To lubricate the leather fibres so as to reduce internal friction while in use and to
increase durability.

 To form physical or chemical crosslinks between the fibres, thereby to avoid
collapsing or sticking even after drying.
 To achieve softness, pliability, stretch, compressibility and tensile strength.
Fatliquors
Fatliquors are oils, fats and waxes, synthetic or natural prepared in such a way so that they
become emulsifiable in water and suitable for use on leather in a water float. Emulsification
is a means of enabling a water insoluble material to be dispersed in water. The solution lies in
breaking the oils into tiny droplets and suspending them in liquid which can enter into the
leather. Such liquid-in-liquid dispersions are known as emulsions. All emulsions are opaque
like milk and of different shades of white colour (the actual shade depending upon the
particle size of the oil droplets). Emulsions meant for leather lubrication are known as
‘Fatliquors’. Of the three kinds of dispersions- coarse, colloidal and molecular, fatliquors
belong to the coarse dispersion type. The size of the oil particle in a fatliquor may range from
1-5 microns and sometimes even 25 microns, also.
Emulsifiers and Emulsification
Water has no affinity for oil and hence it ejects out all oil when introduced into it. So, if an oil
droplet is to stay in water, it needs the help of a mediator for which both oil and water have a
liking. Necessarily the mediator molecule should have a dual structure to play the dual role of
making friends with both oil and water. This dual structure is symbolically indicated as RX.
In this formula, R is an alkyl (i.e. a hydrocarbon) chain. It has good affinity for oil and is
hence known as ‘oleophilic’ part. (O = oil; Philic= loving) and oleophilic part is
automatically ‘hydrophobic’ (hydro= water, phobic= hating) also. Similarly, X in the formula
is a polar part and it has good affinity for water and hence known as ‘hydrophilic’ part. And,
now, if a layer of RX is spread over an oil surface, the RX molecules orient themselves over
the oil surface such that the oleophilic R’s remain buried within the oil and X’s only just out
into the outer space. So, now, if this protected oil droplet is introduced into water, the
hydrophilic X’s only are in contact with water and water tolerates them. Thus, a stable
emulsion is formed.
Emulsions are of two types- 1. Oil in water (O/W) and 2. Water in oil (W/O). The type of
emulsion formed depends upon the relative strengths or Balance (B) of the Hydrophobicity

(H) of R and the Lipophilicity (L) of X. This relative strength is known as HLB value of the
emulsifier. It can be calculated using the formula:
HLB = 20(1-S/A) where S= saponification value and A= acid value
In the table below, HLB values of emulsifiers and the resulting properties are indicated.
HLB values Nature of dispersion Use
1-4 Insoluble
3-6 Poor W/O emulsifier
6-8 Milky during mixing Wetting Agent
8-10 Stable milky dispersion O/W emulsifier
10-13 Transparent/colourless dispersion O/W emulsifier
13- Colourless solution O/W solution
Sodium soap represented by the general formulae RCOONa is a well-known emulsifier in

daily use. In this case, RCOO - alone is the true emulsifier and Na is only a counter ion which
makes the whole molecule electrically neutral. Since the emulsifier role here is played by the
anion RCOO-, RCOONa is called an anionic emulsifier. [R 4N]+Cl- is the structure of cationic
emulsifiers in which R corresponds to the R part of RX and N + only is the polar X part. There
are also amphoteric and non-ionic emulsifiers. In all, there are four classes of emulsifiers—
anionic, cationic, nonionic and amphoteric.
Whatever be the emulsifier, it is absorbed by the leather (protein) after fatliquor penetration.
And from the broken emulsion, the freed raw oil spreads in the interspace between fibres. It
should be noted that raw oil is the real lubricant.
Classification of Fatliquor
Based on their application in leather industry, fatliquors are classified into
 Anionic fatliquors
 Sulfated Fatliquor
 Sulphonated Fatliquor
 Sulphited Fatliqour
 Cationic fatliquors

 Nonionic fatliquors
 Multicharged or Amphotric fatliquors
Based on the Origin of the Oil, fatliquors are classified into
 Animal Based
 Vegetable Based
 Synthetic Fatliquor
Anionic Fatliquor
Sulfated and Sulphonated Fatliquor
Anionic fatliquors are oils emulsified with anionic emulsifier. Treatment with sulphuric acid
is one of the ways of converting oil into anionic emulsifier. Based on the reaction of oil with
sulphuric acid the fatliquor may be either sulphated or sulphonated.
In sulphated fatliquor, the S-atom is attached to carbon atom of the oil chain through the
mediating O atom, whereas in the oil-sulphonate the S atom is diretly attached to the C atom
of the oil chain. Sulphonated oil emulsions have fine particles than sulphated. But sulphated
oils have better lubrication power than sulphonated oils. As generality, the degree of
sulfonation of natural raw materials does not exceed 40% as the softening properties decrease
at higher values.
Sulphited Fatliquor
If oils are reacted with bisulfite (NaHSO 3) to make the sulphonated products, a lower
temperature will do and there is no need for use of alkali also, since the required alkali is
already available packed in the reagent NaHSO 3. Oils sulphonated by the sulphitation
procedure are specially known as “sulphited Oils”. Sulphitation is carried out in two steps
namely, oxidation and sulphitation and hence is known as “oxidative sulphitation” also. In
general, sulfited fatliquoring agents show good electrolyte (salts) stability. This allows them
to be used during mineral tanning as changes of float pH only slightly affect the stability, the
emulsifying power and the electrolyte stability. In some cases, higher pH values may lower
the electrolyte stability and increase the emulsifying power for neutral oils.

Note that the sulphonated oil obtained through sulphitation is free from soap. Since sulphited
fatliquors do not require neutralization, they penetrate into even under-neutralized leather.
Sulfited oils are used as follows:
• Softness and strength for all leathers by deep penetration.

• Woolskins and furskins in mineral tanning baths.
• In shrunken grain production, to minimise loss of tensile strength in the acidic tanning
bath.
Cationic Fatliquor
Fatliquor made with cationic emulsifier is termed as “cationic fatliquor”. The cationic
emulsifier is usually a quaternary ammonium compound (NR 4)+Cl-. Cationic fatliquors in
general are resistant to acids, salts and mineral tanning agents. Cationic fatliquors are
commonly used in chrome tanning for the better distribution of chrome. Cationic fatliquors
are incompatible with anionic materials like tannins, syntans, anionic dyes and fatliquors and
therefore, the two classes should not be mixed. The other properties are
 Positively charged, pH of 10% emulsion of cationic fatliquor in water: 4.0-4.5.
 Low affinity for cationic charged leathers, e.g. chrome tanned.
 High affinity for anionic charged leathers, e.g. vegetable tanned, for lubricating the
outer layers.
 In compatible with anionic fatliquors.
 Used for surface lubrication, and to improve the positive charge characteristics and
thereby, affinity to anionic dyestuffs.
 Cationic fatliquor does not penetrate the vegetable tanned leather.
 Topping with cationic fatliquor effectively arrests the oil migration and consequent
surface cracking.

