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Before hides are tanned it is necessary for them to pass through a series of preparatory processes. The object of these processes is to obtain from the hide the true hide substance in a pure and suitable condition. Each class of leather has its own appropriate processes, the adjustment of which largely determines the quality of the finished article. So prominent is the influence of these preparatory methods that the paradox "good leather is made before tanning" is in trade circles almost a platitude. These processes, sometimes lumped together under the general name of "Wetwork," comprise soaking, liming, beam house work and deliming. These will be discussed in turn.

The term applied to the hide after these processes, but before tannage, is "pelt."

Soaking has for its object the cleansing and softening of the hides, chiefly by means of water. It aims at the removal of dirt, blood, dung, and curing materials by washing. The process is usually simple, and is much the same for all classes of leather. The ideal to be aimed at is to restore the hide to its condition when it left the animal's back. Cleanliness in leather manufacture is as essential at the commencement as anywhere, for the hide is in its most putrescible state. The soluble proteids (blood, lymph, part of dung, etc.) which always adhere to hides encourage the rapid growth of putrefactive bacteria, and cannot be washed away too soon. Dung is often difficult to remove, being caked on the butt end amongst the hair. Soaking only softens it, and mechanical removal is usually necessary. If such substances are not removed, they go forward with the goods into the lime liquors, causing stains, loss of hide substance, and counteracting plumping.

The detailed method and time of soaking are determined mainly by the nature of the cure. One of the purposes of the soak liquors is to dissolve the salt used in curing hides and to rehydrate the hide and make it again soft and pliable. As a 10-per-cent. salt solution exerts a solvent effect on hide substance, it is necessary soon to change the first soak liquor of salted goods.

Market hides, which are uncured, require the least soaking, the cleansing effect being most needed. The hides are inserted into pits ("water dykes") of water for a few hours, and the water changed once or twice. The soaking should not be prolonged as the hides are so putrescible, and where it is customary to leave the goods in a soak liquor overnight, it is advantageous to add a little slaked lime to the water before inserting the goods. This not only softens hard water, but is mildly antiseptic and plumping, and forms a suitable introduction to the liming proper. Each pit contains a "pack" of 30-50 hides, according to its capacity, which varies in different tanneries from 1000 to 2000 gallons. Tainted goods, which are indicated by a characteristic white colour on the flesh side and by loose hair, need a preliminary washing either in a "drum," "tumbler" or in a "paddle." This ensures a rapid change of liquor and the removal of most of the putrefactive agencies. Bad cases may need the application of antiseptics, such as immersion in 0.1 per cent. carbolic acid; but if possible these should be avoided, as they lengthen the time required for liming. After drumming or paddling, tainted goods should be placed directly into a lime liquor.

Salted hides need very similar treatment to uncured hides, but the soaking is longer, because of the dehydration caused by salting. Hence they receive also a greater number of changes of water, three or four usually, but often more. As much loose salt as possible should be shaken from the hides before insertion into any liquor. The employment of drum or paddle before pit soaking is extremely useful to effect the rapid removal of superficial salt, and is also useful after pit soaking to remove the last traces.

Dried and dry-salted goods need a soaking still more prolonged, up to one week if water alone be used. With the assistance of caustic soda, however, the process can be shortened to about two days. The first soak liquor should consist of a 0.1 per cent. solution of caustic soda, and after the goods have been inserted twenty-four hours, they will be materially improved by a few hours' drumming or paddling. Another caustic soda soak will complete the process. Sodium sulphide crystals may replace caustic soda, but about three times the weight will be needed. Carbonate of soda and caustic lime also are a convenient commercial substitute for caustic soda. For 10 lbs. caustic soda, use 36 lbs. carbonate and 7 lbs. lime. Extra lime should be added in all cases when the water is hard. Acid liquors will also soften dried and dry-salted goods, but such processes do not fit in so well with the subsequent liming. The use of putrid soaks and stocks may be now considered out of date.

