A mixture for a chestnut brown, for example, contained gall-nuts, sumach, and the various other mineral const.i.tuents as in the black dye, litharge, alum, copperas, verdigris, salammoniac, antimony, and in addition, red lead and white lead. It is evident in both these instances that the shade obtained was as much the result of mineral dyeing as of vegetable dyeing.

The discovery of America introduced into Europe many new dye substances, chiefly wood extracts such as logwood and Brazilwood, but it was not until the nineteenth century that these materials found their way into the dye formulas of the fur dyer. Most of the processes used in the dyeing of furs were adaptations of methods employed in silk dyeing, the silk fibre being considered as most nearly approaching fur-hair in nature and characteristics. By devious and circuitous paths the formulas of the silk dyers reached the fur people, and so, in the middle of the nineteenth century, dye mixtures containing the various dyewoods as well as the tannin-containing substances were in general use for the dyeing of furs.

The following is a typical recipe of that time for the production of black on furs like wolf, skunk, racc.o.o.n, etc.:

Roasted gall-nuts 1000 parts Sumach 200 Iron mordant 200 Copper vitriol 100 Litharge 80 Alum 60 Salammoniac 50 Crystallized verdigris 40 French logwood extract 30 Rain water 7000

The mixture was boiled up, and after cooling was ready for application by the brush method, the skins being first killed by a killing mixture also applied by the brush. The dye substances in this case are the gall-nuts, sumach and the logwood extract, with the iron mordant, copper vitriol, and alum as mordants. For brown shades a similar formula was used containing Pernambuco wood extract, logwood extract, quercitron bark, gall-nuts and dragonblood, together with iron, copper and alum mordants.

Formulas such as the above were mainly empirical, that is, they were compounded as a result of trial of various combinations of the const.i.tuents, without considering the nature and quant.i.tative character of the reactions, as long as the desired shades could be obtained. Such dye mixtures were frequently found to yield results varying from those expected or originally obtained, because the effectiveness of the formulas depended upon the exact duplication in every detail, of conditions which had given satisfactory results previously, and it was not always possible to attain such an accurate reproduction of circ.u.mstances, especially when the fur dyers were quite ignorant of the scientific relationships of the materials used. So when more light had been shed on the nature and chemical characteristics of the vegetable dye substances, formulas like those described were no longer employed, although the essential ingredients were the same in the new processes. Unnecessary const.i.tuents were eliminated, and proper ones subst.i.tuted where it was required, and the quant.i.ties of the materials used were made to conform to the chemical laws governing the reactions. Since these new formulas were based on a rational understanding of the const.i.tuents and their reactions, it is desirable to study the latter briefly, before further discussing the formulas themselves.

The substances of vegetable origin used in modern fur dyeing may be grouped into two cla.s.ses, one, the tannin-containing materials, and the other, the dyewoods proper. The most important of the tannins are gall-nuts, sumach and chestnut extract. Cutch, which also comes under this cla.s.s, is more frequently used for the production of brown shades, so it is grouped with the dyewoods. Among the latter are logwood, fustic, Brazilwood, quercitron, turmeric, and several others of less significance.

1. _Tannin Materials_

First and foremost under this heading are the nutgalls. These are ball-shaped excrescences produced on certain plants by the punctures of insects in depositing their eggs. There are two chief varieties, the European, and the Chinese. The European galls are formed by the female gall-wasp which drops an egg in the rind of young branches of certain oaks. A swelling (the nutgall) is produced, in which the young insect develops, and from which it finally escapes by piercing a hole through the sh.e.l.l. Those galls which are not pierced have a fresh bluish or green color, are heavy and contain most tannic acid. After the insect has gone out, the galls are of a lighter, yellowish color, and also of inferior quality. The best oak-galls are the Aleppo, and the Turkish or Levant galls, containing 5560% of tannic acid, and about 4% of gallic acid. The Chinese galls are produced by the puncture of a plant-louse on the leaves and leaf-stalks of a species of sumach, and not on oaks. The galls are very light, and very rich in tannic acid, containing often as much as 80%.

For dyeing purposes, nutgalls are usually ground to a powder, and in some instances they are even roasted first and then ground.

Sumach consists of the leaves and sometimes of the small twigs and stems of a species of sumach plant known as the Rhus coriaria. The Sicilian variety is the finest commercial quality, with the Virginian ranking next.

It is sold as a powder, but also in the form of the whole or crushed leaves. The best sumach contains 1525% of tannin. Extracts are also manufactured, a liquid extract of 52 degrees Twaddell, which forms a dark brown, thick paste; and a solid extract, formed by evaporating the liquid extract to dryness.

Chestnut extract is prepared from the wood of the chestnut oak, which contains 810% of tannin. The solid extract has a bright, black color, while the liquid extract is a dark brown paste with a smell like that of burnt sugar.

The tannins all give greyish to black shades with iron salts, and it is this fact which renders them important for fur dyeing.

2. _Wood dyes_

One of the most important of all the natural dye substances, especially for the production of blacks, is logwood. The color is really a red, but with the common mordants it forms blue, violet or black shades. Logwood, or campeachy wood, as it is sometimes called, is the product of a large tree growing in the West Indies, and Central and South America. When freshly cut, the wood is practically without color, but when exposed to the air it soon becomes a dark reddish-brown on the surface. The coloring principle of logwood is called hematoxylin, which is a colorless substance when pure, and is of itself incapable of dyeing; but when it is exposed to the air, especially when moist and in the presence of some alkaline substance, it is converted into hematein, which is the real coloring matter of logwood. To prepare the wood for use, the logs are chipped or rasped, the chips being heaped up and moistened with water. Fermentation occurs, and the heaps are frequently turned to allow free access of air to the wood, and to prevent overheating. As a result of this process, a great part of the hematoxylin is converted to the hematein. The logwood may be used for dyeing in this state as chips, but logwood extracts can now be obtained of a high degree of purity and are easier to work with. The commercial forms of the extract, are the liquid of 51 degrees Twaddell, and the solid extract. Hematein crystals can also be obtained. All these extracts contain mainly hematein, together with a small percentage of hematoxylin which is converted to the former during the dyeing process.

Logwood is never used as a direct dye, but is used to form color lakes with the various mordants, the following colors being produced:

Iron mordants give grey to black shades Copper mordants give green-blue to black shades Chrome mordants give blue to black shades Aluminum mordants give violet shades Tin mordants give purple shades

By combining several of the mordants, any desired shade of black can be obtained, and if other dyewoods are used in conjunction with the logwood, the range can be further increased.

Fustic, yellow-wood, or Cuba wood, as it is variously called, is obtained from a tree also growing in the West Indies, Central and South America.

It is used either as wood chips, or as a paste extract of 51 degrees Twaddell, and occasionally as solid extract. Fustic contains two coloring matters, morintannic acid, possessing the characteristics of a tannin, and which is quite soluble in water, and morin, which is rather insoluble, and which settles out from the liquid extract. Fustic is the most important of the yellow dyes of natural origin, and is used considerably in fur dyeing with logwood for shading the blacks, or for producing compound shades.

With the usual mordants fustic gives the following colors:

With iron salts dark olive With copper salts olive With chrome salts olive-yellow to brownish-yellow With aluminum salts yellow With tin salts bright yellow to orange-yellow

Brazilwood, or redwood, is the product of a tree found in Brazil, and exists in several varieties, such as peach wood, Sapan wood, Lima wood, and Pernambuco wood. They all yield similar shades with the various mordants, and all seem to contain the same coloring principle, brasilin, which, like the hematoxylin, has no dyeing power, but by fermentation and oxidation it is converted to brasilein, corresponding to the formation of hematein. Brazilwood and the related woods are used either as chips or extract, but seldom alone, usually in conjunction with other dyewoods. By combining logwood, fustic and Brazilwood in various proportions, and by employing suitable mordants, all the shades required by the fur dyer can easily be produced.

Quercitron is the inner bark of a species of oak (Quercus tinctoria) found in the United States. It contains two coloring principles, quercetrin and quercetin. The fresh decoction of quercitron bark is a transparent dull orange-red which soon becomes turbid and deposits a yellow crystalline ma.s.s. It is generally used in conjunction with other dyes.

Cutch is the dried extract obtained from a species of acacia, the princ.i.p.al varieties being Bombay, Bengal, and Gambier cutch. It contains two coloring principles, catechin and catechu-tannic acid. Cutch acts as a tannin, and like other tannins discussed above, can be used for the production of grey or black shades with iron mordants. It is employed chiefly, however, for dyeing browns. Aluminum salts give with cutch a yellowish-brown, tin salts give a lighter yellow, copperas gives a brownish-grey, and chrome and copper salts give brown shades.

Turmeric is the underground stem of the Curc.u.ma tinctoria, the coloring principle being called curc.u.min. It may be used as a direct dye, but usually a mordant is used. Turmeric is sometimes used in place of fustic.

While the tannins can be used alone with an iron mordant for producing greyish to black shades, the dyewoods alone yield colors which would be too bright to be suitable for dyeing furs. In order to tone down this brightness, and to give to the dyeings that greyish undertone which is characteristic of the natural furs, and which can only be imitated by means of the iron-tannin compound, it is customary to combine the tannins with the wood dyes. The iron-tannate const.i.tutes the foundation of the color which gets its intensity, and necessary brilliancy and bloom from the wood dyes. Moreover, the presence of the iron-tannin compound helps considerably to increase the fastness of the dyeing. Furs dyed with the combination of the tannins and the wood dyes obtain an additional tanning treatment which materially improves the quality of the leather, for not only do the tannin substances exert this tanning action, but the dyewoods as well, for they are themselves either of the nature of tannins, or contain a coloring principle which is a tannin. It is to the combined effects of the tannin substances and the dyewoods that furs dyed with vegetable dyes owe their beauty of color, l.u.s.tre, naturalness of shade, permanence of the dyeing, and durability of the leather. Wood dyeings on furs have for this reason acquired a just renown, but owing to the introduction of the new kinds of fur dyes, the use of the vegetable dye substances has been greatly reduced.

The dyes of vegetable origin can be applied to furs by either the brush method or the dip method, or both, and since mordants are required with the dyes of this cla.s.s, they are applied in one of the three ways mentioned in a previous chapter: first, by mordanting before dyeing; second, by applying mordant and dye simultaneously; and third, by mordanting after the skins have been treated with the dye.

I. DYEING WITH VEGETABLE DYES BY THE BRUSH METHOD

The use of the brush method in applying the natural dyes to furs is limited to a comparatively few kinds of dyeing, namely to produce special effects on furs, or to give to the upper-hair of furs a coat of dye different from the base color. In a quite recent German patent is described a process for blending a red fox as a silver fox and the procedure affords a good example of brush dyeing with preliminary mordanting. The specification is as follows: "D. R. P. 310, 425 (1918).

A process for dyeing red fox as silver fox. The tanned and dressed skin is first superficially decolorized by applying a dilute mixture of milk of lime, iron vitriol and alum, with a soft brush so as only to penetrate the top-hair. Allow to remain for 46 hours, dry, and beat out the dust.

A dilute solution of iron vitriol is brushed on so as only to wet the top-hair, and the skin is thus allowed to remain moist for 1224 hours.

Then without drying, a solution of iron vitriol, salammoniac, litharge, red argol and wood ashes is brushed on cold with a hard brush so as to penetrate all the hair down to very near the skin. The skin has now completely lost its red color, and has become a pale yellow. It is now ready to be dyed. An infusion of roasted nutgalls, which have been boiled for 34 hours with water, is applied cold with a soft brush to the upper hair. Allow to remain so for 23 hours, and without drying, apply a weaker solution of the roasted nutgalls with a hard brush so as to saturate the hair thoroughly. Dry and beat out. According to the concentration of the solution applied, the hair will be colored blue-grey to black, and the shade can be varied by varying the strength of the solutions used. The different parts of the skin, or those parts of different shades can be dyed accordingly."

In this patent all the operations, including killing, mordanting and dyeing are done by the brush method, and the process, from this point of view is quite similar to one which might have been employed a century previous. It is evident that the time and effort required to carry out the details as described in the patent would only be warranted in exceptional cases, where the value of the dyed fur would be considerably greater than that of the natural skin.

An example of the application at the same time of dye and mordant by the brush method is the original French Seal dye, which is still employed to a limited extent to produce a brilliant, deep, l.u.s.trous black topping on furs which have already been dyed by the dip process. A typical formula for the old French Seal dye is the following:

Green copperas 10 parts Alum 10 Verdigris 10 Gall-nuts 80 Logwood extract (15 degrees Twaddell) 150 Water 1000

This mixture is applied to the top of the hair of the furs, after previous killing, and the skins allowed to remain moist for several hours, and also exposed to the air. The skins are then dried, and beaten out, and if necessary a second coat of dye is brushed on. In dyeing seal-imitation on muskrat, or skunk-imitation on opossum, for example, the black color required on the top-hair, or the upper part of the hair when the furs are sheared, can be produced by applying a mixture similar to the above, to the furs after they have received their base color by the dip process with natural dyes or with the Oxidation Colors. Occasionally, the dyeing is given an after-treatment with a dilute solution of sodium bichromate to help develop the color, the action in this case being that of an oxidizing agent, and not of a mordant.

As far as the third method of mordanting is concerned, that of first applying the dye, and then the mordant, it is rarely practised with the brush method. The procedure, however, consists in first brushing on a solution of the desired dye, then drying and brushing on a mordant solution. These operations are repeated perhaps two or three times until the proper shade is obtained, exposing the furs to the air for the color to be developed.

II. DYEING WITH VEGETABLE DYES BY THE DIP METHOD

It was in the application to furs by the dip process that the use of the vegetable dyes attained great importance, and although at the present time, natural organic dyes have largely been superseded by the Oxidation Colors and Aniline Black dyes, yet for certain purposes, and especially for the production of blacks, the wood dyes still are able to hold their own.

The dyeing of black formerly const.i.tuted probably the most important branch of the fur dyeing industry, and was undoubtedly the most difficult one. For it is possible to obtain as many different kinds of black as there are dyers of this color, but only a few certain shades are desirable. The division of the cla.s.ses of furs into those derived from the various kinds of sheep, and those obtained from other animals is particularly marked in the dyeing of black, and both the composition of the dye formulas and the methods of dyeing are somewhat different for the two groups. For the dyeing of black on Persian lambs, broadtails, caraculs, etc., a combination of logwood and nutgalls with the requisite mordants is used, while on hares, Chinese sheep, foxes, racc.o.o.ns, opossum, etc., a mixture of logwood and turmeric or fustic, with the proper mordants is used.

The general procedure is as follows: The dye substances to be used are ground up to a powder in a mill constructed for the purpose, after which they are boiled with water in a copper-lined kettle or cauldron, heated from the outside by steam. The customary arrangement is to have a jacketed kettle, supported on a stand, and having taps and valves to enable the liquor to be drawn off, or pivoted, so that the kettle can be tilted, and the contents poured out. The use of the copper-lined vessel is to be preferred, as it is unaffected by any of the dye substances, and so cannot cause any rust stains. After the dyes have gone into solution and have cooled, the mordant chemicals, previously dissolved in water, are added, and the mixture stirred up. The dyeing in this instance is effected by the simultaneous application of dye and mordant. The dye mixture is now run off, or poured out in the proper quant.i.ty into a number of small vats of 2530 gallon capacity, or into a paddle vat, which can be closed, while the paddle is rotating. The latter device is to be preferred because it permits the dye to retain its temperature better and for a longer period of time, but when lambs are being dyed only the open vats are used. The temperature of the dye mixture is between 40 and 45 C., for only at this temperature can the hair absorb the dye properly without injuring the leather. The killed skins are immersed in the dyebath for a time, usually overnight, after which they are removed, drained and hung up, with the hair-side exposed to the air, so as to permit the dye to develop, which takes place with the aid of the atmospheric oxygen. The dyebath is again brought to the proper temperature, and the skins are again entered, to go through the same process as often as is necessary to obtain the desired depth of shade. The dyed skins are thoroughly washed to remove excess dye, then dried and finished. The following are a few dye formulas used in the production of blacks:

Logwood extract 100 grams Chestnut extract 14 c.c.

Turmeric 38 grams Iron acetate 6 Be. 50 c.c.

Water 1200 c.c.

or,

Cutch 15 grams Soda 14 grams Logwood extract 120 grams Verdigris 19 grams Iron acetate 5 Be. 16 c.c.

Water 1200 c.c.

A recently published formula for dyeing China goat skins black, is the following:

Dissolve 50 lbs. of dark turmeric and 45 lbs. of logwood extract and make up to 300 gallons of solution, at 95 F. Enter the killed skins and leave them in the liquor until they rise to the surface. Then take them out and add 25 lbs. of logwood extract, 10 lbs. of sumach, 10 lbs. of blue vitriol, 5 lbs. of fustic extract, and about 60 lbs. of iron acetate liquor. Stir up well, and immerse the skins for 18 hours. Draw them up, and expose to the air for 12 hours. Heat the liquor again to 95 F. and put the skins back for 12 hours. Draw out, hang up in the air for a time, then wash thoroughly, hydro-extract, dry and finish.

In a German patent, D. R. P. 107,717 (1898), is described a method for dyeing lambs black, consisting in treating the skins for 24 hours in a logwood bath, then rinsing in cold water, and mordanting for 15 hours in a solution of bichromate of potash. The skins are then washed and treated with a solution of iron salt, then dried. This process, while of not much practical importance, is an ill.u.s.tration of mordanting subsequent to the dyeing treatment.

As far as the production of other shades is concerned, the procedure is quite similar to the regular black method. For a dark brown, for example, the skins are dyed in a mixture containing

Gall-nuts 40 parts Verdigris 10 Alum 10 Copperas 5 Brazilwood extract (15 Twaddell) 150 Water 1000