Nonionic Fatliquor
These fatliquors are emulsified with compounds made by condensing ethylene oxide in the
presence of an aliphatic alcohol. All nonionic emulsifiers are extremely stable to acid, salt
and alkali and these can be used for the preparation of nonionic fatliquor. These fatliquors
can be formulated with anionic or cationic fatliquors in order to improve the stability. It is the
most versatile fatliquoring agent and also gives body to the leather. They can absorb moisture
and hence are good humectants and keep the leather flexible.
The following points apply to these fatliquors:
• High stability to metal ions, salts, hard water and wide pH tolerance.
• Miscible with cationic and anionic reagents.
• Little or no affinity for anionic or cationic charged leathers.
• The non-ionic emulsifier increases the hydrophilicity of leather.
• Used for fatliquoring zirconium(IV) or aluminium(III) tanned leathers, which are
highly cationic charged.
• As a crusting fatliquor for suede splits, i.e. Merely to prevent fibre resticking on drying, to
aid rewetting.
• May be formulated with anionic or cationic fatliquors, to improve stability.
Multi-charged and Amphotric Fatliquors

These fatliquors are formulations of nonionic, cationic and anionic fatliquors, in which the
presence of nonionic species prevent precipitation of cationic and anionic species. They are
more stable to a wider pH range than a singly charged fatliquors and hence more stable to
variations in leather charge.
Alternately, raw oil is emulsified with an amphoteric reagent, i.e. one containing both acidic
and basic groups, (e.g. amino propionic acid and alkyl substituted betaines). This is an
amphoteric fatliquor. The choice of pH of the fatliquor depends on the charge of the leather
and the requirement of surface reaction or penetration. They are extremely stable to acids,
alkalis and salts. In view of the fine handle and good fastness to dry-cleaning, they are best
suited for garment leathers. They fix very well to proteins and expensive too.
Synthetic Fatliquors
These are normally based on high molecular paraffins of chain length 15-30 carbon atoms,
and are produced by sulfonation of paraffins. In contrast to glycerides they are less chemical

reactive, and are not manufactured using sulphuric acid or sulfites. It is common, however, to
use one of the following procedures:
 The simultaneous catalytic reaction with oxygen and sulphur dioxide known as
sulfoxidation, followed by neutralization of the paraffin sulfonic acid with alkali.
 The catalytic reaction with gaseous chlorine and sulphur dioxide, the so called sulfo-
chlorination. In this event sulfo-chlorinates are produced as reactive intermediates, with
hydrochloric acid as a by- product for neutralization with alkali. By neutralising the sulfo-
chlorides with alkali metal hydroxides, salts of the paraffin sulfonic acids are formed.
R-H + SO2 +Cl2 R-SO2Cl + HCl

Paraffin sulfo-chloride
R-SO2Cl + 2NaOH R-SO3-Na+ + NaCl + H2O

Paraffin sulfonic acids
 Base containing nitrogen can also be used as neutralizing agents. They often result in
products with special technical properties.
RSO2Cl + NH3 R-SO2NH2
+ H2N-CH2-COOH R-SO2NH-
CH2-COOH
+H2N-CH2-SO3H R-SO2NH-CH2-
SO3H
Paraffin sulfonamides
The sulfonic acid group does not enter the carbon chain at a predetermined position but, with
statistical distribution, multiple sulfonations of the same paraffin molecule are possible. In
addition to these procedures, an interesting property of the intermediary paraffin sulfo-
chlorides is that they can be used as direct fatliquors. As they are reactive, they combine with
collagen, and as they then become non extractable, they are particularly useful for garment
and chamois type leather manufacture. In this application, it is essential to neutralize the free
hydrochloric acid produced interaction.
Advantages

1. Light weight of the fatliquored goods without over loading which is very important in
respect of garment and suede leathers.
2. Absence of spue formation, as it contains no free fatty acid.
3. No discolouration due to oxidation, as it contains no double bond and hence useful for
pastel shades and white leathers.
4. No smell.
5. No gummy or sickly material formation as no polymerization takes place within the
leathers.
The disadvantages of synthetic fatliquor are
1. Give no body and gives a dry feel only.

2. Expensive.
Properties of Synthetic Fatliquors
 In general, sulfited fatliquoring agents show good electrolyte (salts) stability. This
allows them to be used during mineral tanning as changes of float pH only slightly
affect the stability, the emulsifying power and the electrolyte stability. In some cases,
higher pH values may lower the electrolyte stability and increase the emulsifying
power for neutral oils. Synthetic fatliquors, however, are not affected in stability nor
in their emulsifying power by changes of the pH value.
 The type of emulsion and technical properties of a fatliquor largely depend on the
degree of sulfonation, type of raw material, choice of chemical processing, and the
technique of manufacture. This enables the development of a wide variety of
fatliquoring agents with very specific properties.
 As a generality, the degree of sulfonation of natural raw materials does not exceed
40% as the softening properties decrease at higher values. However, sulfonation
degrees of around 60% are common with synthetic fatliquoring agents. In this case,
the chain length of the raw material significantly influences the technical properties.
Long chain paraffins produce better softening and filling effects whereas, short
chained ones serve better as wetting agents.
 These emulsifying components also carry other products in the fatliquor emulsion.
These can stem from the incomplete sulfonation of raw materials, fatty acids formed
as side reactions in both sulfonaiton and also the addition of selected synthetic oils.

 These emulsifying properties also extend to the important dispersion of natural grease.
The ratio of emulsifying and emulsified components varies for each fatliquoring
product.
Influence of Fatliquor on the Leather Characteristics
Softness: A basic requirement for good softness is to keep the fibre boundless and fibrils
separated after drying so that they will not stick together. This is largely provided by the
sulfonated/sulfited/sulfoxidated fatliquor components.
Elasticity and tear strength: Physical lubrication for the fibres is provided by the non-
modified fatliquor components and additives released from emulsion during the fatliquoring
process. If the fibers are lightly coated with a lubricant they slide well and maintain a higher
tensile strength.
Grain tightness: Tightness of the grain is very dependent on the type and the amount of
fatliquor used, in conjunction with the structural difference between the grain and the
reticular layer. The task of the fatliquoring agent, together with techniques used in retanning,
is to help compensate for these differences.
Handle and fullness: The filling effect and handle is largely dependent on the properties of
the basic raw materials and additives used in the faliquor blend. As a generality, the increase
in filling effects are, in order:
Mineral oil <vegetable oils (castor) < fish oil <wool grease <neats- foot oil <high molecular
paraffins.
Finishing: The uniformity of fatliquor distribution across the grain surface, and the
dispersion of natural grease by the fatliquor, affects both the uniformity of finish and
penetration of the first coat. This in turn affects the uniformity of colour, cover, and major
physical properties such as the wet and dry adhesion.
The stability of fatliquoring components
 In general, the emulsifying components in the fatliquor such as acid esters and
sulfonic acid groups- can link to basic collagen amino acids by ionic bonds. As the
degree of sulfonation increases, in addition to changing leather properties, the amount
of extractable or migrating substances in the leather reduces because of these
bondings.
 The emulsified components, however, can only develop weak bonds by polar groups,
hence a higher level of extraction and an increased tendency to migrate. Problems can
be created by free or saponified carboxylic groups as these can form complexes with
trivalent metal compounds in the leather. These in turn can produce colour
irregularities and finishing problems due to their water repellency properties.
 In addition, highly unsaturated fatty substances may suffer autoxidation within the
leather. This is one cause of yellowing on aging and, if excessive, can lead to a
reduction tensile strength.
Water – proofing –cum- reactive fatliquor
It is common to refer to treatments for leather with hydrophobic reagents as waterproofing.

