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

*** Comparison of skin or and leather:
Skin or hides pliability permanence Soon lose pliability and become hard and brittle Putresce very quickly leather Retains pliability Extremely permanent, attacked by bacteria not

Water resistance Boiling water Mechanical strength

Adsorb water and are permeated easily by it Are converted to gelatin by hydration Fairly good

Possesses great resistance to water Attacked with great difficulty Very good

the washing is done in a cylindrical wooden vessel. 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. Drying. 3. during which the hide losses part of its moisture by dehydration and gains weight through salt adsorption. The three common processes are 1. 4. because if losted moisture from hides during curing process is not restored. Curing has several advantages 1. the hide will not respond properly to different operations. The main objectives of soaking are 1. There are several methods to cure hides and skins. To restore the lost moisture so that the chemical treatments that follows will achieve optimum result. The trimmed hides and skins are then ready to undergo next treatment soaking. Soaking: Soaking as well as washing of the hides are very important. 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. Paddle method: In the paddle method. In the first two processes common salt is used to dehydrate the hides & skins. Flaying: Removal of hides & skins from the parental body is called flaying. Trimmed hides are sorted for size and weight and formed into batches. the main chemical constituents consisting of protein make them liable to bacterial attack and sound growth which being to decompose. 4. Soaking operation can be carried out in pits. Dry salting 3. 3. It provides greater protection before tanning It requires no washing of hides before soaking back. containing a rotor or paddle in 5 ft diameter. In presence of such high quantity of moisture. Produces leather of plumper grain. In the second process further dehydration is achieved by natural control drying. . paddles or drums. Hides and skins obtained after flaying contain water up to 60-70% of weight. KAFI Processes: (pre tanning process) 1. It is more rapid and uniform. Curing is very important because for only well cured hides and skins can produce high quality leather. Curing: Curing creates an environment for the hides & skins in which the protein destroying organisms cannot function. All three processes reduce the moisture content of hides and skins. 2. Wet salting 2.H. This paddle operates at approximately 15 rpm. usually about 9 ft wide and 5 ft depth. 2. This method of curing requires a minimum of 3 or 4 weeks at about 130C.P age |2 DEWAN A. In many cases further protection is given by introducing chemical and anti bacterial agent. The method and duration of soaking very according to the available equipment at a tannery and also depend upon the condition of raw stock.

DEWAN A. Easy to operate and construct. Disadvantage: this method can damage on the hides. Hard water softens hides more slowly than soft water and will precipitate soap from wetting agent. 2. Main disadvantage is necessary high ratio of water to hide. This action may be represented as R-S-S-CH2-R + H2O €p RSH + RCH2OH RCH2SOH €p RCHO +H2S . Removal of interfibrillary proteins to make the final leather pliable and soft to touch. Drum method: In the drum method. surface active agents are added which greatly accelerate soaking. Soaking operation is carried out in two stages 1. 2. Condition of water use in soaking: 1. a cylindrical wooden drum about 8 ft in diameter and internally fitted with wooden pegs or shelves is used. To remove natural fats in the leather by saponification in order to obtain non patchy and uniform surface in the final leather. Is not so liable to injure the hides as is the drum method. The epidermis and hair are chiefly composed of keratin is a protein containing cystine residue which is easily attacked by alkali.6. 3. Use little power. Lime water derives its power to loosen hair from its alkaline character. The drum is rotated and gives the hides a tumbling effect during washing. KAFI Disadvantage: 1. 2. 3. (3 lb water/1 lb hide) and required hand removal of hides from paddle. 3. Small amount of sodium polysuphide. Lime attacks the disulfide link in the keratin and thus softens the hair and removes the epidermis. 4. It combined with water to form Ca(OH)2 . Water contain organic matter will accelerate bacterial growth which damage the hide. Liming: Liming is a means of loosening and removing the epidermis and hair from the hide.At 200C saturated lime solution is approximately N/20 strength with a PH of 12.H. The equipment is cheap. To remove the epidermis layer and at the same time to loosen the hair. Due to its limited solubility in water it has mild action on hides and skin. Lime is most widely used agent for hair loosening . Water used for soaking should be soft medium hard. Dirt soak 2.lime (CaO) is sparingly soluble in water. Main soak 5.P age |3 Advantage: 1. The main objectives of liming process are 1.

