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DYEING (0. Eng. dedgian, dealt ; Mid....

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Originally appearing in Volume V08, Page 746 of the 1911 Encyclopedia Britannica.
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DYEING (0. Eng. dedgian, dealt ; Mid. Eng. deyen), the art of colouring textile and other materials in such a manner that the colours will not be readily removed by those influences to which they are likely to be submitted—e.g. washing, rubbing, light, &c. The materials usually dyed are those made from the textile fibres, silk, wool, cotton, &c., and intended for clothing or decoration; but in addition to these may be mentioned straw, fur, leather, paper, &c. The art of dyeing dates from prehistoric times, and its practice probably began with the first dawn of civilization. Although we Historical cannot trace the successive stages of its development sketch. from the beginning, we may suppose they were some- what similar to those witnessed among certain uncivilized tribes to-day—e.g. the Maoris of New Zealand. At first the dyes were probably mere fugitive stains obtained by means of the juices of fruits, and the decoctions of flowers, leaves, barks and roots; but in course of time methods were discovered, with the aid of certain kinds of earth and mud containing alumina or iron, whereby the stains could be rendered permanent, and then it was that the true art of dyeing began. There is no doubt that dyeing was, in the early period of its history, a home industry practised by the women of the household, along with the sister arts of spinning and weaving, for the purpose of embellishing the materials manufactured for clothing. Historical evidence shows that already at a remote period a high state of civilization existed in Persia, India, and China, and the belief is well founded that the arts of dyeing and printing have been practised in these countries during a long succession of ages. In early times the products and manufactures of India were highly prized throughout Southern Asia, and in due course they were introduced by Arabian merchants to Phoenicia and Egypt, with which countries commercial intercourse, by way of the Persian and Arabian Gulfs, seems to have existed from time immemorial. Eventually the Egyptians themselves began to practise the arts of dyeing and printing, utilizing no doubt both the knowledge and the materials derived from India. Pliny the historian has left us a brief record of the methods employed in Egypt during the first century, as well as of the Tyrian purple dye celebrated already moo B.C., while the chemical examination of mummy cloths by Thomson and Schunck testifies to the use by the Egyptian dyers of indigo and madder. The Phoenician and Alexandrian merchants imported drugs and dyestuffs into Greece, but we know little or nothing of the methods of dyeing pursued bythe Greeks and Romans, and such knowledge as they possessed seems to have been almost entirely lost during the stormy period of barbarism reigning in Europe during the 5th and succeeding centuries. In Italy, however, some remnants of the art fortunately survived these troublous times, and the importation of Oriental products by the Venetian merchants about the beginning of the 13th century helped to revive the industry. From this time rapid progress was made, and the dyers formed important guilds in Florence, Venice and other cities. It was about this time, too, that a Florentine named Rucellai rediscovered . the method of making the purple dye orchil from certain lichens of Asia Minor. In 1429 there was published at Venice, under the title of Mariegola dell' ante de tentori, the first European book on dyeing, which contained a collection of the various processes in use at the time. From Italy a knowledge of dyeing gradually extended to Germany, France and Flanders, and it was from the latter country that the English king Edward III. procured dyers for England, a Dyers' Company being incorporated in 1472 in the city of London. A new impetus was given to the industry of dyeing by the discovery of America in 1492, as well as by the opening up of the way to the East Indies round the Cape of Good Hope in 1498. A number of new dyestuffs were now introduced, and the dyewood trade was transferred from Italy to Spain and Portugal, for the East Indian products now came direct to Europe round the Cape instead of by the old trade routes through Persia and Asia Minor. Eastern art-fabrics were introduced in increasing quantity, and with them came also information as to the methods of their production. In Europe itself the cultivation of dye-plants gradually received more and more attention, and both woad and madder began to be cultivated, about 1507, in France, Germany and Holland. Under the influence of Spain the Dutch largely developed their industries and made considerable progress in dyeing. The Spaniards, on their first arrival in Mexico (1518), noticed the employment of the red dyestuff cochineal by the natives, and at once imported it to Europe, where an increasing demand for the new colouring matter gradually developed in the course of the century. A further impetus was given to the trade by the Dutch chemist Drebbel's accidental discovery, in 1630, of the method of dyeing a brilliant scarlet on wool by means of cochineal and tin solutions. The secret was soon communicated to other dyers, and the new scarlet was dyed as a speciality at the Gobelin dyeworks in Paris, and some time later (1643) at a dyeworks in Bow, near London. In 1662 the newly established Royal Society in