This implies that water is completely excluded from the cross section of the leather, so that
no transmission of moisture occurs. The most effective method of waterproofing chrome
leather was that worked out by Dr. George H von Fuchs (1948-66). It consists in treating
chrome leather with ASA’s (Alkyl Succinic Acids). This kind of water proofing chrome
leather through complexion of ASA’s to chrome is known as ‘Bavon process’. The
peculiarity of this product is that while its R’s, if sufficiently long, act as a lubricant, the two
carboxyls by complexing with chromium already bonded to collagen, merges the lubricant
with the leather. ASA’s, therefore, are in a way reactive fatliquors also.
The Bavon process was used commercially for some time, but is the typical inconsistent
process. The principle lies in a stepwise mechanism:
1. Reaction between the alkyl succinyl dicarboxylate and bound chromium(III).

2. Creation of a second layer of the reagent, when the alkyl groups interact in a
hydrophobic bonding arrangement.
3. When the dry leather is wetted, a water-in-oil emulsion structure is formed at the
carboxylate surface, preventing the passage of water through to the fibre surface.
Compared to the simplistic barrier approaches to water resistance of the past, what is needed
in the modern industry is chemical treatments that do not adversely affect the handle and
‘breathability’ properties of the leather.

The silicone reaction is readily understood: the chain of Si–O moieties provides many oxygen
atoms that can interact electrostatically with collagen or leather. In this way, the fibre
structure becomes coated with a surface of water repellent alkyl groups. This is an effective
type of treatment, although it is more commonly used in conjunction with other chemistries,
which facilitate the delivery of the silicone.
The current industry standard for making water resistant leather from chrome tanned stock is
partially esterified acrylic polymers. The process is simple, if the conditions set out above are
adhered to. Here the mechanism involves complexing available carboxyl group in the
polymer with bound chromium(III), therefore presenting the surface of the fibre structure as
covered with alkyl groups. These groups also act as spacers within the fibre structure,
functioning like a lubricant.
Currying
Currying is a process of applying fat and oils to leather. There are different ways of doing this
but only stuffing and oiling come under this definition. Though the objects of fatliquoring
and currying are more or less the same but their different ways of oil application to leather
have kept these two systems distinctly separate. The main differences between fatliquoring
and currying are presented in Table 2:
Table 2. Main Difference between Fatliquoring and Currying
Fatliquoring Currying
1. Oils are applied to leather in the form of 1. Oils are not applied in the form of
emulsion emulsions. They are applied generally in
2. Since oils are used in the form of the raw condition.
emulsion, the penetrating powers of the 2. Penetrating powers of the oils in to the
oils into the wet leather are not so wet leather are important.

important 3. Moisture content of the leather to be
3. Moisture content of the leather to be curried must be carefully controlled.
fatliquored is not at all important 4. Comparatively larger quantity of oil is
4. Small quantity of oil can lubricate large required to lubricate the same number of
number of fibres. fibre.
5. Penetration is very slow.
5. Penetration of oil into wet leather is
very quick. 6. Electrical charges are not so important
6. Electrical charges on the leather surface
7. Leather surface becomes oily if special
as well as of the emulsion are important
care is not taken.
7. Leather does not become oily if
properly fatliquored.
Objectives of currying:
The main objects of currying are:
1) To increase the tensile strength and flexibility of leather.

2) To prevents grain crackiness.
3) To prevent oxidation of the surface tannins, and
4) To increase the waterproofness of the leather.
Selection of oil for currying
The oil or oils to be used for currying must have some specific properties so that they can
penetrate into the very narrow capillary spaces of the leather and, displacing water, can
spread over the wet surfaces of the fibres; or in other word the oils, selected for currying,
must have penetrating and spreading powers into the wet leather. The penetrating power of an
oil is governed by its viscosity. An oil of very high viscosity cannot penetrate through the
capillaries of the leather and therefore unsuitable for currying.
Drying

After completing all stages of wet processing, the leathers are dried and prepared for the
subsequent finishing process. As drying is mostly performed under the action of heat for
efficiency reasons the drying conditions should be adjusted to the respective tanning method. The
maximum temperatures should not exceed 30 - 35 °C for vegetable/synthetically tanned leathers
and 60 °C for chrome- tanned leathers in order to avoid changes of the leather properties. The
water in collagen can be divided into three main groups: structural water, b o u n d w a t e r
a n d bulk water. Bulk water has a liquid-like character and can form ice crystals at 0oC.
Bound water exhibits a structure between solid and liquid, so it does not freeze at 0oC.
Structural water molecules are part of the fibre structure and behave like a solid. Figure
illustrates the observed progress of drying.
α - the constant rate period (removal of water from between the fibres)
β – the first falling rate period ( water situated between the fibrils)
χ- the second falling rate period (water located within the fibrils)
In the earliest stage of drying, there may be sufficient bulk water on the
surface of a leather for it to act like a liquid water surface. Evaporation
occurs at a constant rate, which is directly proportional to the surface area of
leather (A), mass transfer coefficient (Kg) and to the difference between the
vapour pressure of the water at the surface temperature (Ps) and the partial

pressure the water vapour in the air (Pa):
dW /dt =AKg (Ps – Pa )
This indicates that the rate of drying is dependent on the temperature and the relative
humidity of the air. In theory, fast drying conditions can be used during this phase of drying,
as long as the losses of the bound and structural water molecules are prevented. After this
constant rate of drying period is completed, the rate of drying is controlled by the diffusion of
moisture/vapour from the higher concentration in the centre of the leather to the lower
concentration at the surface. During this period the rate of drying is entirely dependent on the
ease of diffusion of water vapour through the structure. Consequently, the factors that affect
the diffusion rate will control the drying rate.
Different Methods of Drying Leather
Hang-drying
– Air drying without supply of energy
Low-price drying method, however dependent on weather conditions and therefore only
economical in regions of suitable climate. This method has a gentle drying effect.
– Air drying with supply of energy
(Drying room, tower or rack drying method with supply of hot air, drying in channels or
tunnels by a through-feed or rotary system, without or with separate temperature zone
sectors). Quick drying methods whereby, a uniform residual moisture content is kept in
the leather, especially in the case of sector drying
– Cold-air drying by air dehumidification
This method consists of drying of batches at room temperature in a tightly closed drying
chamber. The recirculated air is cooled by means of a cooling cell and the water
contained in the air condenses as dew. On reheating this air, which has a highly reduced
content of water, it has a quick-drying effect on the leather (principle of the heat pump). It
is a very gentle, softening drying method.
Paste drying
Mainly used for firm upper leathers with corrected grain. The wet leathers are flattened by
means of a sleaker onto both sides of glass panels to which adhesive has been applied and
dried in a hot air stream at 50 - 60 °C by the chamber through-feed method. The advantage
of this method compared to hang-drying is a considerable gain of area. The composition of
the adhesive is important. The adhesive should remain on the glass panel when the