when lime is sharpened with Na2S. dimethyl amine etc. Process of liming: Liming is usually done in wooden or concrete vats. Partly chemically combined with collagen The main objective of deliming process is removal of alkali and the adjustment of PH for next batting process. KAFI Types of liming: There are two types of liming process:1.P age |4 DEWAN A. The hydrolyzed proteins form a culture medium for further growth of bacteria. 7. 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. 2. Fleshing: Limed hides and skins are called pelts. The process of removal of sticky flesh from the skin by hand or fleshing machine is called fleshing. they are usually placed in a vat of warm water which tends to shrink them and permits the easier removal of hair. This action takes place primarily at the surface of hair. After liming the skin or hide become more swollen and sticky. Straight liming. causes rapid loosening of hair. This high concentration of strong reducing agent can cause breakdown of S-S linkage of keratin. 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. which is insoluble in water and gives darker color and harsh feel to the grain. Flesh adhered to the flesh side can easily be removed. 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. After the hides the hides have passed through his series of lime vats.H. Then hides enter a fresher lime vat. remain in each one a day. The action is very rapid and destruction of hair takes place in a matter of minutes. It takes about 8to 12 days depending on temperature. 6. These vats are drained and lime charge renewed about every 2 weeks in summer and 4 to 5 weeks in winter. Otherwise vegetable tannins will precipitate forming calcium tannate. The hair and epidermis are brought in contact with a roller set with dull knife blades which rub off the loose hair and epidermis. Deliming: The alkaline chemicals used in liming process are still present in relatively large amounts in two forms1. Straight liming generally adopted for vegetable tanned leather. Rapid liming  Straight liming: When liming alone is used. The hides are moved ahead daily in a series of consisting of three to seven vats. Partly as free alkali 2.  Rapid liming: The liming processes can be accelerated by adding sharpening agent like sodium sulphide. The chrome salt will combined with alkali to form higher basicity chrome compound. the process is known as straight liming. 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. .

Bating is carried out in paddles or drums. acetic acid. The concept of softening hides by treating these in warm infusion of animal dung has been termed as bating. The fully delimed pelts produce softer leather. traces of epidermis are all loosened and become easily removed. the amount applied should be such that the PH of deliming bath does not fall below 5. formic acid.H. NH4Cl. color pigments. Acid: HCl.5 batting. Free alkali which is in soluble in water is removed partially by washing the pelts in water. Strong acids are rarely used. 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. since in neutralizing lime CaSO4 forms which gives more filling action. dark colored pigments. is considered to be better. In deliming. sodium bisulphate etc. Modern bating procedures employ pancreatic enzymes or proteolytic enzymes of bacterial origin. It is only the steps in leather processing where enzymatic process cannot be substituted by chemical process. 3. ammonium salts. Objectives of batting: 1. . Ammonium salt :(NH4)2SO4. 3. 5. When NH4Cl is used CaCl2 is formed which is soluble in water and this NH4Cl delime more quickly. etc. Batting: The skin contain non-leather making constituent such as degraded protein. Acid salts: sodium bisulphate. While using these agents. 4. H2SO4. Among these (NH4)2SO4. NH4Cl are most regularly used. In concentrated form they swell the grain and produce cranky leather. lime and for further refinement are subjected to a process called batting. 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. the deliming chemicals are employed to neutralize the alkalinity.8. lactic acid etc. 13. Increase the degree of starch possessed by the finished leather. 2. (NH4)2SO4. Bated pelts are slippery. While firm or harder types complete deliming is not desired.4. A limed pelt has PH of 12. The pelts are now ready for 8. so that they can easily be removed by scrapping. non-elastic or flaccid. More commonly used chemicals for deliming process are 1. After washing chemically combined alkali is removed by neutralizing it with acids. this PH brought down to 8.P age |5 DEWAN A. Among the acid formic and lactic acid are generally used as they are very weak and do not swell the grain of the pelts. 6. grease. 2. They are used if at all in dilute form. 2. grease and lime soaps. Then to speedup the deliming process.2 . KAFI In deliming process: 1. Remove most of lime Produces a silky grain Removes all swelling and plumping. acid salt. The remains hypodermic tissue (flash) is loosened. Short hairs.

