Ferrous acetate is prepared in a manner similar to the aluminum acetate, and is occasionally employed instead of the ferrous sulphate. Inasmuch, however, as the solution of ferrous acetate is very easily oxidizable when exposed to the air, a more stable form is used, and this comes on the market as iron pyrolignite or iron liquor. This can be prepared by dissolving iron in crude acetic or pyroligneous acid, or by treating a solution of iron sulphate with calcium pyrolignite. Iron liquor is really a solution of ferrous acetate that contains certain organic impurities which prevent, or rather, considerably r.e.t.a.r.d the oxidation of the iron salt, but which in no way interfere with its mordanting properties. The commercial product can be had in various concentrations, but 10 degrees Beaume is the most usual and most convenient.
COPPER MORDANTS
The most important copper salts used in fur dyeing processes are copper sulphate, or blue vitriol, occurring in large blue crystals, very soluble in cold and in hot water; and copper acetate, which is formed by treating a solution of copper sulphate with a solution of the requisite quant.i.ty of lead acetate. Copper acetate can also be obtained in the form of blue-green crystals, very soluble in water, the solution becoming turbid on prolonged heating, due to the formation of a greenish basic copper acetate. This insoluble compound is known commonly as verdigris, although it is not usually produced in the manner mentioned. Numerous fur dyeing formulas contain verdigris, but inasmuch as the basic copper acetate is insoluble and thus incapable of reacting with any of the substances used in dyeing, it is a.s.sumed that the soluble normal copper acetate was meant, for this compound is also sometimes called verdigris.
In addition, there must be mentioned here a compound which formerly found extensive use in fur dyeing. This is a double salt of copper and iron, a.n.a.logous to alum, ferrous copper sulphate, known as blue salt. It is very seldom used at the present time, being more effectively replaced by other substances.
CHROMIUM MORDANTS
The typical chromium mordant is chrome alum, which is a pota.s.sium or ammonium chromium sulphate, const.i.tuted just like the aluminum alums, and forming crystals like these. More frequently used, nevertheless, than the chrome alum, is chromium acetate, which is prepared from it, either by treating a solution of the chrome alum with a solution of lead acetate, or in the following manner:
50 grams of chrome alum are dissolved in 500 cubic centimeters of boiling water. To this is added 15 grams of 20% ammonia, diluted with 15 grams of water.
The precipitate which forms is filtered off, and preserved, the filtrate being discarded. After thoroughly washing the residue on the filter it is dissolved in dilute acetic acid, heating if necessary, to effect solution.
Other chromium compounds of an entirely different type are also used in fur dyeing, these being chromates and bichromates, the latter finding greater application than the former. Sodium bichromate is the salt most usually employed. This forms orange-red crystals which are very soluble in water, and in addition to its use as a mordant it also serves as an oxidizing agent for developing or fixing certain dyes on furs.
TIN MORDANTS
Compounds of tin find only limited application in fur-dyeing, the only one of importance being tin salts, stannous chloride, which occurs in the form of white, hygroscopic crystals, which must be preserved in closed vessels.
It is very soluble, but in dilute solutions it readily forms a basic salt, so stannous chloride is usually used in very concentrated solutions.
ALKALINE MORDANTS
After the furs have been treated with the solution of some alkali for the purpose of killing the hair, they are always pa.s.sed through a slightly acidulated bath to remove any alkali which may still be adhering. This operation must always be gone through before the skins can be mordanted or dyed, for if it were neglected, very uneven and uncertain results would be obtained. This process, however, entails the expenditure of no small amount of time, labor and chemicals when large lots of skins are being handled. In order to eliminate this extra step of "souring"
between killing and mordanting or dyeing, it has been proposed to use alkaline mordants which combine the killing and mordanting functions, and accomplish these two processes at the same time. The advantages of employing such mordants are easily apparent. c.u.mbersome manipulation and handling of the skins, with the attendant consumption of much time and labor are reduced to a minimum, and besides there is no needless waste of chemicals as is the case in the ordinary methods of killing the furs.
The principle of alkaline mordants is not a strictly new one. If it be remembered that the old killing formulas used by the fur dyers of an earlier age, contained metallic salts with mordanting properties in addition to the alkaline substances, which alone were effective as killing agents, it would seem that the suggested alkaline mordants were merely a revival in modified form of the old processes. This is undoubtedly true in a large measure, for the killing mixtures which the old masters used certainly embodied the fundamental principle of simultaneous killing and mordanting, although it was not recognized at that time.
Modern alkaline mordants have therefore been devised which can be employed for killing and mordanting furs at the same time. They are prepared as follows:
ALKALINE ALUMINUM MORDANT
250 grams of pota.s.sium alum are dissolved in 1 liter of boiling water. To this solution is added 300 grams of soda ash, previously dissolved in 750 c.c. of water, and the resulting precipitate is filtered off, washed and pressed, and then dissolved in a solution of 65 grams of caustic soda in 1 liter of water.
ALKALINE CHROMIUM MORDANT
250 c.c. of chrome acetate mordant of 20 degrees Beaume 320 c.c. of caustic soda solution of 38 degrees Beaume (32.5%) 10 c.c. of glycerine 30 degrees Beaume (95%)
The solution of these substances is brought up to a volume of 1 liter by the addition of 420 c.c. of water.
ALKALINE IRON MORDANT
138 grams ferrous sulphate are dissolved in 362 c.c. of warm water. Cool and add 25 c.c. of glycerine. Then slowly and carefully add 25.5 c.c. of concentrated ammonia, taking care that no precipitate forms.
While these alkaline mordants seem to have much in their favor, there are certain possible objectionable features which must be considered.
The solutions of the mordants are generally very alkaline, and not every fur can withstand more than a limited quant.i.ty of alkaline substance for longer than a comparatively short time. Suitable mordanting usually requires a longer time than killing does, so with the use of the alkaline mordant, if the skins remain in the solution until sufficiently killed, they may be insufficiently mordanted, while if the furs are treated long enough to be properly mordanted, the hair may have been over-killed.
However, the idea of the alkaline mordant is a good one, and it is only a matter of time and patient, scientific experimentation when the difficulties of the method will be eliminated, and a much-desired process will become a practical realization.
The general methods for applying the various mordants of all sorts follow closely the procedure adopted for the killing formulas, and similar precautions must be observed, in order to obtain consistently uniform results. With the exercise of care, there is little reason for the mordanting operations to go wrong.
After proper treatment of the skins in the mordants, they are removed and drained off, then rinsed lightly in running water to remove the excess of mordant liquor, after which they can be directly entered into the dye bath. If it is not feasible to dye the mordanted skins at once, as is often the case, the skins are kept moist, and under no circ.u.mstances allowed to dry.
CHAPTER XII
FUR DYEING
MINERAL COLORS USED ON FURS
Before the introduction of the fur dyes now used, certain inorganic chemical substances were employed in addition to the vegetable dyes, for the production of colors on furs. Even to this day such materials are used to obtain certain effects in special instances. The idea of employing mineral chemicals undoubtedly originated in the textile-dyeing industry, which at one time was dependent to an appreciable extent on mineral substances for the production of certain fast shades. Compounds of iron, lead, manganese, also of copper, cobalt and nickel were all used for dyeing, either singly or in various combinations. In the application on furs, the brush method was the only one practicable, as the skins would have been ruined by dipping them into solutions of these chemicals in the concentrations necessary for dyeing.
The dyeing of furs with mineral colors involves the precipitation on the fibre in a more or less permanent form of the sulphide, oxide or other insoluble compound of a metal, and can be brought about in several ways. By what is known as double decomposition, that is, by the use of two solutions successively applied, the ingredient of one causing a precipitate to form when in contact with the const.i.tuent of the second, the color is produced on the hair. Another method is to use solutions of chemicals which decompose on contact with the hair, forming an insoluble compound. In the first method the hair is alternately treated with the two solutions of the requisite chemicals, drying between each brushing, the process being repeated until the desired shade is obtained. The second method merely requires the solution of the chemical to be applied to the hair, which is then dried, the color forming by itself.
One of the most important of the mineral dyes, and which is occasionally used to this day, is lead sulphide, formed by the double decomposition method by precipitating a soluble lead salt with ammonium sulphide, or any other alkaline sulphide. By simply brushing an aqueous solution of lead acetate, also known as sugar of lead, on a white fur such as white hare or rabbit, a light, brownish coloration is obtained due to the combination of the lead with the sulphur of the hair. If the lead solution is carefully applied several times on this type of fur, until a sufficiently dark color is produced, it is possible to get a fairly good imitation of the stone marten. The brown color is very fast, being actually formed within the hair. In most cases, however, for dyeing lead sulphide shades it is necessary to use the two solutions. Thus the pale greyish or slightly brownish-grey shades of the lynx can be reproduced on white rabbit or hare by this process. A solution containing 60 grams of lead acetate per liter of water is brushed on to the hair of the fur which has previously been killed in the usual manner, and the hair is then dried. A solution of 50 grams of ammonium sulphide per liter of water is next brushed on, and the fur again dried. Care must be exercised in handling the ammonium sulphide as it is a very malodorous liquid, the fumes of which are poisonous when inhaled. The alternate brushings are repeated until the desired depth of shade is obtained. A very dark brown, approaching a black can be obtained in this way. This color can be used for the production of certain attractive effects. By brushing over the tips of the hair, which has previously been dyed a dark brown by means of the lead sulphide color, with a dilute solution of hydrochloric acid, or with peroxide of hydrogen, the hair will become white in the parts so treated, due to the formation of lead chloride or lead sulphate, respectively. Thus white tipped furs can be obtained, but the process is applicable only when the furs have been dyed by the lead sulphide method.
Pota.s.sium permanganate is occasionally used to produce dyeings of a brown shade on furs. Considerable care has to be taken in applying this substance, as it is possible to affect the hair. The strength of the solution must be varied according as the hair to be dyed is weak or strong. A cold solution of 10 to 20 grams of pota.s.sium permanganate per liter of water is brushed on to the hair, which is then dried. A brown precipitate of manganese is formed on the hair after a short time, and the process is repeated until the required shade is obtained. For furs with harder hair, stronger solutions can be used. The dyeing is very fast, but it is seldom used, cheaper and better shades being obtained in other ways. Spotted white effects can be produced on the brown dyeing with permanganate of potash by applying a solution of sodium bisulphite, the brown color being dissolved by this chemical.
The compounds of other metals, such as iron, copper, cobalt and nickel are not used in practise as the dyeings are not fast, and can be better produced in other ways.
CHAPTER XIII
FUR DYEING
VEGETABLE DYES
With the exception of the few shades which could be produced solely by means of coloring matters of a chemical character, all dyeings on furs up to about thirty years ago were made with dye substances obtained from the vegetable kingdom, either alone, or in conjunction with the aforementioned mineral colors. The colors of vegetable origin used in comparatively recent times were mainly extracts of the wood of certain trees; so the name "wood dyes" has come to be applied generally to the dyes of this cla.s.s. The use of the vegetable or natural dyes on furs dates back to quite ancient times, as frequent allusions and descriptions in Biblical and other contemporaneous literature testify. There are numerous pictures on monuments and tablets ill.u.s.trating the dyeing of furs among the ancient Egyptians, the evidence indicating that the juice of certain berries, and extracts of certain leaves were used for the purpose. At a later period, in the Roman era, henna, which was used over two thousand years ago as to-day for the beautification of the hair of women, was also used to color fur skins. The instances cited here are merely of scientific and historical interest, and are not of practical importance as far as fur dyeing methods are concerned.
It was not until many centuries later that the dyeing of furs took on the aspects of a commercial art, and the substances then employed were chiefly tannin-containing materials such as gall-nuts and sumach, which in conjunction with certain metallic salts, particularly those of iron, were capable of producing dark shades. The use of iron compounds to form dark grey or black colors on leather tanned by means of the tannins, had been common for a long time, and it was natural that fur dyers should try to produce such shades on furs in a similar fashion. The use of the iron-tannin compound as a dye proved to be very effective, and to this day the production of blacks by means of the vegetable coloring matters has as a basis an iron-tannate. A formula in common use in the latter seventeenth and the eighteenth centuries for producing black shades on furs, is the following:
Lime water 1117 parts Gall-nuts 1500 Litharge 500 Salammoniac 65 Alum 128 Verdigris 64 Antimony 64 Minium 32 Iron filings 128 Green copperas 384
All these substances except the gall-nuts, the copperas and half the lime water were boiled up in a cauldron; then the gall-nuts and the copperas were placed in a bucket and the contents of the cauldron poured in, and the rest of the lime water added. The mixture was stirred up, allowed to settle for an hour, and when cool, was ready to be applied by the brush method. For dyeing by the dip process, a similar mixture was used, only considerably diluted with water. A study of the formula discloses the fact that in it are combined killing and mordanting substances as well as dyeing materials. The lime water, in conjunction with the salammoniac serves as a killing agent, the verdigris, copperas and alum are mordants, while the litharge and the minium, both compounds of lead, could possibly act as mineral dyes, and the iron filings and the antimony took virtually no part at all in the dyeing, except, perhaps to act in a mechanical way.
The formulas for other shades were made up along similar lines, the chief const.i.tuent of vegetable nature being either gall-nuts, sumach, or both.