leathers are pulled off and should be easy to remove.
Vacuum Drying
This drying method is based on the property of water to boil at low temperatures under
reduced air pressure and thus to evaporate more quickly. The wet leathers are flattened by
means of a sleaker onto a heatable metal plate without creases and then hermitically covered
by means of an air- tight bell. The inside air pressure is reduced by evacuation and the leather
is dryed in about 4 - 10 minutes depending on the preset vacuum, the heating temperature of
the metal plate, and on the thickness and moisture content of the leather. The area yield,
thickness and softness of the leathers can be influenced by changing the vacuum, the counter
pressure and the temperature.
Drying by Radiation
Infrared Drying:
Drying is performed by means of heat radiation from inside the leathers. Suitable for chrome
tanned leathers and leathers tanned by combined tanning agents and especially for thin
leathers. Less suitable for purely vegetable tanned leathers because signs of charring occur,
especially at the end of the drying process.
High-frequency Drying:
This drying method is carried out by means of electromagnetic waves having a very high
oscillation frequency and is mainly performed in a through-feed process. The advantage of
this method consists in the exact regulation of the residual moisture content in the leather. It
is less economic for complete drying of wet leathers, but a very suitable redrying method.
Small sections of leather can be dried very quickly in microwave devices to achieve
adjustment of shade without producing serious colour differences with regard to the entire lot.

Mechanical Treatment
The machine work, the mechanical treatment of hides, skins and leathers made of these until
to the finished state is of greatest importance for the success in leather making. The
mechanical treatment at various stages of leather processing significantly influences the
quality and area of the final leather. The principle involved in some of the important
mechanical treatment of semi-finished leather is discussed below.
Sammying
It is a process by which lot of water about 30% out of 50-55% present in wet blue is squeezed
out. Because the next process of splitting requires about 20-25% moisture. If the wet blue
hide/skin contains more moisture, then the splitting operation would not give better results.
Leather will slip and may stick to the grooved roller.
There are two types of sammying machines found in tanneries
– Alternating cylinder machines

– Through feed felt type machines
However through feed machines are preferred due to their high productivity.
Alternating Cylinder Sammying Machine: Manual

Sammying out machines comprise a pair of squeezing rollers and a fan or auxiliary roller, just
to remove folds. Squeezing rolls holds the leather tight by means of hydraulic pressure and a
motor rotates them. The felt sleeves on both the rollers squeeze out water from leather (see
Figure 11).
Working Principle
 More than half of the hide is inserted into an open machine and spread evenly over the
supporting cylinder.
 The machine is then closed.
 Cylinder B presses the hide against cylinder A under pressure.
 Then cylinder A and B rotate to extract the hide from the machine
 While the hide is being extracted, cylinder D pushes the hide against cylinder C to spread
and flatten the hide at the same time the hide gets squeezed between the pressing
cylinders.

 When the hide comes completely out of the machine, cylinders A and B stop rotating and
the machine is opened.
 Then the second half is processed in a similar fashion.

Figure 11: Alternating Cylinder Sammying Machine
Through Feed Sammying Machine

These type of machines do not spread or tension the hide and make it free of wrinkles.
Through feed machines also have a pair of squeezing rollers but the bottom roller is
enveloped inside an endless felt conveyor having extra support rollers to keep conveyor in
tension. In addition of above, some machines are also provided automatic belt centring
system.

Figure 12: Through Feed Sammying Machine
Splitting
Splitting is the process of separating the thicker bovine leather into one or more horizontal
layers. The process is carried out with the splitting machine in which the wet blue is pushed
by two cylinders against a band blade which cuts the skin in two layers parallel to its
surface.The top layer is the grain (typical design of the skin of the animal, the external part)
this is the full grain part, while the lower layers are the flesh split. In general, the thinner
skins (sheep, goats and calves) are skived but not split. Splitting can be done after liming or
after chrome tanning. The choice depends on the product we want to achieve.
Differences in moisture content of wet blue after sammying can result in a trade-off between
areas loss, operation time and splitting accuracy. Although it was initially found to be slower
to manually feed wetter hides into a splitter, once started the hides fed thorough the rollers
more easily, and with less operator intervention, as the hides were able to spread out as they
fed through.
In contrast, hides that had been heavily sammyed were easier to initially feed into the splitter
but required more operator intervention to spread out sammer-induced folds and creases as
the hides feed through the splitter.

Because the wetter hides could spread out, as they feed through the splitter rollers, there was
less gouging or cutting of folds and creases compared with the more heavily sammyed hides.
This was the case whether feeding tail to neck or belly- to- belly.
Modern splitting machines are capable of being programmed to compensate for differences in
the hide structure and moisture content. The adverse effect of feeding high moisture content
material to a splitter is a loss of thickness accuracy. This requires more correction in shaving.
Figure 13: Schematic of Splitting Machine
Shaving
Shaving is the operation which brings the leather to a uniform thickness throughout the entire
surface of the skin/hide. Shaving removes loosely attached tissues and fibers from the flesh
side. The hides and skins are naturally thicker in the butt and neck region and much thinner in
the belly area. The thickness has to be equalized and reduced to some degree depending on
the finished articles they are to make.
Wetter hides were physically easy to handle in a shaving machine as folds and creases were
less pronounced and the material tends to set our more readily. The result was less damage
especially in the neck and forward leg areas. Shaving of wetter material requires careful
attention to the thickness profile to ensure that the correct thickness is obtained after drying.
The shaving operation, if not moderated, can also have a dramatic effect on the area yield of
leather. It has been estimated that in some operations up to 10% area was removed from

hides at the shaving stage. Some of the area is lost in unworkable areas of hides but much is
lost when the neck and leg areas are shaved.
In tannery trials typically up to 0.6-0.8 mm was removed in shaving. It was determined that
the shaving of wet blue caused stretching, ranging from 5-10%. The stretching forces on wet
blue during the shaving operation caused tearing apart of the fibrous structure in weak
regions of hides.
Operating Principle of a Shaving Machine
 The pressing roller “C” and back-up roller “B” feed the hide “A”.
 Then the hide passes between the knife cylinder “D” and back-up roller “B”.
 It is shaved by the blades, which removes the excess material from the flesh.
 The knife cylinder is provided with a series of helical blades that have a cutting edge. The
cylinder rotates at high speed.
 The desired hide thickness is obtained by appropriately setting the distance between the
backup roller B and knife cylinder D.
Figure 14: Shaving Machine
Staking
Staking operation makes the leather more soften and flexible. Staking achieves desired
softness and feel without causing damage to the fibres in the leather. Before staking, the dried
leathers are conditioned in order to avoid fibre breakage. The machinery is also adjusted to
suit leather quality, softness and moisture content. The objective of conditioning process is to
give the leather a moisture content of 18-22% to allow mechanical softening. The dried
leathers have different levels of moisture from drying at 8-14% because of the different
thickness and conditions. In practice, leathers are dried to the lowest level at the first drying,
so that subsequent conditioning can produce uniform moisture content and allow a uniform
softening. Conditioning adds a controlled amount of water to the leather, usually on the flesh
side. This is normally a simple spray application combined into a string conveyor, and a great
improvement over the use of damp sawdust. The moistened leathers are piled flat and stand
for 24 hours to allow the moisture to reach equilibrium.
The main objective of staking operation is to mechanically stretch the leather, separating the
fibres, which have become attached to each other during drying. It is important that the
moisture content is correct, if the leather has too much moisture, there is insufficient
movement of the fibres and the resultant leather is not soft enough after drying out; if the
leather is too dry, the fibres are damaged by the mechanical action.
Although several types (models) of staking machines are available all over the world in the
tanning industry, only two types are most common. They are Jaw-type staking (Slocomb
Staking) and Vibrating staking machine (Mollisa Staking):
The conveyor driven vibrating staking machine is excellent for most leathers, and causes less
damage than earlier types. It also has an advantage that the operators need less training. The
older jaw-type staking (Slocomb) machine is still suitable for special softness required for
suede and glove leathers. For Slocomb staking, the operators should be skilled because it has
a poor safety record. The manual operations do not allow adequate guards to be fitted on all
the moving parts.