London took a useful step in advancing the art of dyeing, and in order to inform and assist practical dyers, caused the publication of the first original account, in the English language, of the methods employed in dyeing, entitled " An apparatus to the history of the common practices of Dyeing." Ten years later the French Minister Colbert sought to improve as well as control the operations of dyeing, by publishing a code of instructions for the use of the woollen dyers and manufacturers in France. From this time, too, a succession of eminent chemists were appointed by the French government to devote some of their attention to the study of the industrial arts, including dyeing, with a view to their progress and improvement. Dufay, Hellot, Macquer, Berthollet, Roard and Chevreul (1700-1825) all rendered excellent service to the art, by investigating the chemical principles of dyeing, by publishing accounts of the various processes in vogue, by examining the nature and properties of the dyestuffs employed, and by explaining the cause of the several phenomena connected with dyeing. With the advent of the 18th century, certain old prejudices against the use of foreign dyewoods gradually disappeared, and very rapid progress was made owing to the birth of the modern chemistry and the discovery of several useful chemical products and processes—e.g. Prussian Blue (1710), Saxony Blue or Indigo Extract (1740), sulphuric acid (1774), murexide (1776), picric acid (1788), carbonate of soda (1793), bleaching powder (1798). Experiments on the practical side of bleaching and dyeing were made during this period, in England by Thomas Henry, Home and Bancroft, and in France l'v Dambourney, Gonfreville and others, each of whom has left interesting records of his work. Down to the middle of the 19th century natural dyestuffs alone, with but few exceptions, were at the command of the dyer. But already in the year 1834 the German chemist Runge noticed that one of the products obtained by distilling coal-tar, namely, aniline, gave a bright blue coloration under the influence of bleaching powder. No useful colouring matter, however, was obtained from this product, and it was reserved for the English chemist Sir W. H. Perkin to prepare the first aniline dye, namely, the purple colouring matter Mauve (1856). The discovery of other brilliant aniline dyestuffs followed in rapid succession, and the dyer was in the course of a few years furnished with Magenta, Aniline Blue, Hofmann's Violet, Iodine Green, Bismarck Brown, Aniline Black, &c. Investigation has shown that the products of the distillation of coal-tar are very numerous, and some of them are found to be specially suitable for the preparation of colouring matters. Such, for example, are benzene, naphthalene and anthracene, from each of which distinct series of colouring matters are derived. In 1869 the German chemists Graebe and Liebermann succeeded in preparing Alizarin, the colouring matter of the madder-root, from the coal-tar product anthracene, a discovery which is of the greatest historical interest, since it is the first instance of the artificial production of a vegetable dyestuff. Another notable discovery is that of artificial Indigo by Baeyer in 1878. Since 1856, indeed, an ever-increasing number of chemists has been busily engaged in pursuing scientific investigations with the view of preparing new colouring matters from coal-tar products, and of these a few typical colours, with the dates of their discovery, may be mentioned: Cachou de Laval (1873); Eosin (1874); Alizarin Blue (187;1; Xylidine Scarlet (1878); Biebrich Scarlet (1879); Congo Red (1884); Primuline Red (1887); Rhodamine (1887); Paranitraniline Red (1889); Alizarin Bordeaux (189o); Alizarin Green (1895). At the present time it may truly be said that the dyer is furnished with quite an embarrassing number of. coal-tar dyestuffs which are capable of producing every variety of colour possessing the most diverse properties. Many of the colours produced are fugitive, but a considerable number are permanent and withstand various influences, so that the general result for some years has been the gradual displacement of the older natural dyestuffs by the newer coal-tar colours. During this period of discovery on the part of the chemist, the mechanical engineer has been actively engaged in devising machines suitable for carrying out, with a minimum of manual labour, all the various operations connected with dyeing. This introduction of improved machinery into the dyeing trade has resulted in the production of better work, it has effected considerable economy, and may be regarded as an important feature in modern dyeing. The art of dyeing is a branch of applied chemistry in which the dyer is continually making use of chemical and physical principles in order to bring about a permanent union in this respect an intermediate position. These differences may be to some extent due to differences of physical structure in the fibres, but they are mainly due to their different chemical composition. On the other hand, a given fibre, e.g. cotton, behaves quite differently in dyeing towards various colouring matters. Some of these are not at all attracted by it, and are incapable of being used as dyestuffs for cotton. For others cotton exhibits a marked attraction, so that it is readily dyed by mere steeping in a hot solution of the colouring matter. Again, for other colouring matters cotton has little or no attraction, and cannot be dyed with them until it has been previously impregnated or prepared with a metallic salt, tannic acid or some other agent