Encyclopedia Britannica, 11th ed. (1910) v. XVI pp. 330-345
LEATHER (a word which appears in all Teutonic languages; cf. Ger. Leder, Dutch leer or leder, Swed. lδder, and in such Celtic forms as Welsh llader), an imputrescible substance prepared from the hides or skins of living creatures, both cold and warm blooded, by chemical and mechanical treatment. Skins in the raw and natural moist state are readily putrescible, and are easily disintegrated by bacterial or chemical action, and if dried in this condition become harsh, horny and intractable. The art of the leather manufacturer is principally directed to overcoming the tendency to putrefaction, securing suppleness in the material, rendering it impervious to and unalterable by water, and increasing the strength of the skin and its power to resist wear and tear.
Leather is made by three processes or with three classes of substances. Thus we have (1) tanned leather, in which the hides and skins are combined with tannin or tannic acid; (2) tawed leather, in which the skins are prepared with mineral salts; (3) chamoised (shamoyed) leather, in which the skins are rendered imputrescible by treatment with oils and fats, the decomposition products of which are the actual tanning agents.
Sources and Qualities of Hides and Skins.
[Heavy Leathers] The hides used in heavy leather manufacture may be divided into three classes: (1) ox and heifer, (2) cow, (3) bull. Oxen leathers. and heifer hides produce the best results, forming a tough, tight, solid leather. Cow hides are thin, the hide itself being fibrous, but still compact, and by reason of its spread or area is used chiefly for dressing purposes in the bag and portmanteau manufacture and work of a similar description. Bull hides are fibrous; they are largely used for heel lifts, and for cheap belting, the thicker hides being used in the iron and steel industry.
A second classification now presents itself, viz, the British home supply, continental (Europe), British colonial, South American, East Indian, Chinese, &c.
In the British home supply there are three chief breeds: (1) Shorthorns (Scotch breed), (2) Herefords (Midland breed), (3) Lowland, or Dutch class. From a tanners standpoint, the shorthorns are the best hides procurable. The cattle are exposed to a variable climate in the mountainous districts of Scotland, and nature, adapting herself to circumstances, provides them with a thicker and more compact hide; they are well grown, have short necks and small heads. The Hereford class are probably the best English hide; they likewise have small heads and horns, and produce good solid sole leather. The Lowland hides come chiefly from Suffolk, Kent and Surrey; the animals have long legs, long necks and big heads. The hides are usually thin and spready. The hides of the animals killed for the Christmas season are poor. The animals being stall-fed for the beef, the hides become distended, thin and surcharged with fat, which renders them unsuitable for first-class work.
The continental supply may be divided into two classes: (1) Hides from hilly regions, (2) hides from lowlands. All animals subject to strong winds and a wide range of temperatures have a very strong hide, and for this reason those bred in hilly and mountainous districts are best. The hides coming under heading No. I are of this class, and include those from the Swiss and Italian Alps, Bavarian Highlands and Pyrenees, also Florence, Oporto and Lisbon hides. They are magnificent hides, thick, tightly-built, and of smooth grain. The butt is long and the legs short. A serious defect in some of these hides is a thick place on the neck caused by the yoke; this part of the hide is absolute waste. Another defect, specially noticeable in Lisbon and Oporto hides, is goad marks on the rump, barbed wire scratches and warbles, caused by the gadfly. Those hides coming under heading No. 2 are Dutch, Rhine valley, Danish, Swedish, Norwegian, Hungarian, &c. The first three hides are very similar; they are spready, poorly grown, and are best used for bag and portmanteau work. Hungarian oxen are immense animals, and supply a very heavy bend. Swedish and Norwegian hides are evenly grown and of good texture; they are well flayed, and used a great deal for manufacturing picker bands, which require an even leather.
New Zealand, Australian and Queensland hides resemble good English. A small quantity of Canadian steers are imported; these are generally branded.
Chinese hides are exported dry, and they have generally suffered more or less from peptonization in the storing and drying; this cannot be detected until they are in the pits, when they fall to pieces.
Anglos are imported as live-stock, and are killed within forty-eight hours. They come to Hull, Birkenhead, Avonmouth and Deptford from various American ports, and usually give a flatter result than English, the general quality depending largely on whether the ship has had a good voyage or not.
Among South American hides, Liebigs slaughter supply the best; they are thoroughly clean and carefully trimmed and flayed. They come to London, Antwerp and Havre, and except for being branded are of first-class quality. Second to the Liebig slaughter come the Uruguay hides.
East Indian hides are known as kips, and are supposed to be, and should be, the hides of yearling cattle. They are now dressed to a large extent in imitation of box calf, being much cheaper. They come from a small breed of ox, and have an extremely tight grain; the leather is not. so soft as calf.
Calf-skins are largely supplied by the continent. They are soft and pliant, and have a characteristically fine grain, are tight in texture and quite apart from any other kind of skin.
[Light Leathers] The most valuable part of a sheep-skin is the wool, and the value of the pelt is inversely as the value of the wool. Pure Leicester and Norfolk wools are very valuable, and next is the North and South Downs, but the skins, i.e. the pelts, of these animals are extremely poor. Devon and Cheviot cross-bred sheep supply a fair pelt, and sometimes these sheep are so many times crossed that it is quite impossible to tell what the skin is. Welsh skins also supply a good tough pelt, though small. Indian and Persian sheep-skins are very goaty, the herds being allowed to roam about together so much. The sheep-skin is the most porous and open-textured skin in existence, as also the most greasy one; it is flabby and soft, with a tight, compact grain, but an extremely loose flesh. Stillborn lambs and lambs not over a month old are worth much more than when they have lived for three months; they are used for the manufacture of best kid gloves, and must be milk skins. Once the lambs have taken to grass the skins supply a harsher leather.
The best goat-skins come from the Saxon and Bavarian Highlands, Swiss Alps, Pyrenees, Turkey, Bosnia, Southern Hungary and the Urals. The goats being exposed to all winds yield fine skins. A good number come from Argentina and from Abyssinia, the Cape and other parts of Africa. Of all light leathers the goat has the toughest and tightest grain; it is, therefore, especially liked for fancy work. The grain is rather too bold for glacι work, for which the sheep is largely used.
The seal-skin, used largely for levant work, is the skin of the yellow-hair seal, found in the Northern seas, the Baltic, Norway and Sweden, &c. The skin has a large, bold, brilliant grain, and being a large skin is much used for upholstery and coach work, like the Cape goat. It is quite distinct from the fur seal.
Porpoise hide is really the hide of the white whale; it is dressed for shooting, fishing and hunting boots. Horse hide is dressed for light split and upper work; being so much stall-fed it supplies only a thin, spready leather. The skins of other Equidae, such as the ass, zebra, quagga, &c. are also dressed to some small extent, but are not important sources.
Structure of Skin.
Upon superficial inspection, the hides and skins of all mammalia appear to be unlike each other in general structure, yet, upon closer examination, it is found that the anatomical structure of most skins is so similar that for all practical purposes we may assume that there is no distinction (see SKIN AND EXO-SKELETON). But from the practical point of view, as opposed to the anatomical, there are great and very important differences, such as those of texture, thickness, area, &c.; and these differences cause a great divergence in the methods of tanning used, almost necessitating a distinct tannage for nearly every class of hide or skin.
The skins of the lower animals, such as alligators, lizards, fish and snakes, differ to a large extent from those of the mammalia, chiefly in the epidermis, which is much more horny in structure and forms scales.
The skin is divided into two distinct layers: (1) the epidermis or epithelium, i.e. the cuticle, (2) the corium derma, or cutis, i.e. the true skin. These two layers are not only different in structure, but are also of entirely distinct origin. The epidermis again divides itself into two parts, viz, the horny layer or surface skin, and the rete Malpighi, named after the Italian anatomist who first drew attention to its existence. The rete Malpighi is composed of living, soft, nucleated cells, which multiply by division, and, as they increase, are gradually pushed to the surface of the skin, becoming flatter and drier as they near it, until they reach the surface as dried scales. The epidermis is thus of cellular structure, and more or less horny or waterproof. It must consequently be removed together with the hair, wool or bristles before tannage begins, but as it is very thin compared with the corium, this matters little.
The hair itself does not enter the corium, but is embedded in a sheath of epidermic structure, which is part of and continuous with the epidermis. It is of cellular structure, and the fibrous part is composed of long needle-shaped cells which contain the pigment with which the hair is coloured. Upon removal of the hair some of these cells remain behind and colour the skin, and this colour does not disappear until these cells are removed by scudding. Each hair is supplied with at least two fat or sebaceous glands, which discharge into the orifice of the hair sheath; these glands impart to the hair that natural glossy appearance which is characteristic of good health. The hair bulb (b, fig. I) consists of living nucleated cells, which multiply rapidly, and, like the rete Malpighi, cause an upward pressure, getting harder at the same time, thereby lengthening the hair.
|c,||Hair sheath showing epidermic structure.|
|d,||Dermic coat of hair sheath.|
|e,||Outer root sheath.|
|f,||Inner root sheath.|
|n and p,||Epidermis.|
|R,||Sweat or sudoriferous gland.|
|S,||Opening at sweat duct.|
The hair papilla (a. fig. 1) consists of a globule of the corium or true skin embedded in the hair bulb, which by means of blood vessels feeds and nourishes the hair. Connected with the lower part of each hair is an oblique muscle known as the arrector or erector pill, seen at k, fig. I; this is an involuntary muscle, and is contracted by sudden cold, heat or shock, with an accompanying tightening of the skin, producing the phenomenon commonly known as goose flesh. This is the outcome of the contracted muscle pulling on the base of the hair, thereby giving it a tendency to approach the vertical, and producing the simultaneous effect of making the hair stand on end.
The sudoriferous or sweat glands (R, fig. I) consist of long spirallike capillaries, formed from the fibres of the connective tissue of the corium. These glands discharge sometimes directly through the epidermis, but more often into the orifice of the hair-sheath.
The epidermis is separated from the corium by a very important and very fine membrane, termed the hyaline or glassy layer, which constitutes the actual grain surface of a hide or skin. This layer is chemically different from the corium, as if it is torn or scratched during the process of tanning the colour of the underlying parts is much lighter than that of the grain surface.
The corium, unlike the epidermis, is of fibrous, not cellular structure; moreover, the fibres do not multiply among themselves, but are gradually developed as needed from the interfibrillar substance, a semi-soluble gelatinous modification of the true fibre. This interfibrillar substance consequently has no structure, and is prepared at any time on coming into contact with tannin to form amorphous leather, which fills what would in the absence of this substance be interfibrillar spaces. The more of this matter there is present the more completely will the spaces be filled, . and the more waterproof will be the leather. An old bull, as is well known, supplies a very poor, soft and spongy leather simply because the hide lacks interfibrillar substance, which has been sapped up by the body. The fibres are, therefore, separated by interfibrillar spaces, which on contact with water absorb it with avidity by capillary attraction. But a heifer hide or young calf supplies the most tight and waterproof leather known, because the animals are young, and having plenty of nourishment do not require to draw upon and sap the interfibrillar substance with which the skin is full to overflowing.
The corium obtains its food from the body by means of lymph ducts, with which it is well supplied. It is also provided with nodules of lymph to nourish the hair, and nodules of grease, which increase in number as they near the flesh side, until the net skin, panniculus adiposus, or that which separates the corium from meat proper, is quite full with them.
The corium is coarse in the centre of the skin where the fibres which are of the kind known as white connective tissue, and which exist in bundles bound together with yellow elastic fibres, an loosely woven, but towards the flesh side they become more corn pact, and as the hyaline layer is neared the bundles of fibres get finer and finer, and are much more tightly interwoven, until finally next the grain itself, the fibres no longer exist in bundles, but as individual fibrils lying parallel with the grain. This layer is known as the pars papillaris. The bundles of fibre interweave one another in every conceivable direction. The fibrils are extremely minute and are cemented together with a medium rather more soluble than themselves.
There are only two exceptions to this general structure which need be taken into account. Sheep-skin is especially loosely woven in the centre, so much so that any carelessness in the wet work or sweating process enables one to split the skin in two by tearing This loosely-woven part is full of fatty nodules, and the skin is generally split at this part, the flesh going for chamois leather and the grain for skivers. The other notable exception is the horse hide, which has a third skin over the loins just above the kidneys, known as the crup; it is very greasy and tight in structure, and is used for making a very waterproof leather for seamen's and fishermen's boots. Pig-skin, perhaps, is rather peculiar, in the fact that the bristles penetrate almost right through the skin.
Tannin or tannic acid is abundantly formed in a very large number of plants. and secreted in such diverse organs and members as the bark, wood, roots, leaves, seed-pods, fruit, &c. The number of tannins which exists has not been determined, nor has the constitution of those which do exist been satisfactorily settled. As used in the tanyard tannin is present both in the free state and combined with colouring matter and accompanied by decomposition products, such as gallic acid or phiobaphenes (anhydrides of the tannins), respectively depending upon the series to which the tannin belongs. In whatever other points they differ, they all have the common property of being powerfully astringent, of forming insoluble compounds with gelatine or gelatinous tissue of being soluble in water to a greater or lesser extent, and of forming blacks (greenish or bluish) with iron. Pyrogallol tannins give a blue-black colouration or precipitate with ferric salts, and catechol tannins a green-black; and whereas bromine water gives a precipitate with catechol tannins, it does not with pyrogallol tannins There are two distinctive classes of tannins, viz. catechol and pyrogallol tannins. The materials belonging to the former series are generally much darker in colour than those classified with the latter, and moreover they yield reds, phlobaphenes or tannin anhydrides, which deposit on or in the leather. Pyrogallol tannins include some of the lightest coloured and best materials known, and, speaking generally, the leather produced by them is not so harsh or hard as that produced with catechol tannins. They decompose, yielding ellagic acid (known technically as bloom ) and gallic acid; the former has waterproofing qualities, because it fills the leather, at the same time giving weight.