Figure 15: Staking Machine
Buffing
Buffing consists of grinding the leather surface with an abrasive, and is similar to
sandpapering. It is used to remove the loose fibers on the flesh side. It is also used on the
grain to remove surface blemishes and thus provide a more uniform surface, to which
pigment and other finishes can be applied. This is often referred to as “snuffing”. On the
suede leather production, buffing lifts the surface fibres and grinds them to a uniform length
to produce a level nap. There are several types of buffing machine, of which Figure 16
illustrates the through feed buffing machine.
Figure 16: Through Feed Buffing Machine

Finishing Techniques
The History of Leather Finishing
The term ‘Leather finishing’ relates to those operations which give the leather its final
appearance and make it useful, attractive and appealing to its users. Finishes on leather also
serve as a protective coating. Earlier leather finishing was done by coating varying mixtures
of natural dyewoods, mucilage’s, oxblood, milk and white of eggs on the leather surface.
This gave an even and pleasing appearance to the finished leather. This method of finishing
continued for a long time until the period 1916 – 1918 when American leather manufacturers
introduced first ‘pigment finished leathers’ in the market. The introduction of pigment
finishing created a revolution in the technology of leather finishing and has thus made it
possible to produce leather of uniform appearance even from raw materials with defective
grain. By the finishing process, the grain surface of the leather is coated with various
substances and is then submitted to different mechanical operations, depending upon the
purpose intended whereby the appearance of leather can be highly influenced to make it more
useful, attractive and appealing to users.
Objectives of Finishing
Ñ The main objective of finishing is to give a decorative coat to the leather grain surface
to protect it against dirt, staining, wetting etc.
Ñ To protect the leather from damages caused by mechanical stresses like rubbing,
scuffing, flexing etc.
Ñ To improve the aesthetic appeal and the sales value of the product.
Ñ To level or make uniform the colour of the grain surface, hiding grain blemishes and
upgrading its quality.
Ñ To maintain the original beauty of the finish for long period.
Principles of Finishing
A normal finish essentially consists of 3 coats.
Bottom Coat
The bottom coat may be either sealing or impregnation coat and clearing coat. The object of
sealing or impregnating coat is to seal the grain to control the penetration of the season coat.
The season coat should give a leveled and uniform filmed colour coating and not overload the
grain. Sealing should uphold firmly on the leather surface. Impregnation coat is applied for
soft grain tightening and filling effects. The objective of the clearing coat is to make the grain
devoid of any oils or fats and to improve the absorbance of the season coat by the leather.
Season Coat
The season coat is to impart a desired colour to the leather and level out the surface defects.
The effects like glossy or matt, soft or hard feel can be brought about by proper choice of
auxiliaries added to the season coat. This coat can be done either by pad or hand spray or
Auto spray. By spraying on we can achieve levelness in film formation.
Top Coat
Top coat serves the purpose of protecting the season coat. It gives properties like appearance,
handle, fastness to wet and dry rub.
Classification of Finishing
Aqueous Leather finishes Non-aqueous Leather finishes
Protein Finish Resin Finish
Plated finish Lacquer finish
Aniline Semi-Aniline Glaze finish
Lacquer finishes Vinyl resin finishes Polyurethane Finishes
Protein Finish
This type of finish uses binders mostly based on proteins. The film formed is not continuous,
which facilitates the friction glazing at high temperature. The leathers will have a natural look
and feel. The finish would also be resistant to cold weather.

Aniline Finish
Aniline finish is a transparent/translucent finish, which keeps the natural appearance so that
the original grain pattern of leather surface is easily visible. This is a lighter finish without
loading the surface of the good quality leathers. It will have good fastness to light and
bleeding. Most of the colour matching is competed in the wet finishing stage itself. Aniline
finish is done only in full grain leathers to retain the natural grain clearly visible.
Aniline leather need not have full grain. Buffed leather with aniline finish/look can also be
produced. Aniline leather need not be completely free of pigments. The finish may be done
with small amounts of finely dispersed pigments.
Semi-aniline or aniline look or mock-aniline finish

Finishing based on transparent pigments and little of opaque (covering) pigments for hiding
slight grain blemishes. Sometimes opaque finishing is done first to hide the grain defects and
on which an aniline look/mock aniline effect is given by applying dyestuffs and/or
transparent pigments etc. Full grain leather with slight defects is snuffed to even the surface.
In case of deeper grain damages it is necessary to snuff the leather deeply. So heavy coating
with season is required. This may result raised grain. Applying impregnation coat with
medium hard resin can eliminate it. This treatment not only improves sealing it also tighten
the grain. On this artificial grain patterns are printed after season coat.
Resin Finish (Aqueous or Aqueous Cum Non Aqueous)

This finish is primarily based on polymer emulsions and top coated with lacquer. This has a
continuous film which is thermoplastic. The resin finished leathers can only be plated at
pressure and temperature and not capable of being friction glazed. The film has more filling
effect than protein finishes. Unlike protein finish, the film is internally plasticised and hence
possesses intrinsic elasticity. The new easier form of film forming products like acrylates or
vinyl or butylenes polymers or polyurethane or nitrocellulose are offered by the chemical
industry. The new modern finishes has been accepted by the tanner as it is possible to
upgrade the poor quality raw material by this finishes.
Lacquer Finish
This finish is generally based on nitrocellulose or cellulose nitrate. Here both lacquers
(solvent dilutable) and lacquer emulsions (water dilutable and solvent dilutable) are used. The

film formed is firm, but may crack at low temperatures. Some of the lacquers with suitable
plasticisers can be friction glazed.
Polyurethane finish (non- aqueous)

Urethane finishes have come into extensive use in leather finishing in the current decade.
Polyurethanes represent a class of versatile, high performing polymers. The reaction of poly
isocyanates with polyols is the basis for polyurethane chemistry. This finish gives a film,
which has exceptionally excellent abrasion resistance, balance of flexibility and toughness,
high gloss, gloss retention, solvent resistance, covering, better handle, softness and levelness,
brilliancy of the finish, dry and wet rub fastness, and better adhesion. At the same time, the
finish has one disadvantage in that it makes the leather look like plastic. Urethanes are
normally used as top coats for leathers finished with polymer emulsions.
Method of Application
There are essentially two methods of application (I) by pad / brush and (ii) by spray. In most
cases the two methods are used in combination. Finishing using pad / brush coats have better
anchorage of finish than by mere spraying. Instead of hand padding & spray automatic
padding and automatic spraying are also used in big production units. Airless spray is also
used for certain types of finishes. Besides the composition of finishing techniques adopted
and drying the mechanical treatment of leather surface during finishing plays an important
part.
In recent years another application methods have been developed by curtain coating and
roller coating. Base coats applied by roller coating machine cover more rapidly than base
coats applies by other methods, like pad/spray coats and also a better smooth finish is
obtained. Roller coating is thus more economical from the point of view of product costs and
wage cost. Curtain coaters are used where very thick coat of finish has to be applied such as
on patent leathers.
Various Constituents used in Finishing Formulations

