Page |1 DEWAN A.H.

KAFI

Leather
Leather is a material created through the tanning of hides and skins of animals, primarily cattle hide. The
tanning process converts the putrescible skin into a durable, long-lasting and versatile natural material for
various uses.

Classification of Animal skin:

a. Hide: Large animal skin such as bulls, horses, cows & oxen.
b. Skin: small animal skin such as goat, sheep etc.
c. Kip: premature skin. Example: Skin of animals is smaller than a full grown calf.

Composition of hides and skins:

1. Water : 60% - 70%.
a. Free water – removed by pressure
b. Bound water – removed by chemical treatment.
2. Proteins : 19.2% - 32.7%.
3. Fats : 1.5% - 12.25%
4. Mineral matters : 0.36% – 0.5%
5. Coloring pigments – trace amount.

Steps of leather manufacturing:

1. FLAYING 10. TANNING
2. CURING OF SKINS a. VEGETABLE TANNING
3. TREMMING b. CHROME TANNING
4. SOAKING 11. NEUTRALIZATION
5. LIMING 12. RETANNING
6. FLESHING 13. DYEING
7. DELIMING 14. FAT LIQUORING
8. BATING 15. FINISHING
9. PICKING

*** Comparison of skin or and leather:

Skin or hides leather

pliability Soon lose pliability and become hard and brittle Retains pliability

permanence Putresce very quickly Extremely permanent, not

attacked by bacteria

Water resistance Adsorb water and are permeated easily by it Possesses great resistance to water

Boiling water Are converted to gelatin by hydration Attacked with great difficulty

Mechanical strength Fairly good Very good

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Processes: (pre tanning process)

1. Flaying:
Removal of hides & skins from the parental body is called flaying. Hides and skins obtained after flaying contain
water up to 60-70% of weight. In presence of such high quantity of moisture, the main chemical constituents
consisting of protein make them liable to bacterial attack and sound growth which being to decompose. Hence
the primary concern of tanner is to protect this raw material and the protection treatment administered soon
after the hides & skins are flayed is called curing.

2. Curing:
Curing creates an environment for the hides & skins in which the protein destroying organisms cannot
function. There are several methods to cure hides and skins. The three common processes are –
1. Wet salting
2. Dry salting
3. Drying.
All three processes reduce the moisture content of hides and skins. In the first two processes common salt is
used to dehydrate the hides & skins. In the second process further dehydration is achieved by natural control
drying. In many cases further protection is given by introducing chemical and anti bacterial agent. Curing is
very important because for only well cured hides and skins can produce high quality leather. This method of
curing requires a minimum of 3 or 4 weeks at about 13 0C, during which the hide losses part of its moisture by
dehydration and gains weight through salt adsorption. Curing has several advantages –
1. It is more rapid and uniform.
2. It provides greater protection before tanning
3. It requires no washing of hides before soaking back.
4. Produces leather of plumper grain.
3. Trimming:
Cured hides and skins arriving at a tannery are trimmed to remove to long shanks and other perimeter areas
which do not go into making of good leather. Trimmed hides are sorted for size and weight and formed into
batches. The trimmed hides and skins are then ready to undergo next treatment soaking.

4. Soaking:
Soaking as well as washing of the hides are very important, because if losted moisture from hides during curing
process is not restored, the hide will not respond properly to different operations. The main objectives of
soaking are –
1. To restore the lost moisture so that the chemical treatments that follows will achieve optimum result.
Soaking operation can be carried out in pits, paddles or drums. The method and duration of soaking very
according to the available equipment at a tannery and also depend upon the condition of raw stock.