Liming follows soaking, and consists essentially in immersing the hides for 7-10 days in milk of lime. The chief object in view is to loosen the hair and prepare for its mechanical removal. Liming takes place in pits, the tops of which are level with the limeyard floor. The lime is slaked completely and mixed well with water in the pit, being particularly well plunged just before the insertion of a pack of goods. Saturated limewater is only a 0.13-per-cent. solution. The goods are occasionally "handled" i.e. hauled out of the pit and reinserted after plunging ("hauling" and "setting"). This is necessary to keep the liquor saturated with lime. The hides are inserted one by one, each being "poked down" to ensure its contact with the liquor. The goods are invariably immersed first in a previously used lime liquor. Most tanneries now carry this out in a systematic way, so as to ensure regularity in the process. As the goods are large and heavy it is less laborious to carry out the whole process in one pit. In this "one-pit system" the goods are inserted for (say) four days in an old used lime liquor, with occasional handling; this liquor is then run to the drain and a new liquor made up in the same pit, into which the goods are inserted for (say) five days. They are then hauled and sent to the unhairers. Each pack thus gets two liquors, old and new.

A better method is the "three-pit system." In this case each pack receives three liquors and has (say) three days in each, first an "old lime," then a "medium lime," and finally a "new lime." This system ensures a greater regularity of treatment, and is deservedly the most popular method for liming hides for sole leather. After being used once as a "new lime," a liquor then becomes a "medium lime," and after being thus used becomes the "old lime" which receives the green hides from the soaks. The system involves the goods being shifted twice to another pit, which is more laborious than reinsertion into the old pit, but if the limeyard be arranged in "sets" or "rounds" of three pits, the shift is usually only to the adjacent pit. One special advantage of this system is that the top hides in one pit become the bottom hides in the next pit, and vice versâ. Rounds of more than three pits are sometimes used.

Many factories have now adopted systems in which there is no handling at all. The hides are suspended in lime liquors which are agitated by mechanical contrivances (e.g. Tilston-Melbourne process), or by jets of compressed air (e.g. Forsare process). The goods are soaked and limed "mellow to fresh" by changing the liquors by means of pumps, air ejectors, etc. Thus the hides need no labour from first being inserted until drawn for depilation.

In liming, the whole of the epidermis as well as the hair is loosened, and is subsequently removed in depilation. The corium or true hide substance becomes much more swollen by imbibation of water, and when taken out of the new lime is "plumped" to very firm jelly. This plumping is a matter of prime importance to the tanner. The coarser fibres are thereby split up into the finer constituent fibrils, which fact assists very materially in obtaining a quick and complete tannage, good weight, and a firm leather. During the liming, the natural grease of the hide is saponified or emulsified, which prepares for its removal in scudding. Liming is thus a complex process: the hair is loosened, the hide is plumped, and the grease is "killed." All these results may be hastened by the use of other alkalies in addition, and most heavy leather yards assist the liming by adding also sodium sulphide or caustic soda or both. Sodium sulphide is a powerful depilatant, and will alone unhair hides easily in strong solutions even in a few hours. As in solution it forms caustic soda by hydrolysis, it possesses also the powerful plumping and saponifying powers characteristic of the latter. The addition of arsenic sulphide (As₂S₂) (realgar) to the lime when slaking causes the presence of calcium sulphydrate in the lime liquors thus made. This is also a powerful depilatant, but not much used for heavy leather.

The function of the lime in depilating is complex and has occasioned much discussion. Its main purpose, however, is that of a partial antiseptic. When hides putrefy, one of the first results is that the hair is loosened. In America depilation by "sweating" is carried out commercially by such a mild putrefaction, the lime liquor permits a similar fermentation at a slower rate, and all tannery lime liquors are swarming with putrefactive bacteria. Liming is thus a safer method than sweating, which may be easily carried too far. Various workers have isolated specific organisms—Wood a bacillus, Schmitz-Dumont a streptococcus—but it seems highly probable that the limeyard bacteria are just the common organisms of putrefaction sorted out or selected by the exact nature of the liquor and the method of working the limes. Many putrefactive bacteria are very adaptable and could easily accommodate themselves in this way. It is known that the exact nature of the culture medium has a great influence on the rate of development of such organisms, and which particular species thrive and obtain predominance in any limeyard will depend upon the amount and nature of the dissolved organic matter available as food, and upon the exact alkalinity and the concentration of other apparently inert substances, such as common salt and sodium, calcium and arsenic salts. Hence no two lime liquors operate alike, and approximate regularity is only assured by systematic method. In handling and shifting, the organisms are subjected to further selection, and the most adaptable survive. It is probable that different species may act symbiotically. The depilating organisms of lime liquors are probably mostly anærobes, but some may be anærobic by adaptation. It is probable that ærobic ferments commence the depilation, but this will be done before the goods are put into work, or at any rate before they reach the limes. More strictly, it is the enzymes secreted by bacteria which are directly responsible for the hydrolytic work; these enzymes are chiefly proteolytic (proteid splitting), but the lipolytic (fat splitting) enzymes have also a place.