 Pigment paste
 Dye solution
 Binders
 Fillers
 Plasticizers
 Crosslinkers
 Wax emulsions
 Feel modifiers
 Fixing agents
 Preservatives
Pigments
Pigments are particulate matter characterized by the properties:-
1. Cheapness
2. Colour
3. Opacity
4. Insolubility (though organic pigments may dissolve in the finish film binder and
migrate to the top causing uneven shade- bleeding)
5. Inertness to heat, UV light, atmospheric gases, solvents, dilute acids and alkalies.
6. Innocuousness (i.e. non- toxicity to humans) expressed as TLV (Toxicity Limit
Value) and environment.
Properties of Pigments
 Particle size  Compatibility

 Shape  Flocculation
 Nature of the surface  Bleeding and migration
 Refractive indexes  Abrasion and
 Fastness  Crystallization.
 Particle Size
The covering power of a pigment largely depends upon its particle size. Smaller the particle
size, higher is the covering power. The particle size of commercial pigments vary from the
colloidal particles which are very fine (0.01µm) to relatively close particles. (100µm)
 Shape

The shape of pigment particles determines to a great extent the strength of bondages formed
between the binder and the pigment. The bondage is strong when the particles are irregular in
shape and possess pointed sharp edges.
 Nature of the Surface

The nature of the surface of a pigment particle should be such that it can easily reflect those
light waves which represent the colour of the pigment. When the surface of a pigment particle
becomes harsh, its brilliancy is largely reduced. It has been observed that the surfaces of
many pigments particles become harsh when wet pigment is dried very quickly at a very high
temperature.
 Refractive Index
The covering power of a pigment also depends upon its optical density which can be
represented by its refractive index. Higher the refractive index, higher is the covering power.
 Fastness
Pigments must be fast to light, heat, smoke, dust, different gasses present in the atmosphere,
dilute acids and alkalis, rain water and different common organic solvents. By the fastness of
a pigment, we understand its capacity to retain colour and other properties against all sorts of
environmental influences. A good pigment should therefore be chemically inert.
 Compatibility
A good pigment particle is not chemically inert. They may precipitate out many ingredients
from the binder solution, into which the pigments are dispersed. A good pigment should be
compatible, i.e. it should satisfactorily tolerate all the materials used in paint preparation. The
residual charge or valence retained even after the transformation of the dyes to pigments may
also reduce the compatibility of a pigment.
 Flocculation
A good pigment powder should completely disperse when it is sprinkled on a stirring vehicle
containing other necessary materials at a slightly elevated temperature. If some portion of the
powder form lumps and floats on the surface of the vehicle, the powder is considered as an
inferior type or flocculating type or a pigment.
 Bleeding and Migration

Bleeding and migration of colours are another two important factors. When the colour of the
pigments diffuse into the vehicle, pigment is definitely a bleeding type. Paints prepared with

such pigments, shows bleeding defects when applied on leather. Bleeding materials cannot
therefore be considered as a pigment.
 Abrasion
The particles of a good pigment must show a high degree of resistance to abrasion. High
resistance to abrasion for pigment particles are necessary to protect from internal friction
during flexing of leather.
 Crystallisation
If a pigment crystallizes out when present in a dilute paint emulsion, it must be discarded as a
pigment. The character of a crystal is quite different from its ground particles and so
crystallization is not good for pigments.
Classification of Pigments
It may be recalled that classified into the following two groups depending upon their origin
and compositions.
 Inorganic pigments.
 Organic pigments.
Inorganic pigments are of the two broad categories:
 Earth colours
 Prepared pigments
The overall classification of pigment is presented below.
Overall Classification
Inorganic Organic
Earth Prepared Fluorescent pig. Dye pig. Toners Lakers
White Coloured Sheen
Pearlescent
Prime
Advanced Extenders
Leather Technology – Lpde6031
Iridescent Page 120
/ fillers Metallics
Inorganic Pigments
Inorganic pigments are of the two broad categories:
1. Earth colours
2. Prepared pigments
Earth colours
Earth colours are simply mined ores like Limonite, Hematite, Umber etc. One and the same
kind of ore may exist in different colours, because of associated impurities. While limonites
(Fe2O3xH2O ) of Indian and African origin are bright yellow, the same of USA and France
are dark yellow, and Italian ores specially known as Sienna are medium to dark yellow. The
limonite from Cyprus and Turkey contains carbon and MnO 2 impurities, is of brown and is
known as Umber. Burnt umber refers to dark brown pigment obtained by burning Umber.
The body, covering power and fastness to heat, light and chemicals of earth colours in
general are better than prepared pigments. However, because of processing difficulties and
varying colour strength, earth colours do not find much favour with paint manufacturers,
nowadays.
Prepared Pigments
Prepared pigments belong to numerous chemical classes including elements, oxides,

sulphates, chromates, silicates, phosphates and carbonates. The pigments may be black,
white, coloured, or metallic.
Inorganic- pigments based finish formulations are increasingly used in the upgradation of
poorer quality leathers. Pigments provide protective functions also. Degradation and
embrittlement of film or substrate by UV and other radiations are arrested by pigments.
Pigments increase film durability by changing film permeability or encourage corrosion
retardance by chemical interactions with substrates.
Organic Pigments

Organic pigments are simply dyes either themselves insoluble or insolubilized. The greatest
of all virtue of all organic pigments is their extreme brilliance and consequent high tinctorial
strength. Being dyes, they absorb light in a very narrow range of wave length (i.e. single
colour) and this is responsible for their extra brilliance.
Essentially, they are of the following 4 types:
 Dye pigments
 Toners
 Lakes
 Polymer pigments including fluorescent pigments
Dye-pigments / Pigment-Dyes
Pigment-dyes or dye-pigments are defined as coloured, insoluble, organic compounds which
may be used as pigments without any special treatment. Its insolubility is responsible for their
use as pigments. The brilliance of colour possessed by organic pigments has added a new
dimension to this class of pigments and consequently, they have high tinctorial strength. But,
because of their transparency and low refractive index, organic pigments are noted for low
covering power also and by virtue of this they are used in the semi- aniline finishing of
leathers. Many of the organic pigments suffer from bronziness and poor solvent resistance,
typical of organic lakes. The solubility of these pigments brings about crystallization of
pigments causing a change in colour.
Azo pigments, Basic dye pigments, Phthalocyanin pigments, Quinacridone pigments and vat
dye pigments are some of the examples for organic pigments. Mono azo, diazo, azine, indigo
and anthroquinone dyes are widely used. Though brilliant and quite fast to acids and alkalies,
they bleed in organic solvents and plasticizers.
Toners (acid & basic)

