Animal Proteins Part 10

=Special Qualities of Chrome Leather.=--A few words on the special peculiarities of the leather formed by chroming will not be out of place at this stage. One of the greatest disadvantages of the chrome tannage has been the absence of what is known as the "crust" or "rough leather"

stage. In chrome tanning, the finishing operations have had to follow on immediately after the tannage. Chrome leather, after tanning, may be dried out like other leathers, but if thoroughly dried, or if kept in a dried condition for any time, it will not "wet back" again with water.

Various suggestions have been made to overcome this difficulty but none yet have found much favour in practice. The discovery of the reversibility of the tannage, however, ought to solve this difficulty, and the author would suggest that any of the substances used for "dechroming" might also be suitable for "wetting in" chrome leather which has been well dried out. A piece of chrome leather, dried out well after neutralizing, and kept in a warm place for four years, wetted back easily in ammonium acetate, in the author's laboratory.

Another peculiarity of the chrome tannage is that any defects in the raw material always seem more obvious in chrome than in vegetable leather.

This often necessitates the use of a better quality hide or skin. Weak grain or loose grain becomes very obvious. The presence of short hair which both unhairing and scudding have failed to remove also is usually more evident.

A more serious disadvantage of chrome leather is its tendency to stretch. In the case of belting leather this feature is an obvious nuisance, and has inevitably led manufacturers to use powerful stretching machines upon the goods before they are marketed. In chrome sole leather also there is a tendency to spread and throw the boot out of shape.

Further disadvantages arise from the fact that the chrome tannage is an "empty" tannage. Compared with the vegetable tannage, very little of the tanning agent is adsorbed. Hence there is little matter of any kind between the hide fibres isolated during tannage. The inevitable effect of this is that the leather has not the same solidity and firmness, and needs filling out with other materials. A commercial consequence is also that it is impossible to obtain the same yield of leather from any given quant.i.ty of raw material. In trade parlance chrome tannage does not give good "weight." Another consequence is that (even when well filled with greases in finishing) chrome leather tends to be "woolly" on the flesh side or at cut edges.

On the other hand, chrome tanning has very many advantages over the older process. The most obvious of these is the great saving in time.

Many chrome tannages involve only a day or two, and none more than a week or two. A chrome leather factory therefore needs less capital on account of the quicker turnover. If, moreover, the market be unfavourable, a chrome tanner can stop or reduce his output in a very short time, whereas a vegetable tanner is committed to many weeks'

supply of the goods he is manufacturing. Another notable advantage of chrome leather is its durability. In the finishing processes more grease is usually employed than in vegetable tannage, and this has a preservative effect upon leathers which often get wet. Chrome sole leather and hydraulic leathers are cases in point. Chrome leather will also stand changes of temperature and friction much better than vegetable tannages. The light chrome tannage results, further, in yielding a leather which has great tensile strength, and it is not surprising to find that chrome harness and chrome picking bands are highly thought of. The empty nature of the tannage necessitates the use of stuffing greases, but such large proportions of these may be used that chrome tannage becomes obviously suitable if one wishes to produce a waterproof leather. Hence the popularity of chrome tannage for waterproof soling and hydraulic leathers.

The advantages of the chrome process are very real, and very obviously such as will appeal to manufacturers. Chrome leathers have now been for some time in the forefront as far as boot-uppers are concerned, especially for the best quality goods, in which the popular "box-calf"

and "glace kid" are so largely employed. There seems little doubt that this will continue to be the case. It is an unfortunate fact that in this important branch of tanning, British manufacturers have not quite risen to the occasion. Their products have in the past been faced with very serious compet.i.tion from Continental and American manufacturers of chrome uppers, and there can be no doubt that these compet.i.tors produced a better article, and produced it more economically. The disorganization of the Continental factories owing to the war should give British manufacturers a valuable opportunity of putting such businesses on a better basis. For sole leather also the chrome tannage makes constant headway, and the relative proportion of it becomes gradually greater. A great impetus to chrome sole leather has been given by the war conditions of Britain. Owing to the submarine campaigns of Germany the tonnage question became all-important, and the bulky imports of vegetable tanning materials became a serious item. British tanners were therefore encouraged to make more chrome sole and less vegetable sole.

The urgent need of leather for our armies also a.s.sisted in the same sense. The production of chrome sole progressed therefore enormously during 1917 and 1918, and although some reaction will doubtless occur, there seems little doubt that chrome sole leather has taken a definite and permanent leap forward. Once the general public fully appreciate its qualities of waterproofness and durability its future will be a.s.sured.

On the whole the position and prospects of chrome tanning are good. The chrome tannages are making headway in all directions, and undoubtedly threaten the existence of many of the older processes of vegetable tanning.

REFERENCES.

Procter, "Principles of Leather Manufacture," pp. 198-220.