It has been stated, and perhaps with some truth, that leather cannot be successfully made with catechol tannins alone; pyrogallol tannins, however, yield an excellent leather; hut the finest results are obtained by blending the two.
The classification of the chief tanning materials is as follows:
Myrobalans (Terminalia Chebula)
Gambler (Uncaria Gamblir)
Oakbark (Quercus Robur)
Myrobalans are the fruit of an Indian tree. There are several different qualities, the order of which is as follows, the best being placed first: Bhimley, Jubbalpore, Rajpore, Fair Coast Madras and Vingorlas. They are a very light-coloured material, containing from 27% to 38% of tannin; they deposit much bloom, ferment fairly rapidly, supplying acidity, and yield a mellow leather.
Chestnut comes on the market in the form of crude and decolourized liquid extracts, containing about 27% to 31% of tannin, and yields a good leather of a light-brown colour.
Oakwood reaches the market in the same form; it is a very similar material, but only contains 24% to 27% of tannin, and yields a slightly heavier and darker leather.
Divi-divi is the dried seed pods of an Indian tree containing 40% to 45% of tannin, and yielding a white leather; it might be valuable but for the tendency to dangerous fermentation and development of a dark-red colouring matter.
Algarobilla consists of the seeds of an Indian tree, containing about 45% of tannin, and in general properties is similar to Divi-divi, but does not discolour so much upon fermentation.
Sumach is perhaps tile best and most useful material known. It is the ground leaves of a Sicilian plant, containing about 28% 01 tannin, and yielding a nearly white and very beautiful leather. It is used alone for tanning the best moroccos and finer leather, and being so valuable is much adulterated, the chief adulterant being Pistacia lentiscus (Stinko or Lentisco), an inferior and light-coloured catechol tannin. Other but inferior sumachs are also used. Then is Venetian sumach (Rhus cotinus) and Spanish sumach (Colpoon compressa); these are used to some extent in the countries bordering on the Mediterranean. R. Glabra and R. Copallina are also used in considerable quantities in America, where they are cultivated.
Galls are abnormal growths found upon oaks, and caused by the gall wasp laying eggs in the plant. They are best harvested just before the insect escapes. They contain from 50% to 60% of tannin, and are generally used for the commercial supply of tannic acid, and not for tanning purposes.
Gambier, terra japonica or catechu, is the product of a shrub cultivated in Singapore and the Malay Archipelago. It is made by boiling the shrub and allowing the extract to solidify. It is peculiar material, and may be completely washed out of a leather tanned with it. It mellows exceedingly, and keeps the leather fibre open; it may be said that it only goes in the leather to prepare and make easy the way for other tannins. Block gambier contains from 35% to 40% and cube gambier from 50% to 65% of tannin.
Hemlock generally reaches the market as extract, prepared from the bark of the American tree. It contains about 22% of tannin, has a pine-like odour, but yields a rather dark-coloured red leather.
Quebracho is imported mainly as solid extract, containing 63% to 70% of tannin; it is a harsh, light-red tannage, but darkens rapidly on exposure to light. It is used for freshening up very mellow liquors, but is rather wasteful, as it deposits an enormous amount of its tannin as phlobaphenes.
Mangrove or cutch is a solid extract prepared from the mangrove tree found in the swamps of Borneo and the Straits Settlements; it contains upwards of 60% of a red tannin.
Mimosa is the bark of the Australian golden wattle (Acacia pycnantha), and contains from 36% to 50% of tannin. It is a rather harsh tannage, yielding a flesh-coloured leather, and is useful for sharpening liquors. This bark is now successfully cultivated in Natal. The tannin content of this Natal bark is somewhat inferior, but the colour is superior to the Australian product.
Larch bark contains 9% to 10% of light-coloured tannin, and is used especially for tanning Scotch basils.
Canaigre is the air-dried tuberous roots of a Mexican plant, containing 25% to 30% of tannin and about 8% of starch. It yields an orange-coloured leather of considerable weight and firmness, Its cultivation did not pay well enough, so that it is little used.
Cutch, catechu or dark catechu, is obtained from the wood of Indian acacias, and is not to be confounded with mangrove cutch. It contains 60% of tanning matter and a large proportion of catechin similar to that contained in gambier, but much redder. It is used for dyeing browns and blacks with chrome and iron mordants.
The willow and the white birch barks contain, respectively, 12% to 14% and 2% to 5% of tannin. In combination they are used to produce the, famous Russia leather, whose insect-resisting odour is due to the birch bark. In America this leather is imitated with the American black birch bark (Betula lenta), and also with the oil obtained from its dry distillation.
In the list of materials two have been placed in a subsidiary class because they are a mixture of catechol and pyrogallol tannin. Oak bark produces the best leather known, proving that a blend of the two classes of tannins gives the best results. It is the bark of the coppice oak, and contains 12% to 14% of a reddish-yellow tannage. Valonia is the acorn cup of the Turkish and Greek oak. The Smyrna or Turkish valonia is best, and contains 32% to 36% of an almost white tannin. Greek valonia is greyer in colour, and contains 26% to 30% of tannin. It yields a tough, firm leather of great weight, due to the rapid deposition of a large amount of bloom.
Grinding and Leaching1 Tanning Materials.
(footnote 1. See Lye).
At first sight it would not seem possible that science could direct such a clumsy process as the grinding of tanning materials, and yet even here, the scientific smashing of tanning materials may mean the difference between profit and loss to the tanner. In most materials the tannin exists imprisoned in cells, and is also to some extent free, but with this latter condition, the science of grinding has nothing to do. If tanning materials are simply broken by a series of clean cuts, only those cells directly on the surfaces of the cuts will be ready to yield their tannin; therefore, if materials are ground by cutting, a proportion of the total tannin is thrown away. Hence it is necessary to bruise, break and otherwise sever the walls of all the cells containing the tannin; so that the machine wanted is one which crushes, twists and cuts the material at the same tithe, turning it out of uniform size and with little dust.
The apparatus in most common use is built on the same principle as the coffee mill, which consists of a series of segmental cutters; as the bark works down into the smaller cutters of the mill it is twisted and cut in every direction. This is a very good form of mill, but it requires a considerable amount of power and works slowly. The teeth require constant renewal, and should, therefore, be replaceable in rows, not, as in some forms, cast on the bell. The disintegrator is another form of mill, which produces its effect by violent concussion, obtained by the revolution in opposite directions of from four to six large metal arms fitted with projecting spikes inside a drum, the faces of which are also fitted with protruding pieces of metal. The arms make from 2000 to 4000 revolutions per minute. The chief objection to this apparatus is that it forms much dust, which is caught in silken bags fitted to gratings in the drum. The myrobalans crusher, a very useful machine for such materials as myrobalans and valonia, consists of a pair of toothed rollers above and a pair of fluted rollers beneath. The material is dropped upon the toothed rollers first, where it is broken and crushed; then the crushing is finished and any sharp corners rounded off in the fluted rollers.
It must not be thought that now the material is ground it is necessarily ready for leaching. This may or may not be so, depending upon whether the tanner is making light or heavy leathers.
If light leathers are being considered, it is ready for immediate leaching, i.e. to be infused with water in preparation of a liquor. If heavy leathers are in process of manufacture, he would be a very wasteful tanner who would extract his material raw. It must be borne in mind that when an infusion is made with fresh tanning material, the liquor begins to deposit decomposition products after standing a day or two, and the object of the heavy-leather tanner is to get this material deposited in the leather, to fill the pores, produce weight and make a firm, tough product. With this end in view he dusts his hides with this fresh material in the layers, i.e. he spreads a layer between each hide as it is laid down, so that the strong liquors penetrate and deposit in the hides. When most of this power to deposit has been usefully utilized in the layers, then the material (which is now, perhaps, half spent) is leached. The light-leather maker does not want a hard, firm leather, but a soft and pliable product; hence he leaches his material fresh, and does not trouble as to whether the tannin deposits in the pits or not.
Whether fresh or partially spent material is leached, the process is carried out in the same way. There are several methods in vogue; the best method only will be described, viz, the "press leach" system.
The leaching is carried out in a series of six square pits, each holding about 3 to 4 tons of material. The method depends upon the fact that when a weak liquor is forced over a stronger one they do not mix, by reason of the higher specific gravity of the stronger one; the weaker liquor, therefore, by its weight forces the stronger liquor downwards, and as the pit in which it is contained is fitted with a false bottom and side duct running over-into the next pit, the stronger liquor is forced upwards through this duct on to the next stronger pit. There the process is repeated, until finally the weak liquor or water, as the case may be, is run off the last vat as a very strong infusion. As a concrete example let us take the six pits shown in the figure.
No. 6 is the last vat, and the liquor, which is very strong, is about to be run off. No. 1 is spent material, over which all six liquors have passed, the present liquor having been pumped on as fresh water. The liquor from No. 6 is run off into the pump well, and liquor No. 1 is pumped over No. 2, thus forcing all liquors one forward and leaving pit No. 1 empty; this pit is now cast and filled with clean fishings and perhaps a little new material, clean water is then pumped on No. 2, which is now the weakest pit, and all liquors are thus forced forward one pit more, making No. f the strongest pit. After infusing for some time this is run off to the pump well, and the process repeated. It may be noted that the hotter the water is pumped on the weakest pit, the better will the material be spent, and the nearer the water is to boiling-point the better; in fact, a well-managed tanyard should have the spent tan down to between 1% and 2% of tannin, although this material is frequently thrown away containing up to 10% and sometimes even more. There is a great saving of time and labor in this method, since the liquors are self-adjusting.
Testing Tan Liquors:
The methods by which the tanning value of any substance may be determined are many, but few are at once capable of simple application and minute accuracy. An old method of ascertaining the strength of a tan liquor is by means of a hydrometer standardized against water, and called a barkometer. It consists of a long graduated stem fixed to a hollow bulb, the opposite end of which is weighted. It is placed in the liquor, the weighted end sinks to a certain depth, and the reading is taken on the stem at that point which touches "water mark." The graduations are such that if the specific gravity is multiplied by 1000 and then 1000 is subtracted from the result, the barkometer strength of the liquor is obtained. Thus 1029 specific gravity equals 29 barkometer. This method affords no indication of the amount of tannin present, but is useful to the man who knows his liquors by frequent analysis.
A factor which governs the quality of the leather quite as much as the tannin itself is the acidity of the liquors. It is known that gallic and tannic acids form insoluble calcium salts, and all the other acids present as acetic, propionic, butyric, lactic, formic, &c., form comparatively soluble salts, so that an easy method of determining this important factor is as follows.
Take a quantity, say 100 c.c., of tan liquor, filter till clear through paper, then pipette 10 c.c. into a small beaker (about 1 ½ in. diameter), place it on some printed paper and note how clear the print appears through the liquor; now gradually add from a burette a clear solution of saturated lime water until the liquor becomes just cloudy, that is until it just loses its brilliancy. Now read off the number of cubic centimetres required in the graduated stem of the burette, and either read as degrees (counting each c.c. as one degree), to which practice at once gives a useful signification, or calculate out in terms of acetic acid per 100 c.c. of liquor, reckoning saturated lime water as 1/20 normal. .
The methods which deal with the actual testing for tannin itself depend mostly upon one or other of two processes; either the precipitation of the tannin by means of gelatin, or its absorption by means of prepared hide. Sir Humphry Davy was the first to propose a method for analysing tanning materials, and he precipitated the tannin by means of gelatin in the presence of alum, then dried and weighed the precipitate, after washing free from excess of reagents. This method was improved by Stoddart, but cannot lay claim to much accuracy. Warington and Muller again modified the method, but their procedure being tedious and difficult to work could not be regarded as a great advance. Wagner then proposed precipitation by means of the alkaloids, with special regard to cinchonine sulphate in the presence of rosaniline acetate as indicator, but this method also proved useless. After this many metallic precipitants were tried, used gravimetrically and volumetrically, but without success. The weighing of precipitated tannates will never succeed, because the tannins are such a diverse class of substances that each tannin precipitates different quantities of the precipitants, and some materials contain two or three different tannins. Then there are also the difficulties of incomplete precipitation and the precipitation of colouring matter, &c. Among this class of methods may be mentioned Garlands, in which tartar emetic and sal ammoniac were employed. It was improved by Richards and Palmer.
Another class of methods depends upon the destruction of the tannin by some oxidizing agent, and the estimation of the amount required. Terreil rendered the tannin alkaline, and after agitating it with a known quantity of air, estimated the volume of oxygen absorbed. The method was slow and subject to many sources of error. Commaille oxidized with a known quantity of iodic acid and estimated the excess of iodate. This process also was troublesome, besides oxidizing the gallic acid (as do all the oxidation processes), and entailing a separate estimation of them after the removal of the tannin. Ferdinand Jean (1877) titrated alkaline tannin solution with standard iodine, but the mixture was so dark that the end reaction with starch could not be seen; in addition the gallic acid had again to be estimated. Monier proposed permanganate as an oxidizing agent, and Lowenthal made a very valuable improvement by adding indigo solution to the tannin solution, which controlled the oxidation and acted as indicator. This method also required double titration because of the gallic acid present, the tanning matters being removed from solution by means of gelatin and acidified salt.
The indirect gravimetric hide-powder method first took form about 1886. It was published in Der Gerber by Simand and Weiss, other workers being Eitner and Meerkatz. Hammer, Muntz and Ramspacher did some earlier work on similar lines, depending upon the specific gravity of solutions. Professor H. R. Procter perfected this method by packing a bell, similar in shape to a bottomless bottle of about 2 oz. (liq.) capacity, with the hide-powder, and siphoning the tan liquor up through the powder and over into a receiver. This deprives the tan liquor of tannin, and a portion of this non-tannin solution is evaporated to dryness and weighed till constant; similarly a portion of the original solution containing non-tannins and tannins is evaporated and weighed till constant; then the weight of the 000-tannins subtracted from the weight of the non-tannins and tannins gives the weight of tannin, which is calculated to percentage on original solutions. This method was adopted as official by the International Association of Leather Trades Chemists until September 1906, when its faults were vividly brought before them by Gordon Parker of London and Bennett of Leeds, working in collaboration, although other but not so complete work had been previously done to the same end. The main faults of the method were that the hide-powder absorbed non-tannins, and therefore registered them as tannins, and the hide-powder was partially soluble. This difficulty has now been overcome to a large extent in the present official method of the I.A.L.T.C.