Paddle method:
In the paddle method, the washing is done in a cylindrical wooden vessel, usually about 9 ft wide and 5 ft
depth, containing a rotor or paddle in 5 ft diameter. This paddle operates at approximately 15 rpm.
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Advantage:
1. The equipment is cheap.
2. Easy to operate and construct.
3. Use little power.
4. Is not so liable to injure the hides as is the drum method.
Disadvantage:
1. Main disadvantage is necessary high ratio of water to hide. (3 lb water/1 lb hide) and required hand
removal of hides from paddle.
Drum method:
In the drum method, a cylindrical wooden drum about 8 ft in diameter and internally fitted with wooden pegs
or shelves is used. The drum is rotated and gives the hides a tumbling effect during washing.
Disadvantage: this method can damage on the hides.

Condition of water use in soaking:

1. Water used for soaking should be soft medium hard. Hard water softens hides more slowly than soft
water and will precipitate soap from wetting agent.
2. Water contain organic matter will accelerate bacterial growth which damage the hide.
3. Small amount of sodium polysuphide, surface active agents are added which greatly accelerate
soaking.
Soaking operation is carried out in two stages
1. Dirt soak
2. Main soak
5. Liming:
Liming is a means of loosening and removing the epidermis and hair from the hide. The main objectives of
liming process are
1. To remove the epidermis layer and at the same time to loosen the hair.
2. Removal of interfibrillary proteins to make the final leather pliable and soft to touch.
3. To remove natural fats in the leather by saponification in order to obtain non patchy and uniform
surface in the final leather.
Lime is most widely used agent for hair loosening .lime (CaO) is sparingly soluble in water. It combined with
water to form Ca(OH)2 .At 200C saturated lime solution is approximately N/20 strength with a P H of 12.6. Lime
water derives its power to loosen hair from its alkaline character. Due to its limited solubility in water it has
mild action on hides and skin.
The epidermis and hair are chiefly composed of keratin is a protein containing cystine residue which is easily
attacked by alkali. Lime attacks the disulfide link in the keratin and thus softens the hair and removes the
epidermis. This action may be represented as
R-S-S-CH2-R + H2O  RSH + RCH2OH
RCH2SOH  RCHO +H2S
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Types of liming:
There are two types of liming process:-
1. Straight liming.
2. Rapid liming
 Straight liming:
When liming alone is used, the process is known as straight liming. It takes about 8to 12 days depending on
temperature. Hydrolysis of soft keratin in the hair follicle would allow removal of hair from the hair root
without significant chemical action. The longer duration of straight liming causes growth of bacteria in the lime
liquor. The hydrolyzed proteins form a culture medium for further growth of bacteria. Straight liming generally
adopted for vegetable tanned leather.

 Rapid liming:
The liming processes can be accelerated by adding sharpening agent like sodium sulphide, dimethyl amine etc.
when lime is sharpened with Na 2S, causes rapid loosening of hair. This high concentration of strong reducing
agent can cause breakdown of S-S linkage of keratin. This action takes place primarily at the surface of hair.
The action is very rapid and destruction of hair takes place in a matter of minutes.

Process of liming:
Liming is usually done in wooden or concrete vats. The hides are tied or hooked together and placed in a vat
containing water with 10% of the weight of the hides in lime and 2% of the lime weight in sharpening agent.
The hides are moved ahead daily in a series of consisting of three to seven vats; remain in each one a day.
Then hides enter a fresher lime vat. These vats are drained and lime charge renewed about every 2 weeks in
summer and 4 to 5 weeks in winter.
After the hides the hides have passed through his series of lime vats, they are usually placed in a vat of warm
water which tends to shrink them and permits the easier removal of hair. The hair and epidermis are brought
in contact with a roller set with dull knife blades which rub off the loose hair and epidermis.

6. Fleshing:
Limed hides and skins are called pelts. After liming the skin or hide become more swollen and sticky. Flesh
adhered to the flesh side can easily be removed. The process of removal of sticky flesh from the skin by hand
or fleshing machine is called fleshing.