Bennett, "Manufacture of Leather," pp. 210, 355.

Bennett, _J.S.L.T.C._, 1917, 176.

Stiasny, _Collegium_, 1908, 117.

SECTION II.--GENERAL METHODS OF CHROME LEATHER MANUFACTURE

It has been previously pointed out that the chrome tannage is an "empty"

one; the primary principle in the wet work of goods for chrome leather is to avoid anything which will make this feature more obvious. In the vegetable tannages relatively larger amounts of the tanning agents are used, and these fill the interfibrillar s.p.a.ces; indeed, as we have seen (Part I., Sections III., V. and VI.), effort is made to increase these s.p.a.ces and to fill them to their maximum capacity, thus yielding a leather of which 50 per cent. is the tanning agent. In chrome tanning, however, the tanning agent may only be approximately 5 per cent. of the finished leather, so that any trouble taken to split the hide fibres or to dissolve hide substance is usually not only superfluous, but also calculated to enhance the "emptiness." The governing principle of all the preparatory processes for chrome tannage is therefore the conservation of hide substance, and this principle determines the modifications of the processes of soaking, liming, and deliming, which are in vogue. Now, in most of these processes there is usually some loss of hide substance, and it is the particular problem of chrome tanning to reduce this loss to a minimum in each stage. Whether the loss of hide substance be due to alkaline or fermentive hydrolysis, or to solation of the hide gel, the effect is increased by swelling, and in the wet-work for chrome, therefore, any variations in the degree of swelling are objectionable. The preparatory processes should be carried out with as little change as possible in the volume and elasticity of the pelt.

Whether also the loss of hide be due to hydrolysis or solation, it is increased by time, hence short processes are (other things being equal) much to be preferred. Fermentive hydrolysis is minimized by cleanliness, alkaline hydrolysis by avoiding strongly alkaline liquors, and solation of collagen is reduced by both, and also by avoiding, as far as possible, the presence of calcium and ammonium salts.

Soaking should be quick and clean. The use of the paddle or drum gives the greatest efficiency and also a.s.sists in procuring the softness so essential to the bulk of chrome leathers.

Liming chrome leather satisfactorily is almost an impossible ideal.

Every conceivable arrangement has some objection to it. The time of the process may be shortened either by the use of sulphide or by the use of mellow or old limes. To shorten time by the use of sodium sulphide unfortunately involves the employment of more alkali than is desirable, with a consequent plumping effect and tendency to harshness. If sufficient sulphide be used to make the liming very short, then the grease is not "killed" (saponified or emulsified). If the harshness and alkalinity be removed by using also an excess of calcium chloride, then the lyotrope influence of this substance enhances the solation of the hide gel. On the other hand the use of old lime liquors avoids the plumping effect, but increases considerably the bacterial activity, and the bacterial enzymes produce both hydrolysis and solation of the pelt.

In practice what is generally done is to shorten time by both methods and so to admit both disadvantages to a limited extent. This is theoretically more sound than would appear, for in mellow limes sulphide has less plumping power but is just as strong a depilatant; whilst, on the other hand, a mellow liming shortened by sulphide is less objectionable as there is some evidence that bacterial activity is relatively less in the first few days. Hence a mellow sulphide liming of 7-10 days is very common in practice, but sometimes a 3-4 days' process with more sulphide is also found satisfactory.

It would seem probable that the real solution of the problem would be found by a different process altogether. In this connection it is interesting to note that a Continental proposal to unhair by enzyme action only has been found most practicable with goods for chrome, and, in the author's opinion, some development on these lines, in which a lipolytic enzyme is used in addition to a proteolytic, might solve the difficulty, and give a rapid depilation which dispenses with liming, plumping and deliming with the consequent loss of valuable hide substance.

In the usual short, mellow, sulphide liming it is clear that there is not much advantage in a "round" or "set" of pits. Hence the one-pit system is popular on account of the less labour involved.

The above remarks are less applicable in the case of chrome sole leather. In this case weight is a great consideration and plumping is necessary. In such leather the chrome tannage is supplemented by the use of waxes, which fill up the s.p.a.ces between the fibres and give solidity and waterproofness to the finished article. With this leather an ordinary sole leather liming in sharp liquors is not unsuitable, handling the goods from "mellow to fresh," but there is, on the whole, a tendency to shorten the process to about a week by using more sulphide.

Processes for deliming pelt for chrome leather should also be chosen by our guiding principle of hide substance conservation. Here again short processes involving little change in swelling should be preferred. Now, the ordinary bating and puering processes give (1) neutralization of lime by organic acids combined with weak bases; (2) the solation of some hide substance; and (3) a "pulling down" effect on the swollen pelt.