Meanwhile, Parker and Munro Payne proposed a new method of analysis, the essence of which is as follows:
A definite excess of lime solution is added to a definite quantity of tannin solution and the excess of lime estimated; the tan solution is now deprived of tannin by means of a soluble modification of gelatin, called "collin", and the process is repeated. Thus we get two sets of figures, viz, total absorption. and acid absorption (i.e. acids other than tan); the latter subtracted from the former gives tannin absorption, and this is calculated out in percentage of original liquor. The method failed theoretically, because a definite molecular weight had to be assumed for tannins which are all different. There are also several other objections, but though, like the hide-powder method, it is quite empirical, it gives exceedingly useful results if the rules for working are strictly adhered to.
The present official method of the I.A.L.T.C. is a modification of the American official method, which is in turn a modification of a method proposed by W. Eitner, of the Vienna Leather Research Station. The hide-powder is very slightly chrome-tanned with a basic solution of chromium chloride, 2 grammes of the latter being used per 100 grammes of hide-powder, and is then washed free from soluble salts and squeezed to contain 70% of moisture, and is ready for use. This preliminary chroming does away with the difficulty of the powder being soluble, by rendering it quite in soluble; it also lessens the tendency to absorb non-tannins. Such a quantity of this wet powder as contains 6.5 grammes of dry hide is now taken, and water is added until this quantity contains exactly 20 grammes of moisture, i.e. 26.5 grammes in all; it is then agitated for 15 minutes with 100 cc. of the prepared tannin solution, which is made up to contain tannin within certain definite limits, in a mechanical rotator, and filtered. Of this non-tannin solution 50 c.c. is then evaporated to dryness. The same thing is done with 50 c.c. of original solution containing non-tannins and tannins, and both residues are weighed. The tannin is thus determined by difference. The method does all that science can do at present. The rules for carrying out the analysis are necessarily very strict. The object in view is that all chemists should get exactly concordant results, and in this the I.A.L.T.C, has succeeded.
The work done by Wood, Trotman, Procter, Parker and others on the alkaloidal precipitation of tannin deserves mention.
The hides of oxen are received in the tanyard in four different conditions: (1) market or slaughter hides, which, coming direct from the local abattoirs, are soft, moist and covered with dirt and blood; (2) wet salted hides; (3) dry salted hides; (4) sun-dried or flint hides the last three forms being the condition in which the imports of foreign hides are made. The first operation in the tannery is to clean the hides and bring them back as nearly as possible to the flaccid condition in which they left the animals back. The blood and other matter on market hides must be removed as quickly as possible, the blood being of itself a cause of dark stains and bad grain, and with the other refuse a source of putrefaction. When the hides are sound they are given perhaps two changes of water.
Salted hides, need a longer soaking than market hides, as it is not only essential to remove the salt from the hide, but also necessary to plump and soften the fibre which has been partially dehydrated and contracted by the salt, It must also be borne in mind that a 10% solution of salt dissolves hide substance, thereby causing an undesirable loss of weight, and, a weak solution prevents plumping, especially when taken into the limes, and may also cause buckling, which cannot easily be removed in after processes. Dried and dry salted hides require a much longer soaking than any other variety. Dried hides are always uncertain, as they may have putrefied before drying, and also may have been dried at too high a temperature; in the former case they fall to pieces in the limes, and in the latter case it is practically impossible to soak them back, unless putrefactive processes are used, and, such are always dangerous and difficult to work because of the Rivers Pollution Acts. Prolonged soaking in cold water dissolves a serious amount of hide substance. Soaking in brine may be advantageous, as it prevents putrefaction to some extent. Caustic soda, sodium sulphide and sulphurous acid may also be advantageously employed on account of their softening and antiseptic action, In, treating salted goods, the first wash water should always be rapidly changed, because, as mentioned, strong salt solutions dissolve hide; four changes of water should always be given to these goods.
|FIG 2. Double Acting Stocks|
There are other and mechanical means of softening obstinate material, viz. by stocking. The American hide mill, or double-acting stocks, shown diagrammatically in fig. 2, is a popular piece of apparatus, but the goods should never be subjected to violent mechanical treatment until soft enough to stand it, else severe grain cracking may result. Perhaps the use of sodium sulphide or caustic soda in conjunction with the American wash wheel is the safest method.
Whatever means are used the ultimate object is first to swell and open up the fibres as much as possible, and secondly to remove putrefactive refuse and dirt, which if left in is fixed by the lime in the process of depilation, and causes a dirty buff.
After being thus brought as nearly as possible into a uniform condition, all hides are treated alike. The first operation to which they are subjected is depilation, which removes not only the hair but also the scarf skin or epidermis. When the goods art sent to the limes for depilation they are, first of all, placed in an old lime, highly charged with organic matter and bacteria. It is the common belief that the lime causes the hair to loosen and fall out but this is not so: in fact. pure lime has the opposite effect of tightening the hair. The real cause of loosening of the hair is that the bacteria in the old lime creep down the hair, enter the rete Malpighi and hair sheath, and attack and decompose the soft cellular structure of the sheath and bulb, also altering the composition of the rete Malpighi by means of which the scarf skin adheres to the true skin. These products of the bacterial action are soluble in lime, and immediately dissolve, leaving the scarf skin and hair unbound and in a condition to leave the skin upon scraping. In this first "green" lime the action is mainly this destructive one, but the goods have yet to be made ready to receive the tan liquor, which they must enter in a plump, open and porous condition. Consequently, the "green" lime is followed with two more, the second being less charged with bacteria, and the third being, if not actually a new one, a very near approach to it; in these two limes the bundles of fibre are gradually softened, split up and distended, causing the hide to swell, the interfibrillar substance is rendered soluble, and the whole generally made suitable for transference to the tan liquors. The hide itself is only very slightly soluble; if care is taken, the grease is transformed into an insoluble calcium soap, and the hair is hardly acted upon at all.
The time the goods are in the limes and the method of making new limes depends upon the quality of the leather to be turned out. The harder and tougher the leather required the shorter and fresher the liming. For instance, for sole leather where a hard result is required, the time in the limes would be from 8 to 10 days, and a perfectly fresh top lime would be used, with the addition of sodium sulphide to hasten the process. Every tanner uses a different quantity of lime and sulphide, but a good average quantity is 7 lb lime per hide and 10-15 lb sodium sulphide per pit of 100 hides. The lime, is slaked with water and the sulphide mixed in during the slaking; if it is added to the pit when the slaking is finished the greater part of its effect is lost, as it does not then enter into the same chemical combinations with the lime, forming polysulphides, as when it is added during the process of slaking.
For softer and more pliable leathers, such as are required for harness and belting, a "lower" or mellower liming is given, and the time in the limes is increased from 9 to 12 days. Some of the old mellow liquor is added to the fresh lime in the making, of as just to take off the sharpness. It would be made up as loo sole leather, but with less sulphide or none at all, and then a dozen buckets of an old lime would be added. For lighter leathers from 3 to 6 weeks liming is given, and a fresh lime is never used.
"Sweating" as a method of depilation is obsolete in England so far as heavy leathers are concerned. It consists of hanging the goods a a moist warm room until incipient putrefaction sets in. This first attacks the more mucous portions, as the rete Malpighi, hair bulb and sheath, and so allows the hair to be removed as before. Thee method pulls down the hide, and the putrefaction may go too far, with disastrous results, but there is much to recommend it for sheepskins where the wool is the main consideration, the main point being that while lime entirely destroys wool, this process leaves it intact, only loosening the roots. It is consequently still much used.
Another method of fellmongering (dewooling) sheepskins is to paint the flesh side with a cream of lime made with a 10% solution of sodium sulphide and lay the goods in pile flesh to flesh, taking care that none of the solution comes in contact with the wool, which is ready for pulling in from 4 to 8 hours. Although this process may be used for any kind of skin, it is practically only used for sheep, as if any other skin is depilated in this manner all plumping effect is lost. Since this must be obtained in some way, it is an economy no time and material to place the goods in lime in the first instance.
Sometimes, in the commoner classes of sole leather, the hair is removed by painting the hair side with cream of lime and sulphide, as the came effect is produced by drawing the hides through a strong solution of sulphide; this completely destroys the hair, actually taking it into solution. But the hair roots remain embedded in the skin, and for this reason such leather always shows a dirty buff.
Arsenic sulphide (realgar) is slaked with the lime for the production of the finer light leathers, such as glace kid and glove kid. This method produces a very smooth grain (the tendency of sodium sulphide being to make the grain harsh and bold), and is therefore very suitable for the purpose, but it is very expensive.
Sufficient proof of the fact that it is not the lime which causes skins to unhair is found in the process of chemical liming patented lin Payne and Pullman. In this process the goods are first treated with caustic soda and then with calcium chloride; in this manner lime is formed in the skin by the reaction of the two salts, but the hair remains as tight as ever. If this process is to be used for unhairing and liming effect, the goods must be first subjected to a putrid soak to loosen the hair, and afterwards limed. Experiments made by the present writer also prove this theory. A piece calf skin was subjected to sterilized lime for several months, at end of which time the hair was as tight as ever: then bacterial influence was introduced, and the skin unhaired in as many days.
|FIG. 3. Tanners Beam||FIG. 4. Tanners Knives and Pin.|
After liming it is necessary to unhair the goods. This is done stretching a hide over a tanners beam (fig. 3), when with an unhairing knife (a, fig. 4) the beamsman partially scrapes and partially shaves off the hair and epidermis. Another workman, flesher, removes the flesh or net skin (panniculus adiposus), a fatty matter from the flesh side of the skin, with the fleshing knife (two-edged), seen in b, fig. 4. For these operations several machines have been adopted, working mostly with revolving spiral blades or vibrating cutters, under which the hides pass in a fully extended state. Among these may mentioned the Leidgen unhairer, which works on a rubber bed, which "gives" with the irregularities of the hide, and the Wilson flesher, consisting of a series of knives attached to a revolving belt, and which also give in contact with irregularities.
At this stage the hide is divided into several parts, the process being known as "rounding." The object of the division is this: Lain parts of the hide termed the "offal" are of less value than the butt, which consists of the prime part. The grain of the butt is fine and close in texture, whereas the offal grain is loose, coarse and open, and if the offal is placed in the same superior liquors as the butt, being open and porous, it will absorb the best of the tannin first; consequently the offal goes to a set of inferior liquors, often consisting of those through which the butts have passed. The hides are "rounded" with harp curved butchers knife; the divisions are seen in fig. 5. The bellies, cheeks and shoulders constitute the offal, and are tanned separately although the shoulder is not often detached from the butt until the end of the "suspenders," being of slightly better quality than the bellies. The butt is is divided into two "bends." This separation is not made until the tanning of the butt is finished, when it is cut in two, and the components sold as "bends," although as often as the butt is not divided. In America the hides are only split down the ridge of the back, from head to tail, and tanned as hides. Dressing hides are more frequently rounded after tanning, the mode depending on the purpose for which the leather is required.
The next step is to remove as much "scud" and lime as possible, the degree of removal of the latter depending upon the kind of leather to be turned out. "Scudding" consists of working the already unhaired hide over the beam with an unhairing knife with increased pressure, squeezing out the dirt, which is composed of pigment cells, semi-soluble compounds of lime, and hide, hair sacks and soluble hide substance, &c. This exudes as a dirty, milky, viscid liquid, and mechanically brings the lime out with it, but involves a great and undesirable loss of hide substance, heavy leather being sold by weight. This difficulty is now got over by giving the goods an acid bath first, to delime the surface; the acid fixes this soluble hide substance (which is only soluble in alkalies) and hardens it, thus preventing its loss, and the goods may then be scudded clean with safety. The surface of all heavy leathers must be delimed to obtain a good coloured leather, the demand of the present day boot manufacturer; it is also necessary to carry this further with milder leathers than sole, such as harness and belly, &c., as excess of lime causes the leather to crack Shoulder when finished. Perhaps the best material for this purpose is boracic acid, using about 10 lb per 100 butts, and suspending the goods. This acid yields a characteristic fine grain, and because of its limited solubility cannot be used in excess. Other acids are also used, such as acetic, lactic, formic, hydrochloric, with varying success. Where the water used is very soft, it is only necessary to wash in water for a few hours, when the butts are ready for tanning, but if the water is hard, the lime is fixed in the hide by the bicarbonates it contains, in the form of carbonate, and the result is somewhat disastrous.
After deliming, the butts are scudded, rinsed through water or weak acid, and go off to the tan pits for tanning proper. Any lime which remains is sufficiently removed by the acidity of the early tan liquors.
The actual tanning now begins, and the operations involved may be divided into a series of three: (I) colouring, (2) handling, (3) laying away.
The colouring pits or suspenders, perhaps a series of eight pits, consist of liquors ranging from 16° to 40° barkometer, which were once the strongest liquors in the yard, but have gradually worked down, having had some hundreds of hides through them; they now contain very little tannin, and consist mainly of developed acids which neutralize the lime, plump the hide, colour it off, and generally prepare it to receive stronger liquors. The goods are suspended in these pits on poles, which are lifted up and down several times a day to ensure the goods taking an even colour; they are moved one pit forward each day into slightly stronger liquors, and take about from 7 to 18 days to get through the suspender stage.