7. Deliming:
The alkaline chemicals used in liming process are still present in relatively large amounts in two forms-
1. Partly as free alkali
2. Partly chemically combined with collagen
The main objective of deliming process is removal of alkali and the adjustment of P H for next batting process.
It is essential to remove the surface alkanity of the pelts before subject them to process of tanning either by
vegetable tanning or chrome tanning. Otherwise vegetable tannins will precipitate forming calcium tannate,
which is insoluble in water and gives darker color and harsh feel to the grain.
The chrome salt will combined with alkali to form higher basicity chrome compound. They will fixed on to the
grain and flesh side preventing further penetration of chrome into the pelts and thereby causing patchiness
and roughness on the surface.
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In deliming process:
1. Free alkali which is in soluble in water is removed partially by washing the pelts in water.
2. After washing chemically combined alkali is removed by neutralizing it with acids, acid salt, ammonium
salts.
More commonly used chemicals for deliming process are –
1. Acid: HCl; H2SO4; formic acid, acetic acid, lactic acid etc.
2. Acid salts: sodium bisulphate, sodium bisulphate etc.
3. Ammonium salt :(NH4)2SO4, NH4Cl, etc.
Strong acids are rarely used. They are used if at all in dilute form. In concentrated form they swell the grain
and produce cranky leather. While using these agents, the amount applied should be such that the P H of
deliming bath does not fall below 5.
Among the acid formic and lactic acid are generally used as they are very weak and do not swell the grain of
the pelts.
(NH4)2SO4, NH4Cl are most regularly used. Among these (NH 4)2SO4, is considered to be better, since in
neutralizing lime CaSO4 forms which gives more filling action. When NH 4Cl is used CaCl2 is formed which is
soluble in water and this NH4Cl delime more quickly.

Process of deliming:
Fleshed hides or skins are washed in paddle or drum with running water to remove as much as possible the
free alkali. Then to speedup the deliming process, the deliming chemicals are employed to neutralize the
alkalinity. During the process the tanner may cut the skin with knife and use an indicator to measure the depth
to which the deliming operation has proceeded. The fully delimed pelts produce softer leather. While firm or
harder types complete deliming is not desired.
A limed pelt has PH of 12.5 – 13. In deliming, this PH brought down to 8.2 - 8.4. The pelts are now ready for
batting.

8. Batting:
The skin contain non-leather making constituent such as degraded protein, color pigments, grease, lime and
for further refinement are subjected to a process called batting. It is only the steps in leather processing where
enzymatic process cannot be substituted by chemical process. Modern bating procedures employ pancreatic
enzymes or proteolytic enzymes of bacterial origin. The concept of softening hides by treating these in warm
infusion of animal dung has been termed as bating. Bating is carried out in paddles or drums.

Objectives of batting:
1. Remove most of lime
2. Produces a silky grain
3. Removes all swelling and plumping. Bated pelts are slippery, non-elastic or flaccid.
4. The remains hypodermic tissue (flash) is loosened, so that they can easily be removed by scrapping.
5. Increase the degree of starch possessed by the finished leather.
6. Short hairs, grease and lime soaps, dark colored pigments, traces of epidermis are all loosened and
become easily removed.
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Acid bating:
Normally bating is carried out in the alkaline P H range since enzymes present in pancreatic and microbial bates
are optically active at that P H range. The pelt treated with proteolytic enzymes in acidic P H range derives special
characteristics. The main features of bating in acidic condition are-

1. Bating operation can be carried out at a temperature between 25-32 0 C.

2. Deliming, bating, picking and chrome tanning can be carried out in the same drum.
3. Reduce the operational cost.
4. Partially chrome tanned leather can be treated with acid bate for the manufacture of quality garment
leather. The alkaline bate is not suitable for such treatment.

Sign of batting effect:

The following sign will be indicate the effect of proper bating-
1. The grain of the bated pelts should be fallen silky and slippery.
2. The pelt should be white clean and pores
3. The flesh comes off easily when scratched with finger nail.
After bating the skins and hides are rinsed for 10-12 minutes to remove lime salt and to cool down the pelts.
After rinsing pelts should immediately be transferred to the pickle or tanning bath. This is the only known
method to stop further action of bate enzyme on the pelts.