Now, neutralization is quite superfluous, as the acids of the chrome liquor (one-bath or two-bath) can quite well accomplish this; the solvent effect is undesirable altogether; and the "pulling down" effect is also unnecessary if the goods are not plumped up. With any method of liming, however, some plumping is obtained, and this creates a problem of practical importance. In the huge quant.i.ties of pelt which go for chrome upper leathers, a primary consideration is the soft, "kind," or mellow feel of the grain in the finished leather. This is obtained only by tanning the pelt when the grain at least is in a thoroughly deplumped and inelastic condition. It is essential to delime not only so that the alkaline plumping effect is completely removed, but also so that no acid plumping effect succeeds it. The practical problem is to decide whether, in any particular instance, dung puers and bates are necessary to obtain this result. Bating is clearly not very desirable, on account of the length of the process, during which hide substance would be lost unnecessarily, and also because there will usually be a slight alkaline swelling. Puering with dog-dung infusions is preferable; it is not such a long process, the liquor is just acid to phenolphthalein, and the action is more intense, and by puering for a short time only the loss of hide may be confined to the grain and flesh only, whilst the desired inelasticity of grain-pelt is soon obtained. Many large firms have admittedly found themselves unable to dispense with puering, but others have succeeded in subst.i.tuting for it the use of non-swelling deliming and lyotrope agents like ammonium chloride and boric acid. In all cases it is futile to delime or puer the grain and then allow the goods to stand until the centre lime has diffused outwards. The goods must pa.s.s into the chrome liquors when in the correct condition. For heavy chrome leather a surface deliming with boric acid is all that is necessary.

Even that is superfluous when the goods are to be pickled before tanning.

=Types of Two-bath Chrome Tannage.=--Although the original process of the Schultz patent is quite a practicable one, many modifications have been introduced. These modifications have been made to suit the cla.s.s of goods under treatment, to suit the particular mode of application which is available or suitable, and to effect economies of chrome and other material, and of time, and also to combine with the tannage a pickling effect or a partial alum tannage. Other modifications arise from the precise acid, neutral, or alkaline condition of the pelt, being for example obviously necessary when pickled stock replace neutral pelts.

The many two-bath processes which have been found useful have been cla.s.sified previously by the author[6] into three types: (1) The "Schultz type," in which such quant.i.ties of dichromate and acid are used that there is no excess of free acid (other than chromic), but an excess of unaltered dichromate; (2) the "Acid type," in which the chromic acid is completely free and the liquor contains also some excess of mineral acid also; and (3) the "Neutral type," in which neither of these main const.i.tuents is in excess, just sufficient mineral acid having been used to liberate all the chromic acid from the dichromate.

[Footnote 6: "Types of Two-bath Chrome Tannage," _Leather_, 1909, 227-259.]

Now:--

K{2}Cr{2}O{7} + 2HCl = 2KCl + 2CrO{3} + H{2}O 204 73

Taking the commercial hydrochloric acid as a 30 per cent. solution, 73 parts will be obtained in about 250 parts of commercial acid. Hence 294 parts dichromate need 250 parts commercial hydrochloric acid for the above reaction;[7] in other words, 5 per cent. dichromate needs 4-1/4 per cent. commercial acid. Similarly 6 per cent. and 4 per cent. of dichromate need 5.1 per cent. and 3.4 per cent. respectively of commercial acid. If therefore such quant.i.ties be used we have the so-called "Neutral type" of chroming bath. If less quant.i.ties of acid be used we have the "Schultz type," and if greater quant.i.ties of acid be used we have the "Acid type." The original Schultz patent used 5 per cent. dichromate and 2-1/2 per cent. hydrochloric acid, and well exemplifies its type, for there is much undecomposed dichromate. The composition of some chroming baths in common use on a practical scale are given below under the heading of their type:--

----------+--------------+--------------+-------+------------ Type. | Dichromate. | Hydrochloric | Salt. | Aluminium | | Acid. | | Sulphate.

----------+--------------+--------------+-------+------------ | 5 | 2-1/2 | -- | -- | 5 | 2-1/2 | -- | 3 Schultz | 5 | 2-1/2 | 5 | -- | 5 | 2-1/2 | 10 | -- | 6 | 3 | -- | -- ----------+--------------+--------------+-------+------------ | 4 | 4 | -- | -- | 4 | 4 | 5 | -- | 5 | 5 | 5 | 3 Acid | 5 | 5 | 10 | -- | 6 | 6 | 15 | -- | 3 | 3 | 15 | 4 | 2 | 4 | 10 | -- | 4 | 15 | 24 | -- ----------+--------------+--------------+-------+------------ | 5 | 4-1/4 | 5 | -- | 5 | 4 | -- | 2-1/2 Neutral | Chromic acid | | | | 5 | -- | 5 | -- | 6 | -- | 8 | -- | 4 | -- | 10 | -- ----------+--------------+--------------+-------+------------

[Footnote 7: Commercial acids of course vary in strength, and the amount needed varies accordingly.]

All the figures are percentages of the weight of pelt. As K{2}Cr{2}O7 has a molecular weight of 294, and Na{2}Cr{2}O{7}2H{2}O a molecular weight of 298, in practice they may be considered as interchangeable, weight for weight. The sodium salt is cheaper and more often used. The corresponding amount of chromic acid, 2CrO{3}, has an equivalent weight of 200, hence any weight of dichromate may in practice be subst.i.tuted by two-thirds the weight of commercial chromic acid. Equivalent weights of commercial sulphuric acid are sometimes used in place of hydrochloric.

The quant.i.ty depends upon the strength of the sulphuric acid used.

Aluminium sulphate, Al{2}(SO{4}){3}18H{2}O (mol. wt. 666), may be replaced by ordinary potash alum, K{2}SO{4}Al{2}(SO{4}){3}24H{2}O (mol. wt. 948). In practice 7 parts of the former and 10 parts of the latter may be considered equivalent. It should be remembered that both these salts are hydrolyzed in solution, and therefore increase slightly the amount of free acid present. Their presence decreases the amount of chrome taken up, and as little or no alumina is found in the leather, there is usually small advantage in their employment. The use of salt is common but often unnecessary. It is considered desirable in baths of the acid type to prevent swelling by the excess of acid, and in baths made up from commercial chromic acid to replace correspondingly that normally formed from the reaction of dichromate and acid. It is used also in all baths which are intended to treat pickled goods. Like all electrolytes its presence decreases the adsorption of chromic acid.

All these conceivable modifications will make good leather, and the choice of a process often depends largely upon market prices. On the whole the tendency is to prefer the neutral or acid type, on account of the greater ease and completeness with which the bath may be exhausted.

Pickled stock may be depickled before tanning, by a bath of salt, mixed with borax, whitening, or basic alum solutions. It may also be placed direct in the chroming bath, but the amount of acid thus added with the goods must be determined and allowed for when making up the bath. No allowance is usually necessary, however, if the "pickle" consist only of alum and salt.

The chroming operation is carried out usually in drums or paddles. Drums are preferable because more concentrated baths may be used; these solutions penetrate quicker and are easier to exhaust economically. They are also preferable for hides and heavy skins. Paddles are preferable where grain is important, and for light skins in which little time is needed. Small variations in the ratio of chrome to pelt, or in concentration of liquor, have little influence upon the resulting leather.

The a.n.a.lytical investigation and control of chroming baths is usually simple. A suitable volume of liquor is t.i.trated with N/10 thiosulphate after acidifying with hydrochloric acid and adding pota.s.sium iodide. The operation should be conducted in a stoppered bottle, and the liquor allowed to stand for 10-15 minutes after adding the iodide and before t.i.trating. A little fresh starch infusion should be added towards the end of the reaction. Each c.c. N/10 thiosulphate corresponds to 0.0033 gram CrO{3} or 0.0049 gram K{2}Cr{2}O{7}. The same volume of liquor should also be t.i.trated with N/10 caustic soda and phenolphthalein.

Pota.s.sium chromate is neutral to this indicator, _i.e._ chromic acid acts as a dibasic acid. Any excess of hydrochloric acid is also t.i.trated. More indicator should be added towards the end of the t.i.tration, as it is often oxidized. Each c.c. N/10 soda corresponds to 0.005 gram CrO{3}, 0.01 gram "half-bound" CrO{3} (_i.e._ present as dichromate), 0.0147 gram K{2}Cr{2}O{7}, or 0.00365 gram HCl. If _a_ c.c. N/10 thiosulphate and _b_ c.c. N/10 soda be needed the type of chroming bath may be seen at a glance--

---------------------------+-------------+----------------------- If | The type is | The bath contains ---------------------------+-------------+----------------------- _b_ is greater than 1/3_a_ | Schultz | pota.s.sium dichromate but is less than 2/3_a_ | | and chromic acid _b_ is greater than 2/3_a_ | Acid | chromic acid and free | | hydrochloric acid _b_ equals 1/3_a_ | Neutral | chromic acid only ---------------------------+-------------+-----------------------

If 10 c.c. chrome liquor require _a_ and _b_ c.c. of thiosulphate and soda respectively--

I. 10 c.c. of a Schultz bath contain (b - 1/3a) 0.01 gram CrO{3} and [(a0.0033) - [(b - 1/3a) 0.01]] 1.47 grams K{2}Cr{2}O{7}

II. 10 c.c. of an acid bath contain (a0.0033) grams CrO{3} and [(b - 2/3a) 0.00365] grams HCl

III. 10 c.c. of a neutral bath (a0.0033) grams > CrO{3} _or_ (b0.005) grams /