The reason why the goods are suspended at this stage instead of being laid flat is that if the latter course were adopted, the hides would sink and touch one another, and the touch-marks, not being accessible to the tan liquor, would not colour, and uneven colouring would thus result; in addition the weight of the top hides would flatten the lower ones and prevent their plumping, and this condition would be exceedingly difficult to remedy in the after liquors. Another question which might occur to the non-technical reader is, why should not the process be hastened by placing the goods in strong liquors? The reason is simple. Strong tanning solutions have the effect of drawing the grain of pelt, i.e. contracting the fibres, and causing the leather to assume a very wrinkled appearance which cannot afterwards be remedied; at the same time case tanning results i.e. the outside only gets tanned, leaving the centre still raw hide, and once the outside is case-hardened it is impossible for the liquor to penetrate and finish the tanning. This ccndition being almost irremediable, the leather would thus be rendered useless.
|FIG. 6: Tanner s Hook (without handle).|
After the suspenders the goods are transferred to a series of handlers or floaters, consisting of, perhaps, a dozen pits containing liquors ranging from 30° to 55° barkometer. These liquors contain an appreciable quantity of both tannin and acid, once formed the lay-aways, and are destined to constitute the suspenders. In these pits the goods, having been evenly coloured off, are laid fiat, handled every day in the hinder (weaker) liquors and shifted forward, perhaps every two days, at the tanners convenience. The handling consists of lifting the butts out of the pit by means of a tanners hook (fig. 6), piling them on the side of the pit to drain, and returning them to the pit, the top butt in the one handler being returned as the bottom in the next. This operation is continued throughout the process, only, as the hides advance the necessity for frequent handling decreases.
The top two handler pits are sometimes converted into "dusters," i.e. when the hides have advanced to these pits, as each butt is lowered, a small quantity of tanning material is sprinkled on it.
Some tanners, now that the hides are set flat, put them in suspension again before laying away; the method has its advantages, but is not general. The goods are generally laid away immediately. The layer liquors consist of leached liquors from the fishings, strengthened with either chestnut or oakwood extract, or a mixture of the two. The first layer is made up to, say, 60° barkometer in this way, and as the hides are laid down they are sprinkled with fresh tanning material, and remain undisturbed for about one week. The second layer is a 70° barkometer liquor, the hides are again sprinkled and allowed to lie for perhaps two weeks. The third may be 80° barkometer and the fourth 90°, the goods being dusted as before, and lying undisturbed for perhaps three or four weeks respectively. Some tanners give more layers, and some give less, some more or less time, or greater or lesser strengths of liquor, but this tannage is a typical modern one.
As regards dusting material, for mellow leather, mellow materials are required, such as myrobalans being the mellowest and mimosa bark the most astringent of those used in this connection. For harder leather, as sole leather, a much smaller quantity of myrobalans is used, if any at all, a fair quantity of mimosa bark as a medium, and much valonia, which deposits a large amount of bloom, and is of great astringency. About 3 to 4 cwt. of a judicious mixture is used for each pit, the mellower material predominating in the earlier liquors and the most astringent in the later liquors.
The tanning is now finished, and the goods are handled out of the pits, brushed free from dusting material, washed up in weak liquor, piled and allowed to drip for 2 or 3 days so that the tan may become set.
From this stage the treatment of sole leather differs from that of harness, belting and mellower leathers. As regards the first, it will be found on looking at the dripping pile of leather that each butt is covered with a fawn-coloured deposit, known technically as bloom; this disguises the under colour of the leather, just like a coat of paint. The theory of the formation of this bloom is this. Strong solutions of tannin, such as are formed between the bides from dusting materials, are not able to exist for long without decomposition, and consequently the tannin begins to condense, and forms other acids and insoluble anhydrides; this insoluble matter separates in and on the leather, giving weight, firmness, and rendering the leather waterproof. It is known technically as bloom and, chemically as ellagic acid.
After dripping, the goods are scoured free from surface bloom in a Wilson scouring machine, and are then ready for bleaching. There are several methods by which this is effected, or, more correctly several materials or mixtures are used, the method of application being the same, viz, the goods are "vatted" (steeped) br some hours in the bleaching mixture at a temperature of 110° F. The mixture may consist of either sumach and a light-coloured chestnut extract made to 110° barkometer, and 110° F., or some bleaching extract made for the purpose, consisting of bisulphited liquid quebracho, which bleaches by reason of the free sulphurous acid it contains. The former method is best (though more expensive), as it removes less weight, and the light shade of colour is more permanent than that obtained by using bisulphited extracts.
After the first vatting the goods are laid up in pile to drip; meanwhile the liquor is again heated, and they are then returned for another twenty-four hours, again removed and allowed to drip for 2 to 3 days, after which they are oiled with cod oil on the grain and hung up in the sheds to dry in the dark. When they have dried to an india rubber-like condition, they are piled and allowed to heat slightly until a greyish bloom rises to the surface, they are then set out and stretched in a Wilson scouring machine; using brass slickers instead of the stone ones used for scouring, pinned over by hand (with the three-edged instrument seen in c, fig. 4, and known as a "pin") to remove any bloom not removed by the machine, oiled and dried. When of a damp even colour they are "rolled on" between two heavy rollers like a wringing machine, the pressure being applied from above, hung up in the dark sheds again until the uneven colour so produced has dried in, and then rolled off through the same machine, the pressure being applied from below. They are now dried right out, brushed on the grain to produce a slight gloss, and are finished.
As regards the finishing of harness leather, &c., the goods, after thorough dripping for a day or two, are brushed, lightly scoured, washed up in hot sumach and extract to improve the colour, and are again laid up in pile for two days; they are then given a good coat of cod oil, sent to the sheds, and dried right out. Only sufficient scouring is given to clean the goods, the object of the tanner being to leave as much weight in as possible, although all this superfluous tan has to be washed out by the currier before he can proceed.
When the goods are dried from the sheds they are purchased by the currier. If, as is often the case, the tanner is his own currier, he does not tan the goods so heavily, or trouble about adding superfluous weight, but otherwise the after processes, the art of the currier, are the same.
Currying consists of working oil and grease into the leather to render it pliable and increase its strength. It was once thought that this was a mere physical effect produced by the oil, but such is not the case. Currying with animal oils is a second tannage in itself; the oils oxidize in the fibres and produce aldehydes, which are well-known tanning agents; and this double tannage renders the leather very strong. Then there is the lubricating effect, a very important physical action so far as the strength of the leather is concerned. Mineral oils are much used, but they do not oxidize to aldehydes, or, for the matter of that, to anything else, as they are not subject to decomposition. They, therefore, produce no second tannage, and their action is merely the physical one of lubrication, and this is only more or less temporary, as, except in the case of the heavier greases, they slowly evaporate. Where animal fats and oils are used, the longer the goods are left in contact with the grease the better and stronger will be the leather.
In the "Einbrennen" process (German for "burning in"), the hides are thoroughly scoured, and when dry are dipped into hot grease, which is then allowed to cool; when it is nearly set the goods are removed and set out. This process is not much used in Great Britain.
In hand-stuffing belting butts the goods are first thoroughly soaked in water to which has been added some soda, and them scoured and stretched by machine. They are then lightly shaved to take off the loose flesh and thin the neck. The whole of the mechanically deposited tannin is removed by scouring, to make room for the grease, and they are then put into a sumach vat of 40° barkometer to brighten the colour, horsed up to drip and set out. If any loading, to produce fictitious weight, is to hi done, it is done now, by brushing the solution of either epson salts, barium chloride or glucose, or a mixture, into the flesh and laying away in pile for some days to allow of absorption when, perhaps, another coat is given. Whether this is done o not, the goods are hung up until "tempered" (denoting certain degree of dryness), and then treated with dubbin. Thi~ is manufactured by melting down tallow in a steam-jacketed pan and adding cod oil, the mixture being stirred continually; whet quite clear, it is cooled as rapidly as possible by running cold water through the steam pan, the stirring being continued until it has set. The tempered leather having been set out on a glass table, to which the flesh side adheres, is given a thin coat of the dubbin on the grain, turned, set out on the flesh, and given a thick coat of dubbin. Then it is hung up in a wind shed, and as the moisture dries out the grease goes in. After two or three days the goods are set out in grease with a brass slicker, given a coat of dubbin on the grain slightly thicker than the first coat, then flesh dubbined, a slightly thinner coat being applied than at first, and stoved at 70° F. The grease which is slicked off when setting out in grease is collected and sold. After hanging in the warm stove for 2 or 3 days the butts are laid away in grease for a month; they are then slicked out tight, flesh and grain, and buck tallowed. Hard tallow is first rubbed on the grain, when a slight polish is induced by rubbing with the smoothed rounded edge of a thick slab of glass; they are then hung up in the stove or stretched in frames to dry. A great deal of stuffing is now carried out by drumming the goods in hot hard fats in previously heated drums; and in modern times the tedious process of laying away in grease for a month is either left undone altogether or very considerably shortened.
In the tanning and dressing of the commoner varieties of kips and dried hides, the materials used are of a poorer quality, and the time taken for all processes is cut down, so that whereas the time taken to dress the better class of leather is from 7 to 10 months, and in a few cases more, these cheaper goods are turned out in from 3½ to 5 months.
A considerable quantity of the leather which reaches England, such as East India tanned kips, Australian sides, &c., is bought up and retanned, being sold then as a much better-class leather. The first operation with such goods is to strip them of any grease they may contain, and part of their original tannage. This is effectually carried out by first soaking them thoroughly, laying them up to drip, and drumming for half an hour in a weak solution of soda; they are then washed by drumming in plenty of water, the water is run off and replaced by very weak sulphuric acid to neutralize any remaining soda; this is in turn run off and replaced by weak tan liquor, and the goods are so tanned by drumming for some days in a liquor of gradually increasing strength. The liquor is made up as cheaply as possible with plenty of solid quebracho and other cheap extract, which is dried in with, perhaps, glucose, epsom salts, &c. to produce weight. Sometimes a better tannage is given to goods of, fail quality, in which they are, perhaps, started in the drum and finished in layers, slightly better materials being used all through. and a longer time taken to complete the tannage.
The tannage of dressing hides for bag and portmanteau work is rather different from the other varieties described, in that the goods, after having had a rather longer liming, are "bated" or "puered."
Bating consists of placing the goods in a wheel or paddle with her or pigeon excrement, and paddling for from a few hours to 2 or 3 days. In puering, dog manure is used, and this being rather more active, the process does not take so long. This bating or puering is carried out in warm liquors, and the actions involved are several From a practical point of view the action is the removal of the lime and the solution of the hair sacs and a certain amount of inter fibrillar substance. In this way the goods are pulled down to I soft flaccid condition, which allows of the removal of short hair hair sacs and other filth by scudding with an unhairing knife upon the beam. The lime is partially taken into solution ant partially removed mechanically during the scudding. A large quantity of hide substance, semi-soluble and soluble, is lost by being pressed out, but this matters little, as for dressing work, area, and not weight, is the main consideration. Theoretically the action is due to bacteria and bacterial products (organized ferments ant enzymes), unorganized ferments or vegetable ferments like the yeast ferment, such as pancreadine, pepsin, &c. and chemicals, such as ammonium and calcium salts and phosphates, , all of which an present in the manure. The evolved gases also play their part it the action.
There are several bates upon the market as substitutes for dung bate. A most popular one was the American "Tiffany" bate made by keeping a weak glue solution warm for some hours ant then introducing a piece of blue cheese to start fermentation; when fermenting, glucose was added, and the bate was then ready for work. This and all other bates have been more or less supplanted by "erodin," discovered after years of research by Mr Wood (Nottingham) and Drs Popp and Becker (Vienna). This is an artificial bate containing the main constituents of the dung bate. It is supplied in the form of a bag of nutrient material for bacteria to thrive on and a bottle of bacterial culture. The nutrient material is dissolved in water and the bacterial culture added, and after allowing the mixture to get working it is ready for use. Many tons of this bate are now being used per annum. Its advantages are: (I) that it is clean, (2) that it is under perfect control, and (3) that stains and bate burns, which so often accompany the dung bate, are absolutely absent. Bate burns are caused by not filtering the dung bate through coarse sacking before use. The accumulation of useless solid matter settles on the skins if they are not kept well in motion, causing excessive action in these places.
After pulling down the goods to a soft, silky condition by bating or puering, it is necessary, after scudding, to plump them up again and bring them into a clean and fit condition for receiving the tan. This is done by "drenching" in a bran drench. A quantity of bran is scalded and allowed to ferment. When the fermentation has reached the proper stage the goods are placed, together with the bran liquor, in a suitable pit or vat, and are allowed to remain until they have risen three times; this rising to the surface is caused by the gaseous products of the fermentation being caught by the skin. The plumping action of the bran is due to the acids produced during fermentation and also in part to the gases, and the cleansing action is due to the mechanical action of the particles of bran rubbing against the grain of the skins. After drenching, the goods are washed free from bran, and are ready for the tanning process.
Drenching, now that all kinds of acids are available, is not so much used for heavy hides as for light skins, it being found much more convenient and cheaper to use acids. In fact, bating and puering are being gradually replaced by acid baths in the case of heavy leathers, the process being carried out as deliming for sole leather, only much more thoroughly in the case of dressing leather.
The tanning of dressing hides, which are not rounded into butts and offal, is briefly as follows. They first enter a series of colouring pits or suspenders, and then a series of handlers, by which time they should be plump and coloured through; in this condition they are split either by means of a union. or band-knife splitting machine (fig. 7).
|FIG. 7. Band Knife Splitting Machine.|
This latter is the most popular machine, and consists essentially of an endless band knife a which revolves at considerable speed with its cutting edges close to the sides of a pair of rollers through which the leather is fed and pressed against the knife. The lower of these rollers is made of short segments or rings, each separately capable of yielding so as to accommodate itself to the unequal thicknesses of various parts of a hide. The thickness of the leather to be cut is gauged to the utmost minuteness by means of the hand screws b b which raise or lower the upper roller. The knife edge of the cutter is kept keen by rubbing against revolving emery wheels c as it passes round. So delicately can this machine effect its work that slices of leather uniform throughout and as thin as paper can be easily prepared by it, and by its aid it is quite common to split hides into as many as three useful splits.