9. Pickling:
The two important objectives of pickling are-
1. To condition the pelts for tanning.
2. To preserve delimed and bated pelts for tanning.
It is also serves another useful function at this stage. The skins can be easily sorted for production of different
types of leather

Necessity of pickling:
Delimed and bated pelts have a PH 7.5-8.5. Indicating continued alkalinity. If they are treated with chrome
tanning agents without pickling, the acidity in the chrome tanning agent will be consumed to neutralize the
alkalinity of the pelt. Hence the chrome tanning agents become precipitated and form a heavy deposit on the
surface of the pelt. Hence the chrome tanning agents become precipitated and form a heavy deposit on the
surface of the pelt.
Pickling is a preservation technique. Raw hides and skins putrefy when kept in open atmosphere for even a few
hours. Proteolytic enzymes present in the hides or secrated by bacteria hydrolyze protein. These enzyme and
bacteria will act only when condition of humidity temperature and alkalinity are favorable for the putrefying
action. At low pH or high acid condition of the pickled pelts will prevent the enzyme from acting on the pelts.

Process:
When the pelts are treated in the acid salt pickle liquor they absorb acid, which is partially utilize to,
 Neutralize the free alkanity
 Combine chemically with collagen.

The remaining acid is help up mechanically in the space between the fiber bandles of the pelt and lowered
pH to about 2.0-3.5, depending upon quantity of acid used in the pickling.
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The pickling process first calls for the addition of common salt or brine to the system. If acid is used directly, it
will cause swelling and plumping of pelts on account for the adsorption of water by the collagen in the
presence of acid. If the plumping is not properly checked and controlled, the pelts will be damaged. A certain
minimum concentration of neutral salts is essential to prevent damage to the pelt.

H2SO4+Commonsalt, HCl, HCOOH are used as pickling is important in determining the quality of leather.

Chrome tanning:
About 90% of the world’s production of light leather is chrome tanned. In the chrome process, the
combination of the chromium salts and hide fibers is much more rapid and takes place without degree of
swelling that occurs in vegetable tanning .therefore the chrome leather is more pliable and looser in structure.
Fillers are usually added to give water resistance properties. The chrome leather is characterized by high
content of original hide proteins and mineral matters and by low content of water soluble materials.

Mechanism:
The mechanism of chrome tanning has not been well established. The tanning liquor has the same electrical
charge as the hide. Therefore the mechanism of co-precipitation as given under vegetable tanning is not
applicable. It is possible that the collagen forms coordination compound with the chromium salts.

Process:
Chrome tanning is usually subdivided into two process.
1. One bath process: use basic chromium sulphate .
2. Two bath process: use sodium dichromate.
However in each case chromium salt is used in place of the vegetable tanning agent.

One bath process:

The chrome liquor for one bath process is usually made by reducing acidified solution of sodium dichromate by
slowly adding a solution of glucose to it or by bubbling SO 2 through the dichromte.
Na2Cr2O7 + 3SO2 + H2o  2Cr(OH)SO4 + Na2SO4
The preferred one bath process from stand point of quality and control is to add the chrome liquor to the
wooden drum containing pickled skins and exhausted pickled liquor. Usually mold and mildew inhibitors such s
penta chloro phenol are added. The drum is rotated 5 to 6 hr until the tanning operation is complete.
Page |8 DEWAN A.H. KAFI

Two bath process:

After pickling, the hides are place successively in two drums or paddle vats containing about 5% of the weight
of the hides in Na2Cr2O7 solution with same salt and HCl. The skin are allowed to remain in each liquor over
night and are then pulled out and allowed to drain. After an hour or two, the hides are placed in another
paddle vat containing approximately 15% of the weight of hides in Na 2S2O3. the hides are left in this liquor over
night, pulled out in the morning and washed in a drum containing water. Borax is added to reduce the acidity
of the leather to the desired extent. In the process, the properties and composition of the finished leather are
greatly influenced by many factors that can be controlled during tanning. Such factors are –
1. Salt concentration 3. Agitation
2. Temperature 4. Time proportion of protein to liquor.