These are acid and basic dyes insolubilized by precipitation with appropriate reagents. Acid
dyes are precipitated with metallic salts and similarly, basic ones may be insolubilized by
treatment with either tannic acid or complex inorganic heteropolyacids like PTA (Phospho
Tungstic Acid), PMA (Phospho Molybdic Acid) and PTMA. These acids impart intensity,
strength, stability, good light fastness to these pigments. The dyes present in these pigments
are Auramine O , Rhodmine 6G, Malachite green etc. The metallic ion and acid anion

become integral parts of acid and basic dyes respectively and make the complex toner
pigments.
 Intense shades
 Tinctorial strengths
 Poor light fastness.
Lakes
These are insoluble calcium, barium or manganese salt of a dye co-precipitated with an
insoluble sulphate such as that of aluminium. That is, they are dyed pigments, in a sense.
Many of the organic pigments available in the market are precipitated from dyes in presence
of inorganic carriers like hydrated alumina. The alumina is first dispersed in the dye solution
and then the metallic salt solution or hetero-polyacid is added when both dye and alumina
precipitate out as a homogeneous pigment.
Dye- SO3H + Na2CO3 _____ Dye-SO3Na + H2O +CO2
2Dye- SO3Na + BaCl2 -------- (Dye-SO3)2 Ba + 2NaCl.
Al2(SO4)3 + 3BaCl2 ___ 3BaSO4 + 2AlCl3
AlCl3 + Na2CO3 + H2O ____ Al (OH)3 + NaCI + CO2
Polymer Pigments
Dyes dispersed in polymers are knwn as polymer pigments. The dye is dispersed in
monomeric mixture and then the mixture is subjected to polymerization.
Fluorescent Pigment
These make a special case of polymer pigments in which the dyes incorporated are
fluorescing ones. Dyes include rhodamine or aminonaphthalimides. These absorb radiation at
particular frequencies in UV and visible regions and re-emit the energy at lower frequencies.
This re- emission makes the materials to glow in normal day-light. Their chief disadvantages
are:
1. Poor opacity (particle size 3-4µm)

2. High cost
3. Rapid fading
Difference between Organic and Inorganic Pigments
The amount of light reflected by inorganic pigment of a particular colour is generally more
than that by any organic pigment of same shade. So, the intensity (which is the measure of
reflected light) of an inorganic pigment is more than that of an organic pigment.
Brilliancy being purity of colour, organic pigments are more brilliant than inorganic
pigments.
Organic pigments and some lakes are prepared as precipitates and as such can be of very fine
powders imparting to this class of pigments high colour strength. And inorganics are inferior
to organic pigments in this respect.
In view of their fine particle size, the covering power of organic pigments should be more.
But, due to their very low refractive indices, the covering power of inorganic pigments is
more than that of organic pigments.
The fine size of organic pigments makes them easily wettable, more than inorganic pigments.
Organic compounds being softer solids than inorganic compounds, organic pigments have a
finer texture.
Because of their higher colour value, fine texture and relatively low opacity, organic
pigments are used in many industries such as textiles and printing inks. For that matter, they
are favoured for semi-aniline finishing, where uniformity of colour is needed with maximum
transparency.
A minute percentage of organic pigments dissolve in binder solution and causes uneven
shade in the finish film and this is called ‘bleeding’. Inorganic pigments generally do not
bleed.
Organic pigments are expensive, become fade on exposure to sunlight and provide less body
to the film. Inorganic pigments, on the other hand, are generally cheap, light fast and provide
good body.
Thus, both types of pigments have advantages and disadvantages and therefore, in leather
finishing it is difficult to replace one by the other.
Comparison between Organic and Inorganic:

Organic Inorganic
Good brilliancy Less brilliancy
Less covering power Good covering power
Tendency to cause bleeding No bleeding
Less settling More settling due to high density
Less body Good body
Less fastness to light Good light fastness
Available in the purest form (May contain impurities if made out of

earth colors).
Intensity is more Intensity is less
Particle size is small Particle size is bigger.
Bright, pure and richer in color. Less bright and less richness.
More expensive Less expensive.
Refractive index is very high High refractive index
Polymeric Materials and their Dispersions

Acrylates, Butadienes and Polyurethanes
The common synthetic binders in finishing are acrylates butadienes and polyurethanes. In
order to find out which is the right synthetic binder for a particular application the typical
characteristics for these binders have to be established.
Typical Characteristics of Acrylates

- Good light fastness
- Good hear stability
- Good hydrolytic stability
- Good drying properties
- Good wet properties
- Good adhesion
- Poor embossing properties
- Poor cold flex properties
- Poor covering properties
- Low price range

Typical Characteristics of Butadiene
- Modernity light fasters
- Poor heat stability
- Good hydrolytic stability
- Good wet properties
- Good embossing properties
- Good cold – flex properties
- Excellent covering power
- Sensitive to certain pigments
- Tackiness
- Moderate price range
These basic characteristics mentioned are not dependent on the supplier but can be tracked
back to the chemistry of such products. Compared to acrylates, butadienes contain two more
monomers.
Main Monomers for Polybutadienes
- Butadiene
- Styrene
Both compounds are responsible for the difference between acrylates and butadiene. The
molecular weight of both polymers is > 10, 00,000. The hydrophilic groups are either built-in
or predominantly external. This lowers the dispersion stability of the binder, but improves the
wet fastness of the base coat.
Polyurethanes
The third group of synthetic binders is the polyurethanes. Their build-up is totally different.
The chemical reaction is not a polymerization but a polyaddition;
- The choice of monomers is by far the largest;

- The molecular weight is below 100,000;
- The hydrophilic groups are predominantly built into the polymer chain causing higher
energy demands on drying.

The polyurethanes can be tailor made there are no typical attributes which cover the
majority of polyurethanes and there is no requirement in leather finishing which cannot
satisfied by polyurethane product.
Top Coats in Leather Finishing
Top coat is the final top most layer resting on the intermediate one. The main objects of this
layer are as follows
 To give the required degree of gloss.

 To protect the intermediate layer from scratch, frictional damages and abrasion.
 To make the finish film water proof.
 To protect the leather from damages due to sweat, acid, alkalis and other injurious
materials and vapour with which leather may came in contact.
 To provide extra resiliency, feel and smoothness to the leather.
 To make up the top surface of the leather ideal for embossing.
Types of Top Coats
Lacquer Based Top Coats (Non -Aqueous)
Nitro-cellulose and organic Cellulose Aceto Butyrate (CAB) lacquers contain polymer chains
which are fully mobile in the solvent medium. Free moving polymer chains will form a well-
entangled film during the drying process as shown in the figure 17.
The film formation of organic based top coats is further enhanced by the addition of
plasticizers being added to keep the polymer soft. Another characteristic of NC and CAB
lacquers is the low surface tension of organic solvents compared with water.
Figure17: Film formation of non-aqueous organic Top coats

Water Based Top Coats (Aqueous)
Aqueous top coat systems are completely different from lacquer solutions, as they comprise
discrete particles dispersed in water. Each particle contains a number of entangled polymer
chains. During drying of the top coat, the water evaporates and the particles are packed
together to form a honeycomb structure as illustrated in the figure 18.
Figure 18: Film formation of water based Top coats