Partially chrome tanned leather can be treated with acid bate for the manufacture of quality garment leather. 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. Bating operation can be carried out at a temperature between 25-320 C. 2. Hence the chrome tanning agents become precipitated and form a heavy deposit on the surface of the pelt. The alkaline bate is not suitable for such treatment. After bating the skins and hides are rinsed for 10-12 minutes to remove lime salt and to cool down the pelts. The remaining acid is help up mechanically in the space between the fiber bandles of the pelt and lowered pH to about 2. At low pH or high acid condition of the pickled pelts will prevent the enzyme from acting on the pelts.H. Hence the chrome tanning agents become precipitated and form a heavy deposit on the surface of the pelt. The flesh comes off easily when scratched with finger nail. Pickling is a preservation technique.0-3. This is the only known method to stop further action of bate enzyme on the pelts.5-8. If they are treated with chrome tanning agents without pickling. 9. The pelt should be white clean and pores 3.  Neutralize the free alkanity  Combine chemically with collagen. Raw hides and skins putrefy when kept in open atmosphere for even a few hours. The pelt treated with proteolytic enzymes in acidic PH range derives special characteristics. These enzyme and bacteria will act only when condition of humidity temperature and alkalinity are favorable for the putrefying action. Deliming. Process: When the pelts are treated in the acid salt pickle liquor they absorb acid. 2.5. the acidity in the chrome tanning agent will be consumed to neutralize the alkalinity of the pelt. 2. The main features of bating in acidic condition are1. . which is partially utilize to. 3. Indicating continued alkalinity. 4. Pickling: The two important objectives of pickling are1. After rinsing pelts should immediately be transferred to the pickle or tanning bath. Proteolytic enzymes present in the hides or secrated by bacteria hydrolyze protein. KAFI Acid bating: Normally bating is carried out in the alkaline PH range since enzymes present in pancreatic and microbial bates are optically active at that PH range. To condition the pelts for tanning. To preserve delimed and bated pelts for tanning. Sign of batting effect: The following sign will be indicate the effect of proper bating1. picking and chrome tanning can be carried out in the same drum. bating. Reduce the operational cost.5.P age |6 DEWAN A. depending upon quantity of acid used in the pickling. The grain of the bated pelts should be fallen silky and slippery.

However in each case chromium salt is used in place of the vegetable tanning agent. HCOOH are used as pickling is important in determining the quality of leather. Two bath process: use sodium dichromate.P age |7 DEWAN A. 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 . In the chrome process. H2SO4+Commonsalt. The chrome leather is characterized by high content of original hide proteins and mineral matters and by low content of water soluble materials. .H. If the plumping is not properly checked and controlled. Na2Cr2O7 + 3SO2 + H2o €p 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. Fillers are usually added to give water resistance properties. 2. A certain minimum concentration of neutral salts is essential to prevent damage to the pelt. 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 SO2 through the dichromte. It is possible that the collagen forms coordination compound with the chromium salts.therefore the chrome leather is more pliable and looser in structure. Process: Chrome tanning is usually subdivided into two process. KAFI The pickling process first calls for the addition of common salt or brine to the system. Chrome tanning: About 90% of the world s production of light leather is chrome tanned. HCl. Therefore the mechanism of co-precipitation as given under vegetable tanning is not applicable. Mechanism: The mechanism of chrome tanning has not been well established. If acid is used directly. 1. Usually mold and mildew inhibitors such s penta chloro phenol are added. it will cause swelling and plumping of pelts on account for the adsorption of water by the collagen in the presence of acid. The tanning liquor has the same electrical charge as the hide. the pelts will be damaged. One bath process: use basic chromium sulphate . The drum is rotated 5 to 6 hr until the tanning operation is complete.