The lime, however, not only limits and selects the course of the putrefaction, but also affords more positive assistance. Lime plays its own hydrolytic part and assists the depilation by purely chemical action. Lime will unhair without the assistance of bacteria, but its action is slow and forms a minor part of the operation in the average limeyard. This action is due chiefly to its progressive formation of calcium sulphydrate from the cystine group of the softer keratins. Lime also plays an essential part in assisting the putrefactive fermentation. It softens the keratins and thus assists the bacterial attack, it hydrolyzes other proteids and provides the bacteria with food in solution, the calcium ion increases the proteolytic action of certain enzymes, and finally the apparently inert excess of undissolved lime has an accelerating effect on the bacterial activity.

In the average limeyard these various functions are inextricably mixed up, and it is impossible to assign any definite proportion of the total depilatory effect to any of the factors at work. Lime alone will unhair, bacteria alone will unhair, and sulphides will also unhair without lime or bacteria, but in the limeyard all three agencies are at work. Putrefactive fermentation, however, obtains a good start. Ærobic fermentation commences with the slaughter of the animal, and the anærobic organisms soon commence their part, and are at work in the hide house and soaks. On entering the limes, the purely chemical hydrolytic action of lime is added to that of the bacterial enzymes as well as the action of lime as bacterial assistant, and the three continue to operate side by side. Each gives rise to the formation of calcium sulphydrate, whose own special solvent effect is superadded. If sulphydrates be deliberately added to the liquors there is yet another factor assisting. Speaking broadly, the bacterial enzymes have their maximum activity in the old limes, and the chemical action of sulphydrate formed from the keratin cystine is also at a maximum in these liquors. The chemical action of added sulphide, and the simple hydrolytic action of calcium hydrate have their maximum activity in the new limes. Most observers would agree that in practice the bacteria shoulder the greater part of the work.

From the limeyard is taken about the only waste bye-products of the tannery, viz. the residues from the soak and lime pits. These consist mainly of lime and chalk, with some hair and dung, and possibly a little sulphide. The sludge possesses some value as a manure, especially if from the soak pits on account of the greater nitrogen content. (Part VI., Section I.)

The Beam House Work consists in the mechanical removal of those parts of the hide not wanted for leather manufacture. Unhairing removes the hair and the epidermis made loose in liming. The hides are placed over a sloping "beam" with a convex surface, and the hair scraped off with a blunt concave and double-handled knife. The hides are then thrown into a pit of water. The hair is carefully collected, washed well with water, preferably centrifuged, and then dried out by a current of warm air. It forms a valuable bye-product. White hair is usually kept separate and fetches a higher price. Fleshing is the next process. The hides are again placed over a beam, with the flesh side (i.e. the side nearest the flesh) uppermost. Skilled workmen then cut off, with a sharp convex knife, the fat, flesh and connective tissue left in flaying. Rounding is usually the next process. The unhaired and fleshed hide is spread out flat and cut up into butt, shoulder and a pair of bellies. These parts have different commercial values, and may afterwards be tanned by different methods for very different purposes—for dressing leather, and sometimes even for sole leather. Scudding is the last piece of beam work. The fleshed hides (whether rounded or not) are washed, or at least rinsed, with water, and again placed on the beam grain side up. They are then scraped with a rather sharp concave knife, to remove "scud," which consists of hair roots and sheaths, lime soaps, fat, pigment and other dirt. Short hair is shaved off by a very sharp hand knife.

The beam work demands a certain amount of skill from the workmen, especially from the flesher, whose sharp knife may prove very wasteful in incompetent hands. Hand labour was slowly but surely being replaced by machinery before the war, and war-time conditions have greatly accelerated the rate of transition. Beam house machinery is rapidly becoming universal. The machines are cumbrous and expensive in cost and in power, but machine work is quicker, less laborious, and needs much fewer workmen. Many types of machine have been suggested, but the most useful are those in which the hides pass over rollers and are simultaneously acted upon by a rapidly revolving cylindrical knife with spiral blades, one half being a left-handed and the other a right-handed spiral, so that the hide is scraped outwards as well as in the direction of motion. The part of the hide being acted upon rests on a pneumatic roller. By changing the type of spiral knife cylinder the machine will unhair, flesh or scud.