Vegetable tanning:
The main use of vegetable tanning is for heavy leathers used for soles and belting.
The active ingredients in vegetable tanning reagents consist of a class of organic compounds known as tannins,
which are found quite abundantly in vegetable kingdom. The chief sources that have attained commercial
importance for supplying tannin for leather manufacturing are-
1. Barks 4. Fruits
2. Leaves 5. Pods &
3. Twigs 6. Root of various trees, shrubs
The trees are – Chest nut, Oak, Hemlock, Quebracho, wattle trees, Myrobalan nuts & Gambier.

Two tanning groups:

 Catechol : Chest nut, Oak, Hemlock
 Pyrogallol : wattle tree, myrobalan nut, Gambier.
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 Extraction of tannin:
*** Open vat leaching Method:
It is probably the oldest but most widely and commonly use.

1. Bark, wood or tannin containing materials is chopped into small pieces.

2. Shredded in a bark mill and leaching tank.
3. Leaching tanks are equipped with false bottoms, heating coils and usually arranged in batteries of
eight.
4. The bottom of each tank is fitted with a pipe through which the liquor may be pumped form one tank
to another.
5. Leaching of the bark is accomplished by counter current extraction with water. The bark is the dumped
and discarded.
6. The fresh water enters at its boiling point and by means of heating coils in the vats the temperature
can be controlled, so that it cools slowly and about 16 0C for the last leach.
7. The extract is usually muddy and contains insoluble matter. It is then clarified by filler pressing, settling
decanting or centrifugation. The liquid is concentrated in vacuum evaporators or especially
constructed vacuum driers.

How they acts:

Tannins are complex mixtures of glucosides of various poly phenols. Their action on skin is to combine with the
protein. The tannins are acts as negatively charged colloids and proteins in the skins are positively charged in
acid media. Thus the tannins neutralize the charge on the proteins and co-precipitation or combination of the
tannins and proteins occurs. Other complex processes also take place.
As the proteins have negative charge when is alkaline media, it is necessary to neutralize all of the lime from
the liming process before tanning.
During the tanning process the tannins are liberate sugars which are oxidized to acids and thus keep the liquor
acidic.
Skin + tannin leather + sugar
Sugar (oxidation) acid
After complete precipitation of the protein the aggregate has the capacity to adsorb large quantities of tannin.
Skins may increase in weight as much as 300% during tanning operation.
P a g e | 10 DEWAN A.H. KAFI

Synthetic tannin (syntans):

Syntans are condensation products of sulfonated phenols and formaldehyde capable of converting animal skin
into leather. Syntans may be classified according to use as-
- Auxiliary - Replacement tannin.
- Complimentary
All syntans belonged to the first two classes. They are functioned as-
1. Adjuncts and dye mordants.
2. For bleaching chrome leather.
3. For solubilizing the speed of penetration of the natural tannins into leather.

Vegetable tannin process:

Vegetable tanning is usually done in wooden vats 8 ×7 × 5 ¿6 ft which contain the tan liquors and hides. Since
the hides remains in the liquor for 1 or more months. Many vats are required and they must be cheap and
durable. Hides and tannins are run counter carefully. Hides first enter the oldest and weakest tannin liquor to
prevent complete plugging of the surface pores and subsequent poor penetration of the tannins through the
skins by strong liquor.
They pass successively through liquors of increasing strength until they leave the fresh and strongest liquor as
fully tanned leather. The ratio of liquor to hide is kept as low as possible and usually of 4-6 lb of liquor per
pound of hide.
The art in tanning lies in the careful selection and blending in the proper proportion of various tannins so as to
give the desired type and color of leather.
Sometimes the hides are placed on rockers or paddle for first 15-20 days to give them a gentle movement in
the liquid which tends to accelerate the tanning and make more uniform leather.
Many attempts have recently been made to speed up the tanning time and to shorten the expensive and
tedious aging and mellowing in tan liquors such as-
1. Immediate introduction of hide into a strong tanning agent.
2. Use of formaldehyde
3. Use of different solvent.
4. Use of high temperature
5. Use of alternations of pressure and vacuum.
But it is claimed that a poorer fiber grain and yield are obtained by these means.