wattle trees. Two tanning groups:  Catechol : Chest nut. Time proportion of protein to liquor. The active ingredients in vegetable tanning reagents consist of a class of organic compounds known as tannins. Root of various trees. Oak. The skin are allowed to remain in each liquor over night and are then pulled out and allowed to drain. Twigs 4. Vegetable tanning: The main use of vegetable tanning is for heavy leathers used for soles and belting. . the hides are left in this liquor over night. After an hour or two. Hemlock  Pyrogallol : wattle tree. Leaves 3.H. the hides are placed in another paddle vat containing approximately 15% of the weight of hides in Na2S2O3. the properties and composition of the finished leather are greatly influenced by many factors that can be controlled during tanning. Agitation 4. Hemlock. shrubs The trees are Chest nut. The chief sources that have attained commercial importance for supplying tannin for leather manufacturing are1. Fruits 5. In the process. Temperature 3. pulled out in the morning and washed in a drum containing water.P age |8 DEWAN A. Borax is added to reduce the acidity of the leather to the desired extent. Gambier. Oak. Barks 2. myrobalan nut. Myrobalan nuts & Gambier. Pods & 6. Such factors are 1. 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. Salt concentration 2. KAFI Two bath process: After pickling. which are found quite abundantly in vegetable kingdom. Quebracho.

The liquid is concentrated in vacuum evaporators or especially constructed vacuum driers. . The tannins are acts as negatively charged colloids and proteins in the skins are positively charged in acid media. Shredded in a bark mill and leaching tank. 7.P age |9 DEWAN A. As the proteins have negative charge when is alkaline media. Their action on skin is to combine with the protein.H. 3. KAFI  Extraction of tannin: *** Open vat leaching Method: It is probably the oldest but most widely and commonly use. Bark. 1. Other complex processes also take place. The bark is the dumped and discarded. Skins may increase in weight as much as 300% during tanning operation. The extract is usually muddy and contains insoluble matter. Leaching of the bark is accomplished by counter current extraction with water. wood or tannin containing materials is chopped into small pieces. The fresh water enters at its boiling point and by means of heating coils in the vats the temperature can be controlled. settling decanting or centrifugation. 6. heating coils and usually arranged in batteries of eight. The bottom of each tank is fitted with a pipe through which the liquor may be pumped form one tank to another. Skin + tannin leather + sugar Sugar (oxidation) acid After complete precipitation of the protein the aggregate has the capacity to adsorb large quantities of tannin. How they acts: Tannins are complex mixtures of glucosides of various poly phenols. 4. 5. so that it cools slowly and about 160C for the last leach. Leaching tanks are equipped with false bottoms. Thus the tannins neutralize the charge on the proteins and co-precipitation or combination of the tannins and proteins occurs. During the tanning process the tannins are liberate sugars which are oxidized to acids and thus keep the liquor acidic. it is necessary to neutralize all of the lime from the liming process before tanning. 2. It is then clarified by filler pressing.

The ratio of liquor to hide is kept as low as possible and usually of 4-6 lb of liquor per pound of hide. 2.2kg y betting -8kg y harness.Na2S : 2 kg . Syntans may be classified according to use as. Since the hides remains in the liquor for 1 or more months. Use of formaldehyde Use of different solvent.Replacement tannin. Use of high temperature Use of alternations of pressure and vacuum. 2. Adjuncts and dye mordants.2 kg Tan bark Oil : : 20 kg - Electricity Direct labour y sole. But it is claimed that a poorer fiber grain and yield are obtained by these means.H.Dye : 11 kg . 5. KAFI Synthetic tannin (syntans): Syntans are condensation products of sulfonated phenols and formaldehyde capable of converting animal skin into leather. Immediate introduction of hide into a strong tanning agent. They pass successively through liquors of increasing strength until they leave the fresh and strongest liquor as fully tanned leather. They are functioned as1.Lactic acid : 1.P a g e | 10 DEWAN A. 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 as1.Water : 3122 L .Auxiliary .20kg : 8 MJ : 4. 3.  Commercial preparation of tanning extract: For vegetable tanning: Basis : 125 kg vegetable tan leather. For solubilizing the speed of penetration of the natural tannins into leather. . . Hides and tannins are run counter carefully.4 work-hr . 4. Many vats are required and they must be cheap and durable. 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. 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.Hide : 100 kg .Complimentary All syntans belonged to the first two classes. For bleaching chrome leather. Vegetable tannin process: Vegetable tanning is usually done in wooden vats    which contain the tan liquors and hides.Lime : 10 kg . 3.

0 present basic dyes based on the weight of leather dissolved in warm water (50-600C) being used. Vegetable tanned leather are sometimes bleached also with oxalic acid or sulphuric acid or formic acid before dyeing. Drying: Different drying methods are used depending on the type of leather. Hypo may be used to remove excess acid. Acrylic resins. The goods are dipped in vat containing mild tanning liquor which leaches out the uncombined tannin. about 0. This process is known as fat liquoring.10H2O) : 8 MJ : 25 Kg : 20 Kg : 5Kg : 15 Kg : 2Kg Hide Lime Na2S Water Dye Oil  Commercial aspects of leather: Post tanning operations: The leather after tanning is given variety of treatments according to the end use. semi chromes after dyeing and vegetable tanned leathers after bleaching are fat liquored to improve smoothness. neutralized with mild alkali and again washed. Vegetable tanned leathers are given decorative patterns by embossing with a hydraulic press. Finishing operation: Light leathers are finished by applying pigment coat. The stock is then pressed in a hydraulic press or by passing it through a wringer. Removal of excess water and tan liquor: The leather contains excess water and tan liquor specially in case of vegetable tanning. The drum is rotated for half an hour and then little formic acid added to destroy excess dye. KAFI For chrome tanning: Basis : 80 kg chrome tan leather. 4. Shaving and splitting: This is done with the help of a sharp knife. In case of vegetable tanned leather.20kg Electricity HCl NaCl Na2Cr2O7. the leather is shaved on a shaving machine. Sole leather is finished by applying oil to the grain surface & passing it through heavy roller.P a g e | 11 DEWAN A. . 5. For light leathers. 1. 3. : : : : : : y y y 100 kg 10 kg 2 kg 5000 L 11 kg sole.H. The fat liquoring is done at 40-700C for about half an hour. tensile strength and water resistance. plasticizers etc. Chrome leather is glazed by a machine having rotating glass cylinder. oil is applied on grain side so that evaporation takes place from flesh side surface. lacquers may also be used. they may be sprayed on the grains or applied by hand. The machine has sharp spiral knife blades thus reducing thickness by removing extra stock from flesh side. 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. Neutralizing and coloring: After shaving chrome tanned leather is washed in a drum. The neutralized stock is dyed in direct dye solution in warm water. fuel.5 to 2. 2.2kg betting -8kg harness. Chrome leathers. Chrome tanned leathers are dried by suspending in drying rooms or by passing through air heated tunnels. The excess dye is drained and sulphonated neat foot oil emulsions are applied. The friction improves the glaze and imparts a glassy finish to the waxed or lacquer coated leather. Dyeing is performed in drums.2H2O Na2S2O3 Borax(Na2B4O7.