Deliming is a general name covering a number of similar operations whose primary object is the neutralization and removal of the caustic lime and soda in the plumped pelt, or at any rate on the surface of the hide. This is a preparation for the tan liquors. All the tannins and many associated substances darken rapidly with oxidation when in alkaline solution, so that to place the fully limed hide in a tan liquor would give a dark-coloured leather. A short insertion in a bath of weak acid would secure the elimination of surface lime and the disappearance of this difficulty, but there are other purposes in deliming. The more completely lime is removed the more the plumped pelt "falls" into a soft, pliable, unswollen and relaxed condition, and this change assists very materially in the production of a soft dressing leather, suitable for boot uppers, bags, etc. For such leathers, therefore, the deliming must be much more complete than for sole leather, in which the object is to obtain a firm and plump leather.

In the case of the softer dressing leathers, experience indicates the advisability of allowing some further bacterial action on the interfibrillar substance in order to produce the requisite pliability and softness. This is secured by "bating" the hides. This process consists in immersing the goods into a cold fermenting infusion of hen or pigeon dung. The infusion is made in a special tub or pit with warm water and allowed to stand for a day or two until the fermentation has commenced, and then run into the bating pit through a coarse filter such as sacking. The hides are immersed for some days, but are handled frequently to ensure an even effect. The bate is always slightly alkaline. The caustic alkalinity increases rapidly at first owing to the diffusion of caustic lime, then at a slower rate, afterwards slowly declining. This is explained by the production of organic acids, and their salts with weak bases from the dung infusion by the action of bacteria. The total alkalinity of the bate liquor increases rapidly at first owing to the diffusion of lime and its liberation of organic bases, then very slowly, but towards the end of the operation the total alkalinity increases very rapidly indeed, owing probably to the commencement of a violent anærobic fermentation which produces ammonia and other organic bases, and which heralds the approach of a putrefactive action, which if allowed to continue for even a short time will ruin the hides. Bating is consequently a risky process, and needs experienced oversight. For goods which need only a mild bating, there is the alternative of giving a longer liming in older limes. This of course involves more bacterial hydrolysis, and perhaps does it in a safer, more economical and certainly in a less offensive manner. Bating is often followed by a further deliming by acids. Boric, lactic, acetic, formic and butyric acids are all used, and with care even hydrochloric and sulphuric acids may be employed. Innumerable "artificial" bates have been put on the market, but most are merely weak acids, acid salts or salts of strong acids with weak bases. An American "bacterial bate" consists of a lactic fermentation of glucose in the presence of glue.

Closely similar to bating is "puering," investigated by Wood (see p. 94).

Drenching is another fermentive deliming process. In this the goods are inserted into an infusion of bran. This is made by scalding the bran with hot water, and allowing it to stand until it is about 70°-90° F. The infusion is then "inoculated" with a few gallons of old drench liquor, and the goods are immersed. This fermentation has been examined carefully by J. T. Wood. First the enzyme cerealin converts bran starch into glucose, which is then fermented by the drench bacteria with the production of lactic acid, some acetic acid and small amounts of formic and butyric acids. The butyric fermentation is liable to become too violent. These acids, as they are formed, neutralize the lime in the hides and plump the pelt slightly (see pp. 107-109).

Various gases (carbon dioxide, hydrogen, nitrogen, methane and sulphuretted hydrogen) are involved, and the proportion produced in the pelt itself has a peculiar opening effect on the hide fibres. The activity of the drench can be decreased by dilution and by using a less starchy bran, and can be increased by adding pea meal or rye meal. Drenching usually follows bating. Scudding sometimes follows deliming.

The theory of the volume and elasticity changes of pelt during preparation will be better understood after considering the behaviour of gelatine gels (pp. 200-219). The determining factors are the nett charge of hydroxyl ions on the disperse phase, resulting from ionic adsorptions, and the lyotrope influence of dissolved substances on the continuous phase.

In softening dried hides the swelling may be due to either influence, but the latter tends to loss of hide substance and the production of soft leather.

In liming, the nett adsorption of hydroxyl ions is the principal factor, but the lyotrope influence of the alkali cations and of the impurities is important. Plump pelts are those in which the contained water is in a relatively greater average state of compression. Few substances can assist plumping, but many can hinder it. In plumping all lyotrope influence is objectionable, and "sharp" (pure) alkali solutions are required. Mellow limes reduce elasticity and plumpness by lyotrope influence.