Composition of a water based top coat system
In general, a water based top coat system consist of several components:
 Dull Resins
 Gloss Resins
 Thickener
 Levelling/Wetting agent
 Feel agents
 Defoaming agents
 Crosslinker
 Matting agent
Dulling and Glossy Top Coat Resins

These are mainly polyurethane or acrylic dispersions with selected dulling agents and
auxiliaries. These can provide different degree of hardness, gloss, flexibility, and other
relevant physical properties to cover the needs of modern leather finishing.
Feel Agents
Feel modifiers are used to adjust the handle and the physical properties of the top coat. There
are many different agents that can be used alone or in combination to adjust the feel and or

improve selected physical properties, such as the abrasion fastness. The tactile properties can
be described as dry, waxy, oily, greasy, slippery, silky, and can be achieved to varying
degrees.
Matting agents
Matting agents are mainly used to modify the degree of gloss of the finish, both in base coats
and in top coats. These products are supplied in water and solvent systems and are mainly
based on waxes or in order to obtain a higher matting effect, on silica. They are generally
mixed with different binders - acrylates, polyurethanes, protein and cellulose acetate butyrate.
The addition of matting agents to finishing formulations results in a dried, less tacky surface.
It is important not to use large amounts of matting agents because a white break coloration
can develop in the finish film.
Crosslinkers
Crosslinkers are chemical substances which crosslink the various polymers and improving
fastness properties. Most of the high performance top coats systems require a cross linker to
maximize the physical performance. The molecular structure of the polymer is enhanced by
crosslinking and these products also react with hydrophilic groups of other additives and feel
agents. Main improvements found in fastness to wet rub, water and abrasion resistance.
Types of Crosslinkers
There are four main types of crosslinkers for water based systems.
 Aziridine
This the most powerful and easy to use crossslinker, because it is less temperature dependant
compared with the alternatives. The product can be used in both base and top coats.
 Isocyanate
They have high reactivity and can be used in both base and top coats.
 Carbodiimide

This is the most selective type of product as they only react with carboxylic groups.
Compared with aziridine and diisocyante crosslinkers, they exhibit a medium high reactivity,
and are mainly used in combination with isocyanates to accelerate their reaction speed.
 Epoxy
These products are less effective than aziridine and diisocyanate crosslinkers, hence have a
longer pot life in prepared application mixes. They are mainly used in base coats.
Plasticizers
Dry film of polymeric materials can be, sometimes hard and brittle also. These items call for
flexibilizaiton for uses in surface coatings with satisfactory performance. The agents are
incorporated for the purpose of flexibilization is kwon as plasticizers. The requisites of
plasticizers are:
1. Compatibility with the filmer

2. Miscibility with the solvents
3. Extremely low volatile
4. Good low temperature flexibility
5. Chemical stability
6. Light stability
Moisture Blush, Cotton Blush, and Orange Peel
In the case of lacquer, film is formed by the evaporation of solvents. Some degree of rapidity
of evaporation is a necessity. However, Moisture blush, Cotton blush and Orange peel are
serious defects arising from improper evaporation of solvents
The surface on which lacquer is sprayed, gets cooled as a results of faster evaporation. If the
lowering of temperature gets below the Dew- point, then the moisture condenses on the
surface of the leather. And this moisture may be carried into the finish film by water miscible
co-solvents or even main solvents. The trapped water may cause haziness or blush is known
as Moisture Blush. It may be localized or wide spread whitening of the surface and causing
loss of gloss in coloured film.
Retarders: Retarders are slow boiling solvents (e.g., Butyl alcohol) which are miscible with
water can retard evaporation rate of all solvents and prevents moisture blushing under very
humid condition.

Cotton Blush
If the main solvent evaporates earlier than the diluent, then the NC precipitates and creates
haziness called Cotton Blush. NC is made from cotton and hence the name.
Orange Peel
Presence of solvent in the substrate surface is essential, to form a continuous wet film on the
leather surface before drying. On the other hand, if the solvents evaporates much earlier in its
way from the gun to the surface and it may result in failure to flow out on the surface. This
may result in poor anchorage, poor rub fastness, loss of gloss, poor film strength or non-
smooth film surfaces. These effects are known as Orange Peel.

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Ethiopian Institute of Textile and Fashion

Advance Leather Technology

Study/Teaching Material Prepared by

Dr. Rajan Karthikeyan

Leather Engineering Dept, Faculty of Apparel,

Ethiopian Institute of Textile and Fashion Technology,

Chapter 1- Collagen and skin structure

Chapter 2- Skin and its components

Chapter 3- Curing and preservation of hides and skin

Chapter 4-Pre-tanning operation

Advanced Leather Technology – Lpde6031 Page 2

Chapter 6 -Post tanning

Chapter 8- Cleaner option and future of leather processing

Advanced Leather Technology – Lpde6031 Page 3

Origin of Hides and Skins used by the Leather Industry:

Advanced Leather Technology – Lpde6031 Page 4

 Curing – to preserve skins during transport or storage.

 Soaking – to restore “cured” hides and skins to a natural raw condition.

 Unhairing – to remove the hair.

 Fleshing – to cut away unwanted fat and flesh.

 Deliming – to neutralize the alkali from liming

 Bating – to make the skin softer and cleaner.

Advanced Leather Technology – Lpde6031 Page 5

(c) After Tannage

Heavy leathers, e.g. Sole (or bottom) Leathers

Light leathers, e.g. Shoe Upper Leathers

 Washing – to free from surplus chrome salts.

 Neutralising – to adjust acidity.

 Dyeing – to obtain the required colour.

 Fatliquoring – a method of applying oil to achieve softness or “handle”.

 Setting Out – to remove creases and surplus moisture.

 Staking – to flex and soften the skin.

 Finishing or Seasoning – to improve appearance.

 Glazing – high pressure polishing; or

 Plating – in a hydraulic press to give a smooth, flat surface; or

 Embossing – in a press to produce a fancy design.

Advanced Leather Technology – Lpde6031 Page 8

Grain Layer of Cow:

Advanced Leather Technology – Lpde6031 Page 9

 Also poor merging of grain to corium mostly noticed in fallen hides.

Corium Major of Cow:

 Fibre bundles are more thinner in fallen hides.

Histological Structure of a Buffalo Hide

Epidermis of Buffalo Hide:

 The coarse hairs are lesser in number

Advanced Leather Technology – Lpde6031 Page 10

 The cells of the stratum germinatum contains pigment granules constituting of

Grain Layer of Buffalo Hide:

Corium Major of Buffalo Hide:

 It is also called the reticular layer of its network like appearance.

 The fibre bundles in the corium are relatively much larger.

Advanced Leather Technology – Lpde6031 Page 11

Flesh Layer of Buffalo Hide:

 It approximately covers 3 to 5 % of the total thickness of the hide or skin.

 It contains very much less amount of fat as considered to other skins.

Histological Structure of Goat Skin:

Epidermis of Goat Skin:

Grain Layer of Goat Skin:

Advanced Leather Technology – Lpde6031 Page 12

Corium Layer of Goat Skin: