CHROME LEATHER

Leather is a durable and flexible material created via the tanning of putrescible animal rawhide and skin, primarily cattle hide. It can be produced through different manufacturing processes, ranging from cottage industry to heavy industry.

History of Leather:
From prehistoric times man has used the skins of animals to satisfy his basic needs. He has used hides to make clothing, shelter, carpets and even decorative attire. To the Egyptian lady, a fur piece was highly prized as her jewellery. From leather, manmade footwear, belts, clothing, containers for liquids, boats and even armor. The principle protective armor of the Roman soldier was a heavy leather shirt. In recorded history, pieces of leather dating from 1300 B.C. have been found in Egypt. Primitive societies in Europe, Asia and North America all developed the technique of turning skins into leather goods independently of one another. The Greeks were using leather garments in the age of the Homeric heroes (about 1200 B.C. ), and the use of leather later spread throughout the Roman Empire. During the middle Ages, the Chinese knew the art of making leather. The Indians of North America also had developed great skills in leather work before the coming of the white man. At some time, by accident or by trial and error, man discovered methods of preserving and softening leather treating animal skins with such things as smoke, grease and bark extracts. The art of tanning leather using the bark of trees probably originated among the Hebrews. In primitive societies, the art was a closely guarded secret passed down from father to son. As civilization developed in Europe, tanners and leather workers united in the trade guilds of the middle Ages, as did the craftsmen in other fields. Royal charters or licenses were issued permitting people to practice leather tanning. In the nineteenth century, vegetable tanning, i.e., tanning using the extracts from the bark of certain kinds of trees, was supplemented by chrome tanning. This process uses chemicals and today accounts for about eighty to ninety percent of all tanning done except for the leather used in the soles of shoes and tooling leathers.

Raw material:
The basic raw material for the tanning industry is a by-product of the meat processing industry i.e. animal rawhide and skin (primary cattle hide). Approximately 25 million lambskins, 8 million sheepskins, 2.2 million cattle hides, 1.2 million calfskins, 200,000 goat skins and 400,000 deerskins are available for processing into finished leather products in New Zealand tanning industry. The tanning materials used in the conversion of skin to leather are mostly imported. They are of four types: 1. Vegetable extracts from the bark and wood of trees (oak, wattle etc). 2. Mineral- in the main, trivalent chromium sulfate. This is produced by the reduction of hexavalent chromium in the form of sodium chromate or dichromate by organic or inorganic reducing agents. 3. Aldehydes- formaldehyde, glutaraldehyde or oxazolidine. We shall discuss only chrome tanning (mineral tanning) here

Sources of raw material in Pakistan: Pakistan is fortunate that the raw material required by the industry is available in the country in abundance. Local availability of raw materials and low wage cost gives the country a competitive edge in the world market. The following are the types of basic raw materials which are being used by this industry: - Cow hides - Buffalo hides - Goat skins - Sheep skins. 1) Buffalo 2) Cow 3) Goat 4) Sheep 1. Buffalo: Buffalo is considered as the specialty of Pakistan in World, because of its ample availability in Pakistan 2. Cow: The cow row material is considered a superior raw material upon buffalo because of its fine, tight and comparatively uniform structure. 3. Goat: It is good for making shoe upper leathers, garment and goods leather. 4. Sheep: Leather made from sheep raw materials has a very good and softer touch and considered best for leather garments. The industry is meeting its 75% needs of raw hides from local resources while rest of the 25-30 per cent is met through imports. Pakistan imports leather from Saudi Arabia, Iran, and China, Dubai, Sudan, Kenya, Australia and Italy.

In the leather industry the raw materials are by-products of the meat industry, with the meat having higher value than the skin. Taxidermy also makes use of the skin of animals, but generally the head and part of the back are used. Hides and skins are also used in the manufacture of glue and gelatin.

Process description:
Chrome-tanned leather, invented in 1858, is tanned using chromium sulfate and other salts of chromium. It is more supple and pliable than vegetable-tanned leather, and does not discolor or lose shape as drastically in water as vegetable-tanned. Also known as wet-blue for its color derived from the chromium. More esoteric colors are possible using chrome tanning. When animal is alive, its skin is soft, flexible, very tough and hard wearing: it has ability to allow water vapor to pass out, but it will not allow water in. when the skin dies it loses these characteristics: if it is kept wet it rots, and if it is dried it goes hard and brittle. The process of tanning is to retain the skins natural properties, to stabilize its structure and at the same time to chemically process it so it will no longer be subject to putrefaction. Thus leather is animal skin that has been treated such that its natural properties are retained Chemistry of Skin: Skin is made up of many bundles of interwoven protein fibers which are able to move in relation to one another when the skin is alive. When the skin dies, these fibers tend to shrivel and stick together. Essentially, the purpose of tanning is to permanently fix the fibers apart by chemical treatment, and to lubricate them so they can move in relation to one another. Well tanned leather, therefore, retains the properties of flexibility, toughness and wear. It also continues to 'breathe', allowing water vapor to pass through but remaining reasonably Water-proof. In addition, the process of tanning imparts the advantage of resistance to heat. This is an important factor in many of the uses of leather. In conjunction with chemical processing, the tanner imparts color, texture and finish to the leather, to enhance its appearance and suit it to today's fashion requirements. The basic component of the skin is collagen, a fibrous protein. The latest research indicates that the basic collagen structure consists of twined triple units of peptide chains of differing lengths. The amino acid residues are joined together by peptide links. The peptide chains within the triple helices are held together by hydrogen bonding (Figure 1).

The main processing sequences of leather manufacture are shown in Figure 2. Where skins are processed with the hair or wool on, the unhairing and liming processes are omitted and replaced by a scouring (washing) of the wool or hair. The main chemical processes carried out by the tanner are the unhairing, liming, tanning, neutralizing and dyeing. Skin collagen is usually associated with keratin (the protein in hair, wool and nails). Most mammals have an outer coat of hair, wool or fur, which acts as an insulating layer and keeps the animal warm. Keratin is a fibrous protein and different from collagen in one very important aspect: the polypeptide chains are linked together by cystine linkages. The sulfur-sulfur linkage in cystine is susceptible to the action of alkali, and breaks down quite readily in the presence of alkali and a reducing agent.

Animal skins are converted to leather in nineteen different stages discuss below: 1. Warehousing and sorting in the raw material area the skins are preserved in salt, stored in controlled cool rooms and before processing, presorted for quality and weight. 2. Soaking the skin is soaked to remove dirt and salt. 3. De-Fleshing During this process tissue, flesh and fat remnants are removed by a roller mounted knife. 4. Liming By adding lime and sulphur compound the hair is removed from the skin. The process of liming is a combination of chemical and physical action on the skin structure. The chemicals involved are similar to those in the unhairing operation. A solution of lime and sodium sulfide is used and the skins are immersed in this solution for whatever time is necessary to produce the desired effects. The process of unhairing is taken to completion during the liming process, and there is appreciable modification of the collagen takes place due to the action of alkali.

Skin protein (collagen)

Alkali

1) 2) 3) 4) 5)

Hydrolysis of amide groups Modification of guanide groups Hydrolysis of keto-imide links in protein chains Swelling Removal of unwanted material

After the strong alkaline action, the skin structure is further opened up during the Deliming and bateing process. 5. Bating: Bating is an enzyme digestion process which continues the cleaning up process begun by the alkaline action. Bateing is carried out at pH 9-10. This is achieved by treatment with acid salts (ammonium chloride or ammonium sulfate) or carbon dioxide until the desired pH is reached. Hydrolysis is continued by the enzyme process and further dissolution of unwanted material occurs. The main fibrous network is then cleaned up and the swelling is reduced. 6. Pickling: The main acidification process is that of pickling. The skins are agitated in a solution of salt and sulfuric acid until they are at or near equilibrium at a pH value of 3.0 - 3.5. 7. Tanning: The main chrome tanning material is trivalent chromium sulfate. It is now widely used in all leathers preparation where softness, stretch and suppleness are required. After pickling, when the pH is low, chromium salts (Cr3+) are added. To fixate the chromium, the pH is slowly increased through addition of a base. The process of chromium tanning is based on the crosslinkage of chromium ions with free carboxyl groups in the collagen. It makes the hide resistant to bacteria and high temperature. The chromium-tanned hide contains about 2-3 dry weight percent of Cr3+. The use of chromium in tanning: Chromium, a transition element which forms co-ordination complexes by using 3d orbital to accommodate extra electrons, has an unrivalled position as a tanning agent. The complex is basic by nature and will contain hydroxyl groups associated with the chromium nuclei. There are two main features of chromium chemistry which enable it to act as a tanning agent. Firstly, the complexes formed are of intermediate stability, and thus exchange of co-coordinating ligands can take place comparatively easily. Secondly, chromium has the ability to form polynuclear complexes in which Cr-O-Cr bridges are involved. These come about as follows:

The final process of oxolation is a slow one and is not readily reversed. In a similar manner, long chains may be built up. By means of these polynuclear units the gaps between collagen chains in the skin structure can be bridged, giving the tanning action. Chromium shows a strong tendency to form coordination compounds with molecules containing carboxyl groups. The order of stability of complex ions involving chromium with other differing ligands is:

The chromium-collagen complex lies approximately between (1) and (2) in the range of stabilities, and the order in the series has a number of practical and theoretical implications. Individually these two properties are found in the chemistries of many other elements, and do not give any great tanning ability. But the two properties together give great tanning potency. The process of chrome tanning is now thought to involve the ligand present in the chromium complex being replaced by collagen. Overall during this stage the skin fibers absorb the tanning agents. That's when the skin becomes leather. 8. Samming During this process water is removed. 9. Splitting In order to achieve an even specified thickness the leather is reduced in substance. The resulting splitleather can then be processed further as suede. 10. Skiving the grain leather is brought to an even thickness. Irregularities are removed from the reverse side and the leather is separated into color-batches. 11. Sorting The leather is sorted into various quality grades. 12. Neutralizing After tannage, leather must be neutralized to remove unwanted acids to prevent deterioration during the drying process, and to prepare the leather for the next stages in processing: dyeing and fat liquoring. Neutralizing is often carried out using mild alkalis which have some effect on the chromium complex 13. Dyeing Dyeing is done using a variety of dyestuff types. Commercial dyes are essentially mixtures of chemical compounds which can be fixed (combined) to the material to be dyed and which have appreciable resonance within the molecule giving color. A simple example is Orange II:

Its color comes from the presence of the hydroxide group in conjunction with the azo group, allowing a high degree of resonance. It can be fixed to the material to be dyed by means of the sulphonic acid group. In chrome tanned leathers the most reactive sites are the chromium nuclei, and these form the main points of fixation for dyestuffs. As with other processes, the main factors controlling dyeing are the physical one of locating the dye in the required position within the leather structure and the chemical one of controlling the conditions so that reasonable penetration and fixation are achieved. A wide range of dyes are used in leather processing and some examples are:

The growing awareness of the effects on health of prolonged exposure to certain industrial chemicals has led to the prohibition of the use of certain dye stuffs - examples are direct dye- stuffs based on benzidiene. Consumer requirements for both wash and light fastness in leather goods has lead to a shift away from the more level dyeing direct and acid dyes to the faster pre- metalized and reactive dyes. Dyeing technology has had to keep up to improve the level dyeing properties of these dyes. 14. Greasing or Fat liquoring Fat liquoring is the process in which 'tanned' fibers are treated with reactive oils, which attach themselves to the fibrous structure, and lubricate them so that they can move readily in relation to one another, producing a soft, supple leather. 15. Drying Two methods are used to dry leather. The vacuum process during which moisture is removed by suction and the hanging process, when leather is hung and taken through ovens. The chemical condition is stabilized and the final properties of the leather are determined. 16. Staking Following drying the leather is mechanically staked in order to soften it. Further processes take place in preparation for finishing. 17. Finishing Here the leather is given its final surface treatment and look. Through processes of base coat, coloring, embossing, ironing the leather becomes, depending on the demands of fashion, matt or shiny, two-tone or uni-coloured, smooth or grained by applying a surface coating - pigments or dyes bound in an organic (acrylic, butadiene or polyurethane) or protein (casein) medium.. The art of finishing lies in working in wafer-thin layers without disturbing the natural look of the leather and its characteristics such as suppleness and breath ability 18. Quality Control In between every process quality is controlled. Final control checks to ensure each individual production is to specification and sorting into various trades. 19. Dispatch The leather is measured electronically, wrapped and dispatched

Status of Leather Industry in Pakistan:

The history of leather industry in Pakistan is as old as the country itself. At the time of independence there were only a few tanneries producing sole leather and that too at a very small scale. However, since then this industry has been flourishing and has never looked back. During 1950s, some well-equipped tanneries were set up at Karachi and Lahore, while during 60s and 70s more units were established at Hyderabad Kasur, Sialkot, Multan, Sahiwal and Gujranwala. Starting with the production of picked and vegetable tanned hides and skins, the tanneries, today, are producing not only wet blue and crust, but also fully finished leather. In the early days of independence some tanneries were established in Karachi. In 1950's some were established in Lahore and adjoining areas. The entire production of hides and skins were being exported in a raw form. Thereafter the local tanning industry making at first semi-finished leather made rapid progress due to favorable raw material situation, cheap labor and the existence of growing demand and foreign market. Production capacity of Leather Industry in Pakistan is as follow: Particulars Production Capacity per anum Tanned leather 90 million sq. meter Leather garments 7 million Leather gloves 10 million Leather footwear 200 million Source: Pakistan Tanneries Association Presently, there are some 461 leather garments/apparels making units, which annually produce some 5.0 million pieces against a capacity of producing 7.0 million pieces. The 524 footwear units in the country are currently producing 100 million pairs against a capacity for producing 200 million pairs, while 348 leather gloves units are producing 5.0 million pairs against a capacity of making 10 million pairs annually. These statistics clearly show that the capacity of this sector remains highly underutilized and with a little extra effort Pakistan can substantially increase the production and exports of its shoes and other leather products.

Problems faced by the industry

1. Quality: Good quality leather is mostly exported and is not available for high value-added Leather Garments & Leather Products. Leather garments in Pakistan are made mostly from low grade & medium grade leather. Lack of proper training and inadequacy of skills in slaughtering are among the most important factors leading raw hides and skins towards lower grades or even to rejection. Furthermore, inadequate knowledge of preservation techniques and lack of sufficiently designed collection and storage facilities may cause

problems that are associated with the lowering of the quality and quantity of raw material. Hence, the need for strengthening training facilities for manpower at all levels through hiring of experts. The quality of raw hides and skins generally depends upon the quality of livestock. The hides and skins removed out of young and healthy cattle may be taken as the best in its quality provided the conditions in which these are removed and also their collection, preservation and storage is satisfactory. In fact, there are many factors which affect the quality of leather at pre-slaughtering, during slaughtering and post-slaughtering stages. It is estimated that around 20-25 per cent of the hides and skins are affected by pre-slaughtering damages, like skin-cuts, rashes, diseases, injuries etc.

2. Cost of production: Cost of production is also very high in Pakistan as compared to our competitors like China and India. The high cost of various inputs especially utilities and taxes make our products uncompetitive in international markets. 3. The issue of chrome Chromium III salts are used extensively in the tanning process. Approximately 90% of the leather manufactured is tanned using chromium III. This is because chromium is the most efficient and versatile tanning agent available and it is relatively cheap. It has been used in the leather industry for almost 100 years and when it was introduced as an alternative to vegetable tanning extracts from oak bark and similar sources, it heralded a new era for the leather industry. It reduced the time taken within the tanning process from months to days, and offered leathers with properties that were previously unattainable. The leather industry only uses chromium in its safest and most stable form - chromium III. However, due to misconceptions about chromium and a failure to recognize the distinctions between chromium III and chromium VI, which is generally understood to be toxic, the tanning industry has often been placed under unwarranted pressure by regulatory bodies with regard to both the use and disposal of chromium and chromium-containing materials. Chromium VI compounds are not used by the tanning industry

4. Energy Issues Generally, a leather unit consumes over 0.97-1.87 MJ i.e. 270-300 KWh of energy to produce 100ft2 of finished leather. The absence of energy efficient technologies and lack of proper maintenance of steam

pipes, steam traps and insulation are causing wastage of significant amount of energy in most leather processing units. 5.Environmental challenge Leather tanneries in Pakistan produce all three categories of waste: wastewater, solid waste and air emissions. However, wastewater is by far the most important environmental challenge being faced by Pakistan's tanneries. Wastewater: Although the exact quantity varies widely between tanneries, a normal requirement of around 50-60 liters of water per kilogram of hide is suggested. ETPI's sample audits of tanneries in Pakistan show that in some cases the consumption of water is as high as three times the suggested requirement. The overall water discharge also demonstrates a high degree of seasonal and daily fluctuation. For most part, the current practice is to discharge this water into the local environment without any treatment. Solid Waste: Two types of solid wastes (tanned and untanned) are generated from leather production processes. Solid waste include dusted curing salts, raw trimmings, wet trimmings, dry trimmings, wet shavings, dry shavings, buffing, and packaging material. It is estimated that for a tannery averaging 10,000 kilograms of skins per day, a total of some 5,500 kilograms of solid waste would be produced per day. In general, it is found that solid wastes from tanneries (except for dusted salt) have secondary users in the local market. Glue manufacturing and poultry feed makers are a major user group of this waste. However, an important problem with this use is the presence of chromium in it. The use of chrome contained solid waste for poultry feed preparation could cause serious health problems for poultry consumers. Air Emissions: There are two sources of air pollution from tanneries in Pakistan. The first relates to emissions from generators (diesel-based and operated only during power breakdowns) and from boilers. Emissions were found to be well below the NEQS level. Ammonia emission during processing and washing of drums, though intermittent but important has adverse effects on workers health. Hydrogen sulphide emission during mixing of acid and alkaline wastewater in drain is also a serious health hazardous. Segregated discharge of acidic and alkaline effluent can help to avoid the hydrogen sulphide gas emission. Solid Waste Two types of solid wastes are generated from leather production processes (i.e. tanned and un tanned). Solid waste includes dusted curing salts, raw trimmings, wet-blue trimmings, dry trimmings, wet-blue shavings, dry shavings, buffing, and packaging material etc. On an average a tannery processing 10,000 kilograms of raw material per day produces some 5,500 kilograms of solid waste daily. The solid wastes do have secondary use in glue manufacturing and poultry feed making etc. However, the use of chrome-

containing solid waste for poultry feed preparation can cause serious health problems for poultry consumers.

Future of Leather Industry in Pakistan Recommendations

1. Introducing Brand Names Leather and Leather products from Pakistan have carved a respectable place in the world market. Some of leather products from Pakistan especially leather jackets are much in demand but under the foreign renowned brand names. Made-in-Pakistan label and brands born in Pakistan have yet to come. Steps need to be taken by the industry in this regard. Renowned Pakistani firms need to register trade marks with respect to the leather products they manufacture. In light of the Agreement on trade related aspects of intellectual property rights (TRIPS) of WTO, Pakistan through Trade Marks Ordinance, 2001, provides effective protection and rights to the owner of trade marks. 2. Focusing on Footwear Sector Footwear, the largest segment of the leather industry around the world has been surprisingly neglected in Pakistan. Foreign franchised companies have become household names in Pakistan. This is despite the fact that the entire stuff and skill they use belong to Pakistan. Moreover, having a strong industrial base, Pakistan's leather industry looks treading without shoes. This vacuum in leather industry calls for the attention of the industry leaders to bridge the gap to give a comprehensive look to the leather and leather products industry in Pakistan. One of the options to enter the field of footwear sector is to seek partnership with international brand producers by offering them attractive incentives. 3. Tackling Environmental and Labor Issues Regarding environmental concerns of WTO, the industry has made little progress in this regard. Combined effluent treatment plants need to be built so that hazardous chemicals from the tanneries do not affect the environment. Moreover, the industry needs to tackle all the labor issues to which the consumers in the importing countries are sensitive to. It needs to be ensured that the leather industry in Pakistan adheres to the working condition requirements that have been developed by certain international bodies, particularly, the associations of leather industries in the importing countries of the west. Under the WTO regime, member countries can impose penalties or restrict imports from exporting countries whose industries do not observe environmental/labor concerns or social compliance. 4. Control on Smuggling & Diseases of Livestock Leather manufacturing sector in Pakistan can also suffer because of massive smuggling of livestock to other countries, shortage of raw material and absence of the organized dairy farming in the country. Steps should be taken to overcome these problems Moreover, diseases in the livestock in Pakistan can prove hurdle in the manufacturing and exports of finished products of leather. Concrete measures need to be taken to overcome this threat to the

livestock as a result the live animals are suffering from different diseases that damage the quality of the leather and tarnish the image of products at international level. 5. Reduction of Duties on Machinery The duties on the import of tanneries related machinery need to be further reduced. The machinery made locally is technologically inferior which not only increases the cost of production but restrains from developing at par with the international market.

REFRENCES http://www.dailytimes.com.pk/default.asp?page=2009/12/03/story_3-12-2009_pg5_17 http://pisd-pak.org/leather.php http://jang.com.pk/thenews/jul2009-weekly/busrev-13-07-2009/p4.htm Lahore chambers of commerce and industries Pakistan tanneries association Trade Development Authority of Pakistan (TDAP) Furniture Today magazine, article published on September 16, 2001