 Commercial preparation of tanning extract:

For vegetable tanning:
Basis : 125 kg vegetable tan leather. - Tan bark : 20 kg
- Hide : 100 kg - Oil :
- Lime : 10 kg  sole- 2kg
- Na2S : 2 kg  betting -8kg
- Water : 3122 L  harness- 20kg
- Dye : 11 kg - Electricity : 8 MJ

- Lactic acid : 1.2 kg - Direct labour : 4.4 work-hr

For chrome tanning:

P a g e | 11 DEWAN A.H. KAFI

Basis : 80 kg chrome tan leather.

- Hide : 100 kg  harness- 20kg

- Lime : 10 kg - Electricity : 8 MJ
- Na2S : 2 kg - HCl : 25 Kg
- Water : 5000 L - NaCl : 20 Kg
- Dye : 11 kg - Na2Cr2O7.2H2O : 5Kg
- Oil : - Na2S2O3 : 15 Kg
 sole- 2kg - Borax(Na2B4O7.10H2O) : 2Kg
 betting -8kg

 Commercial aspects of leather:

Post tanning operations:
The leather after tanning is given variety of treatments according to the end use.
1. Removal of excess water and tan liquor:
The leather contains excess water and tan liquor specially in case of vegetable tanning. The goods are dipped
in vat containing mild tanning liquor which leaches out the uncombined tannin. The stock is then pressed in a
hydraulic press or by passing it through a wringer. In case of vegetable tanned leather, oil is applied on grain
side so that evaporation takes place from flesh side surface.
2. Shaving and splitting:
This is done with the help of a sharp knife. For light leathers, the leather is shaved on a shaving machine. The
machine has sharp spiral knife blades thus reducing thickness by removing extra stock from flesh side.
3. Neutralizing and coloring:
After shaving chrome tanned leather is washed in a drum, neutralized with mild alkali and again washed. The
neutralized stock is dyed in direct dye solution in warm water. Vegetable tanned leather are sometimes
bleached also with oxalic acid or sulphuric acid or formic acid before dyeing. Hypo may be used to remove
excess acid. Dyeing is performed in drums, about 0.5 to 2.0 present basic dyes based on the weight of leather
dissolved in warm water (50-600C) being used. The drum is rotated for half an hour and then little formic acid
added to destroy excess dye. The excess dye is drained and sulphonated neat foot oil emulsions are applied.
This process is known as fat liquoring. Chrome leathers, semi chromes after dyeing and vegetable tanned
leathers after bleaching are fat liquored to improve smoothness, fuel, tensile strength and water resistance.
The fat liquoring is done at 40-700C for about half an hour.
4. Drying:
Different drying methods are used depending on the type of leather. Chrome tanned leathers are dried by
suspending in drying rooms or by passing through air heated tunnels. Vegetable tanned leathers are dried by
taking on wooden frames and then stacking in tunnels through which air with controlled temperature and
humidity is passed.
5. Finishing operation:
Light leathers are finished by applying pigment coat, plasticizers etc. they may be sprayed on the grains or
applied by hand. Acrylic resins, lacquers may also be used. Chrome leather is glazed by a machine having
rotating glass cylinder. The friction improves the glaze and imparts a glassy finish to the waxed or lacquer
P a g e | 12 DEWAN A.H. KAFI

coated leather. Sole leather is finished by applying oil to the grain surface & passing it through heavy roller.
Vegetable tanned leathers are given decorative patterns by embossing with a hydraulic press.