The dressing hides are usually split in two. Here we will leave the split (flesh) for a time and continue with the treatment of the grain. After splitting, they enter another series of handlers, are then piled up for a day or two, and thrown into a large drum with sumach mixed to a paste with hot water and a light-coloured extract. They are drummed in this for one hour to brighten and mellow the grain, washed up in tepid liquor, piled for two days, and drummed with cod oil or some other suitable oil or mixture; they are now piled for a day or two to absorb, dried out, flattened on the grain, and flesh folded.
The splits are rinsed up in old sumach liquor and drummed with cheap extracts and adulterants, such as size, glucose, barium chloride, epsom salts, &c. after which they are piled up to drain, dried to a "sammied" condition, rolled to make firm, and dried right out.
In the dressing hide tannage very mellow materials are used. Gambier and myrobalans form the main body of the tannage, together with a little quebracho extract, mimosa bark, sumach and extracts.
Under the head of upper leather are included the thin, soft and pliable leathers, which find their principal, but by no means exclusive, application in making the uppers of boots and shoes, which may be taken as a type of a class of leathers. They are made from such skins as East Indian kips, light cow and horse hides, thin split hides, such as those described under dressing leather, but split rather thinner, and calf. The preparatory dressing of such skins and the tanning operations do not differ essentially from those already described. In proportion to the thinness of the skin treated, the processes are more rapidly finished and less complex, the tannage is a little lighter, heavy materials such as valonia being used sparsely if at all. Generally speaking, the goods have a longer and mellower liming and bating, the lime being more thoroughly removed than for the leathers previously described, to produce greater pliability, and everything must tend in this direction. The heavier hides and hips are split as described under dressing leather, and then tanned right out.
Currying of the Lighter Leathers:
The duty of the currier is not solely directed towards heavier leathers; he is also entrusted with the dressing and fitting of the lighter leathers for the shoemaker, coachbuilder, saddler, &c. He has to pare the leather down and reduce inequalities in thickness, to impregnate it with fatty matter in order to render it soft and pliable, and to give it such a surface dressing, colour and finish as will please the eye and suit the purposes of its consumers. The fact that machinery is used by some curriers for nearly every mechanical operation, while others adhere to the manual system, renders it almost impossible to give in brief an outline of operations which will be consistent with any considerable number of curriers.
The following may be taken as a typical modern dressing of waxed calf or waxed kips. The goods are first of all soaked down and brought to a "sammied" condition for shaving. In the better class leathers hand-shaving is still adhered to, as it is maintained that the drag of the shaving machine on the leather causes the nap finish to be coarser. Hand-shaving is carried out on a beam or strong frame of wood, supporting a stout plank faced with lignum vitae, and set vertically, or nearly so. The knife (fig. 8) is a double-edged rectangular blade about 12 in. by 5 in., girded on either side along its whole length and down the centre with two bars 3 in. wide, leaving each blade protruding 1 in. beyond them; it has a straight handle at one end and a cross handle at the other in the plane of the blade. The edges of this knife are first made very keen, and are then turned over so as to form a wire edge, by means of the thicker of the two straight steel tools shown
|FIG. 8.Currying Knife.|
in fig. 9. The wire edge is preserved by drawing
the thinner of the two steel tools along the interior angle of the wire
edge and then along the outside of the turnover edge. The skin being
thrown flesh uppermost over the vertical beam, the shaver presses his
body against it, and leaning over the top holds the knife by its two
handles almost at right angles to the leather, and proceeds to shave it
by a scraping stroke downwards which the wire edge, being set at right
angles to the knife and almost parallel with the skin, turns into a
cut. The skin is shifted so as to bring all parts under the action of
the knife, the shaver frequently passing a fold ,between his finger to
test the progress of his work. After shaving, the goods are thoroughly
soaked, allowed to drip, and are ready for "scouring." This operation has
for its object the removal of bloom (ellagic acid) and any other
superfluous adherent matter. The scouring solution Consists of a weak
solution of soft soap and borax. This is first well brushed into the
flesh of the leather, which is then "sleeked" (slicked) out with a steel
slicker shown at S fig. 9. The upper part of the "slicker" is wooden, and
into it a steel, stone, brass or vulcanite
|FIG 9.Currying Apparatus.|
R. raising board
blade is forced and fastened. The wooden part is grasped in both hands, and the blade is half rubbed and half scraped over the surface of the leather in successive strokes, the angle of the slicker being a continuation of the angle which the thrust out arms of the worker, form with the body, perhaps 30° to 45°, with the leather, depending upon the pressure to be applied. The soap and borax solution is continually dashed on the leather to supply a body for the removal of the bloom with the steel slicker. The hide is now turned, and the grain is scoured with a stone slicker and brush, with soap and borax solution, it is then rinsed up, and sent to dry; when sammied, it is "set" i.e. the grain is laid smooth with a brass or steel slicker and dried right out. It is now ready for stuffing, which is invariably done in the drum with a mixture of stearine and sod oil, to which is sometimes added cod oil and wool fat; it is then set out on the grain and "canked" on the flesh, the grain side is glassed, and the leather right now out. The goods are rounded, ie. the lighter coloured parts of the grain are damped with a mixture of dubbin and water to bring them to even colour, and then laid in pile, for a few days to mellow, when they are ready for whitening. The goods are damped down and got to the right temper with a weak soap and water solution, and are then whitened, an operation similar to shaving, carried out with a turned edge slicker. By this means a fine flesh surface is obtained upon which to finish by waxing; after this they are boarded with an arm board (R, fig. 9) to bring up the grain, or give a granular appearance to the leather and make it supple, when they may be turned flesh inwards and bruised, a similar operation to graining, essentially to soften and make them pliant. At this stage the goods are known as finished russet, and are stored until ready for waxing.
For waxing, the first operation is to black the goods. In England this is generally done by hand, but machinery is much more used in the United States. The process consists of well brushing into the flesh side of the skins a black preparation made in one of two ways. The older recipe is a mixture of lampblack, oil and perhaps a little tallow; the newer recipe consists of soap, lampblack, logwood extract and water. Either of these is brushed well into the flesh side, which is then glassed up by means of a thick slab of glass, the smooth rounded edges being used with a sucking motion, and the goods are hung up to dry. When dry they are oiled with cod oil, and are ready for sizing. Goods blacked with soap blacking are sized once, those prepared with oil blacking are sized twice. The size used for soap black skins may consist of a mixture of beeswax, pitch, linseed oil, tallow, soap, glue and logwood extract. For oil blacked skins the bottom sizing may be glue, soap, logwood extract and water, after the application of which the goods are dried and the "top sizing" applied; this consists of glue, cod oil, beeswax, tallow, venice turps, black dye and water. The sizings having been applied with a sponge or soft brush, thoroughly rubbed in with a glass slicker, crush marks are removed by padding with a soft leather pad, and the goods, after being dried out, are ready for the market.
In the dressing of waxed grain leathers, such as French calf, satin leather, &c., the preparatory processes are much the same as for waxed leathers described above as far as stuffing, after which the grain is prepared to take the colour by light hand scouring with weak soap and borax solution. The dye is now applied, and so that it may take well on the grain of the greasy leather, a quantity of either soap, turkey red oil or methylated spirit is added to the solution. Acid colours are preferably used, and three coats are given to the dry leather, which is then grained with an arm board, and finished by the application of hard buck tallow to the grain and brushing. The dye or stain may consist of aniline colours for coloured leathers, or, in the case of blacks, consecutive applications of logwood and iron solutions are given.
Finishing dressing Hides for Bag and Portmanteau Work:
The hides as received from the tanner are soaked down, piled to sammy, and shaved, generally by machine, after which they are scoured, as under waxed leather; sumached and hung up to dry; when just damp they are set out with a brass slicker and dried right out. The grain is now filled by applying a solution of either Irish moss, linseed mucilage or any other mucilaginous filling material, and the flesh is sized with a mixture of mucilage and French chalk, after which the goods are brushstained with an aniline dye, to which has been added linseed mucilage to give it body; two coats are applied to the sammied leather. When the goods have sammied, after the last coat of stain, they are printed with a brass roller in a jigger, or by means of a machine embosser. This process consists of imprinting the grain by pressure from a brass roller, on which the pattern is deeply etched. After printing, the flesh side is sponged with a weak milk solution, lightly glassed and dried, when the grain is sponged with weak linseed mucilage, almost dried, and brushed by machine. The hides are now finished, by the application either of pure buck tallow or of a mixture of carnauba wax and soap; this is rubbed up into a slight gloss with a flannel.
So far only the heavier leathers have been dealt with; we will now proceed to discuss lighter calf, goat, sheep, seal, &c.
In tanning light leathers everything must tend towards suppleness and pliability in the finished leather, in contrast to the firmness and solidity required in heavy leathers. Consequently, the liming is longer and mellower; puering, bating or some bacterial substitute always follows; the tannage is much shorter; and mellow materials are used. A deposition of bloom in the goods is not often required, so that very soon after they are struck through they are removed as tanned. The materials largely used are sumach, oak bark, gambier, myrobalans, mimosa bark, willow, birch and larch barks.
As with heavy leathers, so also with light leathers, there are various ways of tanning; and quality has much to do with the elaboration or modification of the methods employed. The tanning of all leathers will be dealt with first, dyeing and finishing operations being treated later.
The vegetable-tanned leather de luxe is a bottle-tanned skin. It is superior to every other class of vegetable-tanned leather in every way, but owing to competition not a great deal is now produced, as it is perhaps the most expensive leather ever put on the market. The method of preparation is as follows.
The skins are usually hard and dry when received, so they are at once soaked down, and when sufficiently soft are either milled in the stocks, drummed in a lattice drum (American dash wheel, fig. 10), or "broken down" over the beam by working on the flesh with a blunt unhairing knife. They are next mellow limed (about 3 weeks), sulphide being used if convenient, unhaired and fleshed as described under heavy leathers, and are then ready for puering. This process is carried through at about 80° F., when the goods are worked on the beam, rinsed, drenched in a bran drench, scudded, and are ready for tanning. The skins are now folded down the centre of the back from neck to butt (tail end), flesh outwards, and the edges are tightly stitched all round to form bags, leaving an aperture at one of the shanks for filling; they are now turned grain outwards and filled with strong sumach liquor and some quantity of solid sumach to fill up the interstices and prevent leakage, after which the open shank is tied up, and they are thrown into warm sumach liquour, where they about like so many pigs, being continually pushed under the surface with a dole. When struck through they are piled on a shelf above the vat, and by their own weight the liquor, is forced through the skins. The tannage takes about 24 hours, and when finished the stitching is ripped up, the skins are slicked out, strained on frames and dried. Straining consists of nailing the skins out on boards in a stretched condition, or the stretching in frames by means of strings laced in the edge of the frame and attached to the edge of the skin.
|FIG. 10.Dash Wheel.|
The commoner sumach-tanned skins (but still of very good quality) are tanned in paddle wheels, a series of three being most conveniently used in the same manner as the three-pit system of liming, each wheel having three packs of skins through it before being thrown away. This paddling tends to make a bolder grain, as the skins are kept in continual motion, and work over one another. Some manufacturers finish the tannage with a mixture of sumach and oak bark; this treatment yields a less porous product. Others, when the skins are strained and in a semi-dry condition, apply neatsfoot or other oil, or a mixture of glycerine and oil, to the grain to lubricate it and make it more supple; the glycerine mixture is generally used for chrome leather, and will be discussed later under that head.
The skins tanned as above are largely dressed as morocco. Originally morocco was produced by the Moors in southern Spain and Morocco, whence the industry spread to the Levant, Turkey and the Mediterranean coast of Africa generally, where the leather was made from a species of sumach. Peculiarly enough, the dyeing was carried out before the tanning, with Roman alum as "mordant" and kermes, which with the alum produced a fine red colour. Such leather was peculiarly clear in colour, elastic and soft, yet firm and fine in grain and texture, and has long been much prized for bindings, being the material in which most of the artistic work of the 16th-century binders was executed. Now, in addition to the genuine morocco made from goat skins, we have imitation or French moroccos, for which split calf and especially sheep skins are employed, and as the appearance of morocco is the result of the style of graining and finish, which can now be imitated by printing or embossing machines, morocco can be made from all varieties of thin leather.
Great quantities of "Persian" (East India tanned) sheep and goat are now dressed as moroccos and for innumerable other purposes, the method being as follows: The goods are tanned with turwar bark and cassia bark, besides being impregnated with sesame oil, even to the extent of 30%. The first operation is to "strip" them of the oil and original tannage as far as possible, by drumming in a solution of soda; the soap thus formed is got rid of by thoroughly washing the goods, when they are "soured" in a weak bath of sulphuric acid to brighten the colour and remove iron stains, after which they are washed up and re-tanned by drumming in warm suinach, allowing about 4 oz. per skin. They are then slicked out, dried and are ready for dyeing.
The tanning of sheep and lamb skins differs very essentially from the tanning of goat and other leathers, mainly in the preparatory processes. As the wool is completely destroyed by lime, other methods have to be resorted to. The process usually practised is known as "sweating"; this consists of hanging the moist skins up in a warm, badly-ventilated chamber and allowing incipient putrefaction to set in. The chamber is always kept warm and saturated with moisture, either by means of a steam jet or water sprinklers. During the process large quantities of ammoniacal vapours are given off, and after two or three days the skins become slimy to the touch, and the wool slips easily; at this stage the goods are removed, for if the putrefaction goes too far the grain of the skin is irretrievably ruined. The wool is now pulled by pullers, who throw it into bins arranged to receive the different qualities; for one pelt may have three different grades of wool on it.
Other methods of dewooling are to paint the flesh with a solution of sodium sulphide, or cream of lime made with a solution of sodium sulphide; in either case the goods are piled flesh to flesh for an hour or so, and care is taken that the dewooling agent does not touch the wool. The pelt is then pulled and rapidly swilled in a stream of running water. The goods are now, in some yards, lightly limed to plump them superficially, by paddling in a milk of lime, and at this stage, or when the goods have been "struck through" with tan liquor, they are "degreased" either by hydraulic pressure or by benzene degreasing. This is to expel the oleaginous or fatty matter with which sheep skins are richly impregnated; the average yield is about 4 oz. per skin. The tannage is carried out in much the same way as for goat skins, the goods being started in old acid bark liquors; the general tannage consists of sumach and bark.
Basils are sheep skins tanned in various ways. English basils are tanned with oak bark, although, as in all other leathers, inferior tannages are now common; Scotch basils are tanned with larch bark, Australian and New Zealand basils with mimosa bark and Turkish basils with galls. The last are the commonest kind of skins imported into Great Britain, and are usually only semi-tanned. Roans are sumach-tanned sheep skins.
Shivers are the grain splits of sheep skins, the fleshes of which are finished for chamois leather. The goods are split in the limed state, just as the grains are ready for tanning, and are subsequently treated much as sumach-tanned goat skins, or in any other convenient way; the fleshes, on the other hand, go back into the limes, as it is necessary to get a large quantity of lime into leather which is to be finished as chamois.
Russia Leather was originally a speciality of Russia, where it was made from the hides of young cattle, and dressed either a brownish red or black colour for upper leather, bookbinding, dressing-cases, purses, &c. It is now made throughout Europe and America, the best qualities being obtained from Austria. The empyreumatic odour of the old genuine Russia leather was derived from a long-continued contact with willow and the bark of the white birch, which contains the odorous betulin oil. Horse hides, calf, goat, sheep skins and even splits are now dressed as Russia leather, but most of these are of a decidedly inferior quality, and as they are merely treated with birch bark oil to give them something of the odour by which Russia leather is ordinarily recognized, they scarcely deserve the name under which they pass. The present-day genuine Russia leather is tanned like other light leathers, but properly in willow bark, although poplar and spruce fir barks are used. After tanning and setting out the goods are treated with the empyreumatic oil obtained by the dry distillation of birch bark. The red colour commonly seen in Russia leather is now produced by aniline colours, but was originally gained by the application of an infusion of Brazil wood, which was rubbed over the grain with a brush or sponge. Some time ago Russia leather got into disrepute because of its rapid decay; this was owing to its being dyed with a very acid solution of tin salts and cochineal, the acid completely destroying the leather in a year or two. The black leather is obtained by staining with logwood infusion and iron acetate. The leather, if genuine quality, is very watertight and strong, and owing to its impregnation with the empyreumatic oil, it wards off the attacks of insects.
Seal Leathers, &c.:
The tannage of seal skins is now an important department of the leather industry of the United Kingdom. The skins form one of the items of the whaling industry which principally centres in Dundee, and at that port, as well as at Hull and Peterhead, they are received in large quantities from the Arctic regions. This skin is that of the white hair seal, and must not be confused with the expensive seal fur obtained from Russian and Japanese waters. These white hair seal skins are light but exceedingly close in texture, yielding a very strong tough leather of large area and fine bold grain, known as Levant morocco. The area of the skins renders them suitable for upholstery work, and the flesh splits are dressed in considerable quantity for "japanned" ("patent") leather and "bolsters", which are used to grain other skins on, the raised buff affording a grip on the skin being grained and thus preventing slipping. When the skins arrive in the tanyard (generally lightly salted) they are drummed in old drench liquors until soft, dipped into warm water and "blubbered" with a sharp knife; they are then alternately dipped in warm water and drummed several times to remove fat, after which they are heavily limed, as they are still very greasy, and after unhairing and fleshing they are heavily puered for the same reason. The tannage takes about a month, and is much the same as for other leathers, the skins being split when "struck through."
Alligator leather is now produced to some extent both in the United States and India. The belly and flanks alone are useful. There are no special tanneries or processes for dressing the skins. Layers are not given. The leather is used mostly for small fancy goods, and is much imitated on sheepskin by embossing.
Snake and frog skins are also dressed to some extent, the latter having formed a considerable item in the exports of Japan; they are dressed mostly for cigar cases and pocket books. The general procedure is first to lime the goods and then to remove any scales (in the case of snake skins) by scraping with an unhairing knife on a small beam, after which the skins are bated and tanned in sumach by paddling.
A considerable amount of leather is now produced in Australia from the skins of kangaroo, wallaby and other marsupials. These skins are both tanned and tawed, the principal tanning agents being mimosa bark, mallet bark and sugar bush, which abound in Australia. The leather produced is of excellent quality, strong and pliable, and rivals in texture and appearance the kid of Europe; but the circumstance that the animals exist only in the wild state renders them a limited and insecure source of leather.
Japan and Enamel Leathers.:
Japanning is usually done on flesh splits, whereas enamelling is done on the grain, and if splits are used they are printed and boarded. The leather should be mellow, soft, free from grease, with a firm grain and no inclination to stretch. It is first shaved very smooth, thoroughly scoured with a stone, sumached, washed, slicked out tight and dried; when "sammied," the grain is buffed to remove scratches and oiled, the goods are then whitened or fluffed, and if too hard, bruised by boarding; enamel goods are now grained. The skins are now tightly nailed on boards and any holes patched up with brown paper, so that the japan shall not touch the flesh when the first thick coat of japan or the "daub" is put on. This is applied so thickly that it cannot soak in, with fine-toothed slicker, and then placed in a hot stove for twenty-four hours until quite dry; the coating is then pumiced smooth and the second thinner coat, termed "blanback," is applied. This is dried and pumiced, and a fine coating of japan or copal varnish is finally given. This is dried and cooled, and if the goods are for enamel they are boarded.
English japans sometimes contain light petroleum, but no turps. The secret of successful japanning lies in the age of the oil used; the older the linseed oil is, the better the result. To prepare the ground coat, boil 10 gallons linseed oil for one hour with 2 lb litharge at 600° F. to jellify the oil, and then add 2 lb prussian blue and boil the whole for half an hour longer. Before application the mixture is thinned with 10 gallons light petroleum. For the second coat, boil 10 gallons linseed oil for 2 hours with 2 lb prussian blue and 2 lb lampblack; when of a thin jelly consistency thin with 5 gallons of benzine or light petroleum. For the finishing coat, boil 5 gallons of linseed oil for 1 hour, then add 1 lb prussian blue, and boil for another hour; thin with 10 gallons petroleum and apply with a brush in a warm room. After drying, the goods are mellowed by exposure to the sun for at least three days.
Wool rugs are, after the preliminary processes, sometimes tanned in oak bark liquors by paddling, but are generally tawed, that is, dressed with alum and salt, and are therefore more suitably dealt with under that head. Tawing implies that the conversion of skins into leather is carried out by means of a mixture of which the more important constituents are mineral salts, such as alum, chrome and iron, which may or may not he supplemented with fatty and albuminous matter, both animal and vegetable.
As an example of alum tawing, calf kid may be taken as characteristic of the process; glove kid is also treated on similar lines. The goods are prepared for tawing in a manner similar to the preparation of tanned leathers, arsenical limes being used to ensure a fine grain. After being well drenched and washed the goods are ready for the tawing process. On the continent of Europe it is usual for the goods to be thrown into a tub with the tawing paste and trodden with the bare feet, although this old-fashioned method is gradually being driven out, and the drum or tumbler is being used.
The tawing paste consists of a mixture of alum, salt, flour, egg yolk and water; the quantities of each constituent diverge widely, every dresser having his own recipe. The following has been used, but cannot well be classed as typical: For 100 lb skin take 9 lb alum, 5 lb salt, dissolve in water, and mix to a thin paste with from 5 to 13 lb flour, using 4 to 6 egg yolks for every pound of flour used. Olive oil is also mixed in sometimes. The skins are drummed or trodden, at intervals, in the warm paste for some hours, removed, allowed to drain, and dried rapidly, damped down or "sammied" and "staked" by drawing them to and fro over a blunt knife fixed in the top of a post, and known as a knee stake; this process softens them very considerably. After staking, the goods are wet back and shaved smooth, either with a moon knife, I.e. a circular concave convex knife, the centre of which has been cut out, a piece of wood bridging the cavity forming the grip, or with an ordinary curriers shaving knife; the skins are now ready for dyeing and finishing.
Wool Rug Dressing.:
Wool rugs are first thoroughly soaked, well washed and clean-fleshed, scoured well by rubbing into the wool a solution of soft soap and soda, and then leathered by rubbing into the flesh of the wet skins a mixture consisting of three parts of alum and two parts of salt until they are practically dry; they are now piled up over-night, and the mixture is again applied. After the second or third application the goods should be quite leathered. Other methods consist of stretching the skins in frames and painting the flesh with a solution of alum and salt, or, better, with a solution of basic alum and salt, the alum being made basic by the gradual addition of soda until a permanent precipitate is produced.
The goods are now bleached, for even the most vigorous scouring will not remove the yellow tint of the wool, especially at the tips. There are several methods of bleaching, viz, by hydrogen peroxide, following up with a weak vitriol bath; by potassium permanganate, following tip with a bath of sulphurous acid; or by fumigating in an air-tight chamber with burning sulphur. The last-named method is the more general; the wet skins are hung in the chamber, an iron pot containing burning sulphur is introduced, and the exposure is continued for several hours.
If the goods are to be finished white, they are now given a vitriol sour, scoured, washed, retanned, dried, and when dry softened by working with a moon knife. If they are to be dyed, they must be prepared for the dye solution by "chloring," which consists of immersion in a cold solution of bleaching powder for some hours, and then souring in vitriol.
The next step is dyeing. If basic dyes are to be used, it is necessary to neutralize the acidity of the skins by careful addition of soda, and to prevent the tips from being dyed a darker colour than the roots. Glauber salts and acetic acid are added to the dye-bath. The tendency of basic colours to rub off may be overcome by passing the goods through a solution of tannin in the form of cutch, sumach, quebracho, &c.; in fact, some of the darker-coloured materials may be used as a ground colour, thus economizing dyestuff and serving two purposes. If acid colours are used, it is necessary to add sulphuric acid to the dye bath, and in either ease colours which will strike below 500° C. must be used, as at that temperature alum leather perishes.
After being dyed, the goods are washed up, drained, and if necessary retanned, the glossing finish is, then produced by passing them through a weak emulsion or "fat liquor" of oil, soap and water, after which they are dried, softened by working with a moon knife and beating, when they are combed out, and are ready for the market.
Blacks are dyed by immersing the goods alternately in solutions of logwood and iron, or a one-solution method is used, consisting of a mixture of these two, with, in either case, varying additions of lactic acid and surnach, copper salts, potassium bichromate, &c.; the time of immersion varies from hours to days. After striking, the goods are exposed to the air for some hours in order to oxidize to a good black; they are then well scoured, washed, drained, retanned, dried, softened and combed.
The first chrome tanning process was described by Professor Knapp in 1858 in a paper on "Die Natur und Wesen der Gerberie," but was first brought into commercial prominence by Dr Heinzerling about 1878, and was worked in a most persevering way by the Eglinton Chemical Company, who owned the English patents, though all their efforts failed to produce any lasting effects. Now chrome tanning is almost the most important method of light leather dressing, and has also taken a prominent place in the heavy department, more especially in curried leathers and eases where greater tensile strength is needed. The leather produced is much stronger than any other leather, and will also stand boiling water, whereas vegetable-tanned leather is completely destroyed at 70° C. and alum leather at 50° C.
The theory of chrome tanning is not perfectly understood, but in general terms it consists of a partial chemical combination between the hide fibre and the chrome salts, and a partial mechanical deposition of chromium oxide in and on the fibre. The wet work, or preparation for tanning, may be taken as much the same as for any other leather.
There are two distinct methods of chrome tanning, and several different methods of making the solutions. The "two bath process" consists of treating the skins with a bichromate in which the chromium is in the acidic state, and afterwards reducing it to the basic state by some reducing agent. The exact process is as follows: To prevent wrinkled or "drawn" grain the goods are first paddled for half an hour in a solution of vitriol and salt, when they are piled or "horsed" up over night, and then, without washing, placed in a solution consisting of 7 lb of potassium bichromate, 3½ lb of hydrochloric acid to each 100 lb of pelts, with sufficient water to conveniently paddle in; it is recommended that 5% of salt be added to this mixture. The goods are run in this for about 3 hours, or until struck through, when they are horsed up for some hours, care being taken to cover them up, and are then ready for the reducing bath. This consists of a 14% solution of plain "hypo," or hyposulphite of soda, to which, during the process of reduction, frequent additions of hydrochloric acid are macic to free the sulphurous and thiosuiphuric acids, which are the active reducing agents. After about 3 hours immersion, during which time the goods will have changed in colour from bright yellow to bright green, one or two skins are cut in the thickest part, and if the green has struck right through, the pack is removed as tanned, washed up, and allowed to drain.
The "single-bath process" consists of paddling, drumming, or otherwise introducing into the skins a solution of a chrome salt, usually chrome alum, which is already in the basic condition, and therefore does not require reducing. The basic solutions are made as follows: For 100 lb of pelts 9 lb of chrome alum are dissolved in 9 gallons of water, and 2½ lb of washing soda already dissolved in I gallon of water are gradually added, with constant stirring. One-third of the solution is added to 80 gallons of water, to which is added 7 lb of salt, and the skins are introduced; the other two-thirds are introduced at intervals in two successive portions. Another liquor, used in the same way, is made by dissolving 3 lb of potassium bichromate in hot water, adding ½ gallon strung hydrochloric acid and then, gradually, about 1½ lb of glucose or grape sugar; this reduces the acidic chrome salt, vigorous effervescence ensuing. The whole is made up to 2 gallons and 5% to 15% of salt is added. In yet another method a chrome alum solution is rendered basic by boiling with hypo, and after the reaction has ceased the solution is allowed to settle and the clear portion used.
After tanning, which takes from 8 hours to as many, and even more, days, depending upon the method used and the class of skin being dressed, the skins tanned by both methods are treated in a similar manner, and are neutralized by drumming in borax solution, when they are washed free from borax by drumming in warm water, arid are ready for dyeing, a process which will be dealt with further on. The goods are sometimes tanned by suspension, but this method is generally reserved for the tanning of the heavier leathers, which are treated in much the same way, the several processes taking longer.
Before leaving mineral tanning, mention may be made of iron tannage, although this has gained no prominent position in commerce. Ferric salts possess powerful tanning properties, and were thoroughly investigated by Professor Knapp, who took out several patents, but the tendency to produce a brittle leather has never been entirely overcome, although it has been greatly modified by the incorporation of organic matter, such as blood, rosin, paraffin, urine, &c, Knapps basic tanning liquor is made as follows: A strong solution of ferrous sulphate is boiled and then oxidized to the ferric state by the careful addition of nitric acid. Next, to destroy excess of nitric acid, ferrous sulphate is added until effervescence ceases and the resulting clear orange-coloured solution is concentrated to a varnish-like consistency. It does not crystallize or decompose on concentration. The hides or skins are prepared for tanning in the usual way, and then handled or otherwise worked in solutions of the above iron salt, the solutions, which are at first weak, being gradually strengthened.
The tannage occupies from 2 to 8 days, and the goods are then stuffed in a ventilated drum with greases or soap. If the latter is used, an insoluble iron soap is precipitated on the fibres of the leather, which may then be finally impregnated with stearin and paraffin, and finished in the usual manner as described under Curried Leathers. A very fair leather may also be manufactured by using iron alum and salt in the same manner as described under ordinary alum and salt.
Leathers tanned by mixtures or separate baths of both mineral and vegetable tanning agents have now taken an important position in commerce. Such leathers are the Swedish and Danish glove leathers, the United States "dongola leather," and French glazed kid. The usefulness of such a combination will be evident, for while vegetable tanning produces fullness, plumpness and resistance to water, the mineral dressing produces a softness unnatural to vegetable tannages without the use of large quantities of oils and fats. It may also be noted that once a leather has been thoroughly tanned with either mineral or vegetable materials, although it will absorb large quantities of the material which has not been first used, it will retain in the main the characteristics of the tannage first applied. The principle had long been used in the manufacture of such tough and flexible leathers as "green leather," "combing leather" and "picker bands," but was first applied to the manufacture of imitation glazed kid by Kent in America, who, about 1878, discovered the principle of fatliquoring, and named his product "dongola leather." The discovery of this process revolutionized the manufacture of combination leathers.
The Swedish and Danish glove leathers were first given a dressing of alum and salt, with or without the addition of flour and egg, and were then finished and coloured with vegetable materials, generally with willow bark, although, in cases of scarcity, sumach, oak bark, madder and larch were resorted to. The "green leathers" manufactured in England generally receive about a weeks tannage in gambier liquors, and are finished off in hot alum and salt liquors, after which they are dried, have the crystallized salts slicked off, are damped back, and heavily stuffed with moellon, degras or sod oil. Kent, in the manufacture of his dongola leather, used mixed liquors of gambier alum and salt, and when tanned, washed the goods in warm water to remove excess of tanning agent, piled up to samm, and fatliquored. In making alum combinations it must be borne in mind that alum leather will not glaze, and if a glazed finish is required, a fairly heavy vegetable tannage should be first applied. For dull finishes the mineral tannage may advantageously precede the vegetable.
Very excellent chrome combination leather is also manufactured by the application of the above principles, gambier always being in great favor as the vegetable agent. The use of other materials deprives the leather of its stretch, although they may be advantageously used where the latter property is objectionable.
Under the head of oil tanning is included "buff leather," "buck leather," "piano leather," "chamois leather," and to a greater or lesser extent, "Preller's crown or helvetia leather." The process of oil tanning dates back to antiquity, and was known as "shamoying," now spelt "chamoising." Chamoising yields an exceedingly tough, strong and durable leather, and forms an important branch of the leather industry. The theory of the process is the same as the theory of currying, which is nothing more orless than chamoising, viz, the lubrication of the fibres by the oil itself and the aldehyde tanning which takes place, due to the oxidation and decomposition of the esters of the fatty acids contained in the oil. The fact that an aldehyde tannage takes place seems to have been first discovered by Payne and Pullman, who took out a patent in 1898, covering formaldehyde and other aldehydes used in alkaline solutions. Their product, "Kaspine leather," found considerable application in the way of military accoutrements. Chamois, buff, buck and piano leathers are all manufactured by the same process slightly modified to suit the class of bide used, the last three being heavy leathers, the first light.
As regards the process used for chamois leather, the reader will remember, from the account of the vegetable tannage of sheep skins, that after splitting from the limes, the fleshes were thrown back into the pits for another three weeks liming (six weeks in all) preparatory to being dressed as chamois leather. It is necessary to lime the goods for oil dressing very thoroughly, and if the grain has not been removed by splitting, as in the case of sheep skins, it is "frized" off with a sharp knife over the beam. The goods are now rinsed, scudded and drenched, dried out until stiff, and stocked in the faller stocks with plenty of cod oil for 2 to 3 hours until they show signs of heating, when they are hung up in a cool shed, This process is repeated several times during a period of from 4 to 6 days, the heat driving the water out of the skins and the oil replacing it. At the end of this time the goods, which will have changed to a brown colour, are hung up and allowed to become as dry as possible, when they are hung in a warm stove for some hours, after which they are piled to heat off, thrown into tepid water and put through a wringing machine. The grease which is recovered from the wringing machine is known commercially as "degras" or "moellon," and fetches a good price, as it is unrivalled for fatliquoring and related processes, such as stuffing, producing a very soft product. They next receive a warm soda lye bath, and are again wrung; this removes more grease, which forms soap with the lye, and is recovered by treatment with vitriol, which decomposes the soap. The grease which floats on top of the liquor is sold under the name of "sod oil," This also is a valuable material for fatliquoring, &c., but not so good as degras.
After being wrung out, the goods are bleached by one of the processes mentioned in the section on wool rug dressing, the permanganate method being in general use in England. In countries where a fine climate prevails the soap bleach or sun bleach is adopted; this consists of dipping the goods in soap solution and exposing them to the suns rays, the process being repeated three or more times as necessary.
The next step is fatliquoring to induce softness, after which they are dried out slowly, staked or perched with a moon knife, fluffed on a revolving wheel covered with fine emery to produce the fine nap or surface, brushed over with french chalk, fullers earth or china clay, and finally finished on a very fine emery wheel.
Prellers Helvetia or Crown Leather:
This process of leather manufacture was discovered in 1850 by Theodor Klemm, a cabinetmaker of Wurttemberg, who being then in poor circumstances, sold his patent to an Englishman named Preller, who manufactured it in Southwark, and adopted a crown as his trade mark. Hence the name crown leather. The manufacture then spread through Switzerland and Germany, the product being used in the main for picker straps, belting and purposes where waterproof goods were required, such as hose pipes and military water bags. No taste is imparted to the water by this leather.
The process to manufacture is as follows: The hides are unhaired by short liming, painting with lime and sulphide, or sweating, and cleansed by scudding and washing, after which they are coloured in bark liquors, washed up through clean water, and hung up to dry partially, When in a sammied condition the goods are placed on a table and a thick layer of the tanning paste spread on the flesh side. The tanning paste varies with each manufacturer, but the following is the mixture originally used by Preller: 100 parts flour, 100 parts soft fat or horse tallow, 35 parts butter, 88 parts ox brains, 50 parts milk, 15 parts salt or saltpetre.
The hides are now rolled in bundles, placed in a warm drum and worked for 8 to 10 hours, after which they are removed and hung up until half dry, when the process is repeated. Thus they are tumbled 3 to 4 times, set out flesh and grain, rinsed through tepid water, set out, sammied, and curried by coating with glycerin, oil, tallow and degras. The table grease is now slicked off, and the goods are set out in grease, grained and dried.
Transparent leather is a rather horny product, somewhat like raw hide, and has been used for stitching belts and picker bands. The goods to be dressed are limed, unhaired, very thoroughly delimed with acids, washed in water, scudded and clean-fleshed right to the veins; they are now stretched in frames, clean-fleshed with a moon knife, and brushed with warm water, when several coats of glycerin, to which has been added some antiseptic such as salicylic or picric acid, are applied; the goods are then dried out, and another coat is applied, and when semi-dry they are drummed in a mixture of glycerin, boracic acid, alum and salt, with the addition of a little bichromate of potash to stain them a yellow colour. After drumming for 2 to 3 hours they are removed, washed up, lightly set out, and stretched in frames to dry, when they are ready for cutting into convenient lengths for use.
A certain class of sheep skin known as Hampshires is generally used in the manufacture of this speciality. The skins as received are first very carefully washed to remove all dirt, dewooled, limed for 3 to 4 weeks, they are then cleanly fleshed, unhaired, rinsed up in water, and thickly split, the poorer hides being ultilized for chamois; they are now re-split at the fatty strata so that all fat may be easily removed, and while the grains are dressed as skivers, the fleshes are tied in frames, watered with hot water, scraped and coated on both sides with a cream consisting of whiting, soda and water, after which they are dried out in a hot stove. In the drying the whiting mixture absorbs the grease from the skins; in fact, this method of degreasing is often employed in the manufacture of wool rugs. When dry, both sides of the skins are flooded to remove the whiting, and are then well rubbed over with a flat piece of pumice-stone, swilled, dried, re-pumiced, again swilled, and when sammied are rolled off with a wooden roller and dried out.
Tar and Peat Tanning:
Tar tanning was discovered by a French chemist named Philippi, who started with the idea that, if coal was a decomposition product of forests, it must still necessarily possess the tanning properties originally present in the trees. However far-fetched such an argument may seem, Philippi succeeded in producing a leather from wood and coal tar at a fairly cheap rate, the product being of excellent texture and strength, but rather below the average in the finish, which was inclined to be patchy, showing oily spots. His method consisted of impregnating the goods with refined tar and some organic acid, but the product does not seem to have taken any hold upon the market, and is not much heard of now.
Peat tanning was discovered by Payne, an English chemist, who was also the co-discoverer of the Payne-Pullman formaldehyde tanning process. His peat or humic acid tannage was patented by him about 1905, and is now worked on a commercial scale. The humic acid is first extracted from the peat by means of alkalis, and the hides are treated with this solution, the humic acid being afterwards precipitated in the hides by treatment with some stronger organic or mineral acid.
Dyeing, Staining and Finishing:
These operations are practised almost exclusively on the lighter leathers. Heavy leathers, except coloured and black harness and split hides for bag work, are not often dyed, and their finishing is generally considered to be part of the tannage. In light leathers a great business is done in buying up crust stock, i.e. rough tanned stock, and then dyeing and finishing to suit the needs and demands of the various markets. The carrying out of these operations is a distinct and separate business from tanning, although where possible the two businesses are carried on in the same works.
Whatever the goods are and whatever their ultimate finish, the first operation, upon receipt by the dyer of the crust stock, is sorting, an operation. requiring much skill. The sorter must be familiar with the why and wherefore of all subsequent processes through which the leather must go, so as to judge of the suitability of the various qualities of leather for these processes, and tc know where any flaws that may exist will be sufficiently sup- pressed or hidden to produce a saleable product, or will be rendered entirely unnoticeable. The points to be considered in. the sorting are coarseness or fineness of texture, boldness or fineness of grain, colour, flaws including stains and scratches, substance, &c. Light-coloured and flawless goods are parcelled out for fine and delicate shades, those of darker hue and few flaws are parcelled out for the darker shades, such as maroons, greens (sage and olive), dark blues, &c., and those which are so badly stained as to be unsuitable for colours go for blacks. After sorting, the goods are soaked back to a limp condition by immersion in warm water, and are then horsed up to drip, having been given, perhaps, a preliminary slicking out.
Up to this point all goods are treated alike, but the subsequent processes now diverge according to the class of leather being treated and the finish required.
Persian goods for glacιs, moroccos, &c., require special preparation for dyeing, being first re-tanned. As received, they are sorted and soaked as above, piled to samm, and shaved. Shaving consists of rendering the flesh side of the skins smooth by shaving off irregularities, the skin, which is supported on a rubber roller actuated by a foot lever, being pressed against a series of spiral blades set on a steel roller, which is caused to revolve rapidly. When shaved, the goods are stripped, washed up, soured, sweetened and re-tanned in sumach, washed up, and slicked out, and are then ready for dyeing.
There are three distinct methods of dyeing, with several minor modifications. Tray dyeing consists of immersing the goods, from 2 to 4 dozen at a time, in two separate piles, in the dye solution at 60° C., contained in a flat wooden tray about 5 ft.X4 ft.X1 ft., and keeping them constantly moving by continually turning them from one pile to the other. The disadvantages of this method are that the bath rapidly cools, thus dyeing rapidly at the beginning and slowly at the termination of the operation; hence a large excess of dye is wasted, much labor is required, and the shades obtained are not so level as those obtained by the other methods. But the goods are under observation the whole time, a very distinct advantage when matching shades, and a white flesh may be preserved. The paddle method of dyeing consists of paddling the goods in a large volume of liquor contained in a semi-circular wooden paddle for from half to three-quarters of an hour. The disadvantages are that the liquor cools fairly rapidly, more dye is wasted than in the tray method, and a white flesh cannot be preserved. But larger packs can be dyed at the one operation, the goods are under observation. the whole time, and little labor is required.
The drum method of dyeing is perhaps best, a drum somewhat similar to that used by curriers being preferable. The goods are placed on the shelves inside the dry drum, the lid of which is then fastened on, and the machinery is started; when the drum is revolving at full speed, which should be about 12 to 15 revolutions per minute, the dye solution is added through the hollow axle, and the dyeing continued for half an hour, when, without stopping the drum, if desired, the goods may be fatliquored by running in the fatliquor through the hollow axle. The disadvantages are that the flesh is dyed and the goods cannot be seen. The advantages are that little labor is required, a large pack of skins may be treated, level shades are produced, heat is retained, almost complete exhaustion. of the dye-bath is effected, and subsequent processes, such as fatliquoring, may be carried out without stopping the drum.
Of the great number of coal-tar dyes on the market comparatively few can be used in leather manufacture. The four chief classes are: (I) acid dyes; (2) basic or tannin dyes; (3) direct or cotton dyes; (4) mordant (alizarine) dyes.
Acid dyes are not so termed because they have acid characteristics; the name simply denotes that for the development of the full shade of colour it is necessary to add acid to the dye-bath. These dyes are generally sodium salts of sulphonic acids, and need the addition of an acid to free the dye, which is the sulphonic acid Although theoretically any acid (stronger than the sulphonic acid present) will do for this purpose, it is found in practice that only sulphuric and formic acids may be employed, because others, such, as acetic lactic, &c., do not develop the full shade of colour. Acid sodium sulphate may also be successfully used.
Acid colours produce a full level shade without bronzing, and do not accentuate any defects in the leather, such as had grain, &c. They are also moderately fast to light and rubbing. They are generally applied to leather at a temperature between 50° and 60° C., with an equal weight of sulphuric acid. The quantity of dye used varies, but generally, for goat, persians, &c., from 25 to 30 oz. are used per ten dozen skins, and for calf half as much again, dissolved in such an amount of water as is most convenient according to the method being used. If sodium bisulphate is substituted for sulphuric acid twice as much must be used, and if formic acid three times as much (by weight).
Basic dyes are salts of organic colour bases with hydrochloric or some other suitable acid. Basic colours precipitate the tannins, and thus, because of their affinity for them, dye very rapidly, tending to produce uneven shades, especially if the tannin on the skin is unevenly distributed. They are much more intense in colour than the acid dyes, have a strong tendency to bronze, and accentuate weak and defective grain. They are also precipitated by hard waters, so that the hardness should be first neutralized by the addition of acetic acid, else the precipitated colour lake may produce streakily dyed leather. To prevent rapid dyeing, acetic acid or sodium bisulphate should always be added in small quantity to the dye-bath, preferably the latter, as it prevents bronzing. The most important point about the application of basic dyes to leather is the previous fixation of the tannin on the surface of the leather to prevent its bleeding into the dye-bath and precipitating the dye. All soluble salts of the heavy metals will fix the tannin, but few are applicable, as they form colour lakes, which are generally undesirable. Antimony and titanium salts are generally used, the forms being tartar emetic (antimony potassium tartrate), antimonine (antimony lactate), potassium titanium oxalate, and titanium lactate. The titanium salts are economically used when dyeing browns, as they produce a yellowish-brown shade; it is therefore not necessary to use so much dye. About 2 oz. of tartar emetic and 8 oz. of salt is a convenient quantity for 1 dozen goat skins. The bath is used at 30° to 40° C., and the goods are immersed for about 15 minutes, having been thoroughly washed before being dyed. Iron salts are sometimes used by leather-stainers for saddening (dulling) the shade of colour produced, iron tannate, a black salt, being formed. It is often found economical to bottom goods with acid, direct, or other colours, and then finish with basic colours; this procedure forms a colour lake, and colour lakes are always faster to light and rubbing than the colours themselves.
Direct cotton dyes produce shades of great delicacy, and are used for the dyeing of pale and art shades. They are applied in neutral or very slightly acid baths, formic and acetic acids being most suitable with the addition of a quantity of sodium chloride or sulphate. After dyeing, the goods are well washed to free from excess of salt. The cosine colours, including erythrosine, phloxine, rose Bengal, &c., are applied in a similar manner, and are specially used for the beautiful fluorescent pink shades they produce; acid and basic colours and mineral acids precipitate them.
The mordant colours, which include the alizarine and anthracene colours, are extremely fast to light, and require a mordant to develop the colour. They are specially applicable to chamois leather, althotigh a few may be used for chrome and alum leathers, and one or two are successfully applied to vegetable-tanned leather without a mordant.
Sulphur or sulphide colours, the first of which to appear were the famous Vidal colours, are applied in sodium sulphide solution, and are most successfully used on chrome leather, as they produce a colour lake with chrome salts, the resulting colour being very fast to light and rubbing. A very serious disadvantage in connection with them is that they must necessarily be applied in alkaline solution, and the alkali has a disintegrating effect upon the fibre of the leather, which cannot be satisfactorily overcome, although formaldehyde and glycerin mixtures have been patented for the purpose.
The Janus colours are perhaps worth mentioning as possessing both acid and basic characteristics; they precipitate tannin, and are best regarded as basic dyes from a leather-dyers standpoint.
The goods after dyeing are washed up, slicked out on an. inclined glass table, nailed on boards, or hung up by the hind shanks to dry out.
Coal-tar dyes are not much used for the production of blacks, as they do not give such a satisfactory result as logwood with an iron mordant. In the dyeing of blacks the preliminary operation of souring is always omitted and that of sumaching sometimes, but if much tan has been removed it will be found necessary to use sumach, although cutch may be advantageously and cheaply substituted. After shaving, the goods, if to be dressed for blue backs (blue-coloured flesh), are dyed as already described, with methyl violet or some other suitable dye; they are then folded down the back and drawn through a hot solution of logwood and fustic extracts, and then rapidly through a weak, cold iron sulohate and connerarp~tate solution.
Immediately afterwards they are rinsed up and either drummed in a little neatsfoot oil or oiled over with a pad, flesh and grain, and dried. When dry the goods are damped back and staked, dried out and re-staked.
After dry-staking, the goods are seasoned, i.e. some suitable mixture is applied to the grain to enable it to take the glaze. The following is typical: 3 quarts logwood liquor, 1/2 pint bullocks blood, 1/2 pint milk, 1/2 gill ammonia, 1/2 gill orchil and 3 quarts water. This season is brushed well into the grain, and the goods are dried in a warm stove and glazed by machine. The skins are glazed under considerable pressure, a polished glass slab or roller being forced over the surface of the leather in a series of rapid strokes, after which the goods are re-seasoned, re-staked, fluffed, re-glazed, oiled over with a pad, dipped in linseed oil and dried. They are now ready for market. If the goods are to be finished dull they are season.ed with linseed mucilage, casein or milk (many other materials are also used), and rolled, glassed with a polished slab by hand, or ironed with a warm iron.
Coloured glacιs are finished in a similar manner to black glacιs, dye (instead of Iogwood and iron) being added to the season, which usually consists of a simple mixture of dye, albumen and milk.
Moroccos and grain leathers are boarded on the flesh side before and after glazing, often being tooth rolled between the several operations. Tooth rolling consists of forcing, under pressure, a toothed roller over the grain; this cuts into the leather and helps to produce many grains, which could not be produced naturally by boarding, besides fixing them.
Many artificial grains and patterns are also given to leather by printing and embossing, these processes being carried out by passing the leather between two rollers, the top one upon which the pattern is engraved being generally steam heated. This impresses the pattern upon the grain of the leather.
The above methods will give a very general idea of the processes in vogue for the dressing of goods for fancy work. The dressing of chrome leathers for uppers is different in important particulars.
Chrome Box and Willow Calf:
Willow calf is coloured calf, box calf is dressed black and grained with a box grain. A large quantity of kips is now dressed as box calf; these goods are the hides of yearling Indian cattle, and are dressed in an exactly similar manner as calf. After tanning and boraxing to neutralize the acidity of the chrome liquor, the goods are washed up, sammied, shaved, and are ready for mordanting previous to dyeing. Very few dyes will dye chrome leather direct, i.e. without mordanting. Sulphide colours are not yet in great demand, nor are the alizarines used as much as they might be. The ordinary acid and basic dyes are more generally employed, and the goods consequently require to be first mordanted. The mordanting is carried out by drumming the goods in a solution containing tannin, and, except for pale shades, some dyewood extract is used; for reds peachwood extract, for browns fustic or gambier, and for dark browns a little logwood is added. For all pale shades sumach is exclusively used. After drumming in the warm tannin infusion for half an hour, if the goods are to be dyed with basic colours the tannin is first fixed by drumming in tartar emetic and salt, or titanium, as previously described; the dyeing is also carried out as described for persians, except that a slightly higher temperature may be maintained. If the goods are to be dyed black they are passed through logwood and iron solutions.
After dyeing and washing up, &c., the goods are fatliquored by placing them in a previously heated drum and drumming them with a mixture known as a fatliquor, of which the following recipe is typical: Dissolve 3 lb of soft soap by boiling with 3 gallons of water, then add 9 lb of neatsfoot oil and boil for some minutes; now place the mixture in an emulsifier and emulsify until cooled to 35° C., then add the yolks of 5 fresh eggs and emulsify for a further half hour. The fatliquor is added to the drum at 55° C., and the goods are drummed for half an hour, when all the fatliquor should be absorbed; they are then slicked out and dried. After drying, they are damped back, staked, dried, re-staked and seasoned with materials similar to those used for persians; when dry they are glazed, boarded on the flesh ("grained") from neck to butt and belly to belly to give them the box grain, fluffed, reseasoned, reglazed and regrained.
Finishing of Bag Hides:
The goods are first soaked back, piled to samm, split or shaved, scoured by machine, finished off by hand, washed up and retanned by drumming in warm sumach and extract, after which they are washed up, struck out, hung up to samm, and "set." Setting consists of laying the grain flat and smooth by striking out with a steel or sharp brass slicker. They are then dried out, topped with linseed mucilage, and again dried. This brushing over with linseed mucilage prevents the dye from sinking too far into the leather; gelatine, Irish moss, starch and gums are also used for the same purpose. These materials are also added to the staining solution to thicken it and further prevent its sinking in.
When dry, the goods are stained by applying a ½% (usually) solution of a suitable basic dye, thickened with linseed, with a brush. Two men are usually employed on this work; one starts at the right-hand flank and the other at the left-hand shank, and they work towards each other, staining in sections; much skill is needed to obviate markings where the sections overlap. The goods may advantageously be bottomed with an acid dye or a dye-wood extract, and then finished with basic dyes. Whichever method is used, two to three coats are given, drying between each. After the last coat of stain, and while the goods are still in a sammied condition, a mixture of linseed mucilage and French chalk is applied to the flesh and glassed off wet, to give it a white appearance, and then the goods are printed with any of the usual bag grains by machine or hand, and dried out. For a bright finish the season may consist of a solution of 15 parts carnauba wax, 10 parts curd soap and 100 parts water boiled together; this is sponged into the grain, dried and the hides are finished by either glassing or brushing. For a duller finish the grain is simply rubbed over with buck tallow and brushed. Hide bellies for small work are treated in much the same manner.
As these goods were tanned in alum, salt, flour and egg, any undue immersion in water removes the tannage; for this reason they are generally stained like bag hides, one man only being employed on the same skin. The skins are first thoroughly soaked in warm water and then drummed for some minutes in a fresh supply, when they are re-egged to replace that which has been lost. This is best done by drumming them for about 1½ hours in 40 to 50 egg yolks and 5 lb of salt for every hundred skins; they are then allowed to be in pile for 24 hours, and are set out on the table ready for mordanting. The mordants universally used are ammonia or alkaline soft soap; 1 in 1000 of the former or a 1% solution of the latter. When the goods have partially dried in, bottoming follows, and usually the natural wood dyestuffs are used for this operation, such as fustic, Brazil wood, peachwood, logwood and turmeric. After application of these colours the goods are sammied and topped with a 1% solution of an acid dye, to which has been added 20% of methylated spirit to prevent frothing with the egg yolk; they are then dried out slowly, staked, pulled in shape, fluffed and brushed by machine. The season, which is sponged on, may consist of 1 part dye, I part albumen, 2 parts dextrine and 1/2 part glycerine, made up to 100 parts with water; when it has been applied, the goods are sammied, brushed and ironed with a warm flat iron such as is used in laundry work.
A committee of the Society of Arts (London) has investigated the question of leather for bookbinding, attention having been drawn to this subject by the rotten and decayed condition often observed in bindings less than fifty years old. This committee engaged in research work extending over several years, and the report in which its results were given was edited for the Society of Arts and the Leathersellers Company (which also did much important work in connection with it) by Lord Cobham, chairman of the committee, and Sir Henry Trueman Wood, secretary of the society. The essence of the report, so far as leather manufacture is concerned, is as follows: The goods should be soaked and limed in fresh liquors, and bating and puering should be avoided, weak organic acids or erodine being used; they should also be tanned with pyrogallol tanning materials, and preferably with sumach. In shaving, they should only be necked and backed, i,e. only irregularities should be removed, as further shaving has a considerable weakening effect on the fibre. The striking out should not be heavy enough to lay the fibre. In dyeing, acid dyes and a few direct colours only arc permissible, and in connection with the former the use of sulphuric acid is strongly condemned, as it absolutely disintegrates the fibre; the use of formic, acetic and lactic acids is permitted. The use of salts of mineral acids is to be avoided, and in finishing, tight setting out and damp glazing is not to be recommended; oil may be advantageously used.
BIBLIOGRAPHY.H. G. Bennett, The Manufacture of Leather (1909): S. R. Trotman, Leather Trades Chemistry (1908); M. C. Lamb, Leather Dressing (1907); A. Watt, Leather Manufacture (1906); H. R. Procter, Principles of Leather Manufacture (1903), and Leather Industries Laboratory Book (1908); L. A. Flemming, Practical Tanning (1910); A. M. Villon, Practical Treatise on the Leather Industry (1901); C. T. Davis, Manufacture of Leather (1897). German works include J. Borgman, Die Rotlederfabrikation (Berlin, 1904-1905), and - Feinlederfabrikation (1901); J. Jettmar, Handbuch der Chromgerbung (Leipzig, 1900); J. von Schroeder, Gerberei-chemie (Berlin, 1898).
(J. G. P.*)