which is capable of combining with the colouring matter and precipitating it as an insoluble coloured compound within or upon the fibre. Such differences of behaviour are to be ascribed to differences in the chemical constitution or atomic arrangement of the various colouring matters. In the case of the coal-tar colours we are, for the most part, well acquainted with their chemical constitution, and in accordance with this knowledge the chemist has arranged classifithem in the following groups:—(1) Nitro Colours. cation of (2) Azo Colours, including Amido-azo, Oxy-azo, colouring Tetrazo and Polyazo Colours. (3) Hydrazone Colours. masers. (4) Oxy-quinone Colours, including Quinone-oxime Colours. (5) Diphenylmethane and Triphenylmethane Colours, including Rosaniline, Rosolic acid and Phthaleine Colours. (6) Quinoneimide Colours, including Indamine, Indophenol, Thiazime, Thiazone, Oxazime, Oxazone, Azine, Induline, Quinoxaline and Fluorindine Colours. (7) Aniline Black. (8) Quinoline and Acridine Colours. (9) Thiazol Colours. (to) Oxy-ketone, Xanthone, Flavone and Cumarine Colours. (11) Indigo. (12) Colours of unknown constitution. This arrangement of the colouring matters in natural chemical groups is well suited for the requirements of the chemist, but another classification is that based on the mode of their application in dyeing. This is much simpler than the previous one, and being better adapted for the practical purposes of the dyer, as well as for explaining the various methods of dyeing, it is preferred for this article. According to this arrangement colouring matters are classified under the following groups:—(r) Acid Colours. (2) Basic Colours. (3) Direct Colours. (4) Developed Colours. (5) Mordant Colours. (6) Miscellaneous Colours. (7) Mineral Colours. It is well to state that there is no sharp line of division between some of these groups, for many colours are applicable by more than one method, and might quite well be placed in two, or even three, of the above groups. This may be due either to the kind of fibre to which the colouring matter is to be applied, or to certain details in the chemical constitution of the latter which give it a twofold character. ACIu Conouxs.—These dyestuffs are so called because they dye the animal fibres wool and silk in an acid bath; they do not dye cotton. From a chemical point of view the colouring matters themselves are of an acid character, this being due to the presence in the molecule of nitro (NO2) or sulphonic acid (HSO3) groups. According to their origin and constitution they may be distinguished as nitro compounds, sulphonated azo compounds and sulphonated basic colours. The acid colours are usually sold in the form of their alkali salts, as variously coloured powders soluble in water. For the alkali salts in neutral or alkaline solution wool and silk have little or no affinity, but dyeing rapidly occurs if the solution is acidified with sulphuric acid whereby the colour-acid is liberated. This addition of acid, however, is necessary not only to set free the colour-acid of the dyestuff, but also to alter partially the chemical composition of the fibre, and thus render it capable of uniting more readily with the free colour-acid. It has been shown, namely, that if wool is boiled with dilute sulphuric acid, and then thoroughly washed with boiling-water till free from acid, it acquires the property of being dyed with acid colours even in neutral solution. By this treatment a portion of the wool substance is converted into so-called lanuginic acid, which has a strong at-traction for the colour-acid of the dyestuff, with which it forms an insoluble coloured compound. For dyeing wool, the general rule is to charge the dyebath with the amount of dyestuff necessary to give the required colour, say from a to 2 or 6% on the weight of wool employed, along with to% sodium sulphate (Glauber's salt) and 4% sulphuric acid (1.84 sp. gr.). The woollen material is then General between the material to be dyed and the colouring principles. matter applied. If cotton or wool is boiled in water containing finely powdered charcoal, or other insoluble coloured powder, the material is not dyed, but merely soiled or stained. This staining is entirely due to the entanglement of the coloured powder by the rough surface of the fibre, and a vigorous washing and rubbing suffices to remove all but mere traces of the colour. True dyeing can only result when the colouring matter is presented to the fibre in a soluble condition, and is then, by some means or other, rendered insoluble while it is absorbed by, or is in direct contact with, the fibre. There must always be some marked physical or chemical affinity existing between fibre and colouring matter, and this depends upon the physical and chemical properties of both. It is well known that the typical fibres, wool, silk and cotton, behave very differently towards the solution of any given colouring matter, and that the method of dyeing employed varies with each fibre. As a general rule wool has the greatest attraction for colouring matters, and dyes most readily; cotton has the least attraction, while silk occupies 746 introduced and continually handled or moved about in the solution, while the temperature of the latter is gradually raised to the boiling point in the course of ; to I hour; after boiling for 's to % hour longer, the operation is complete, and the material is washed and dried. In practice, modifications of this normal process may be introduced, in order to ensure the dyeing of an even colour, i.e. free from such irregularities as cloudiness, streaks, &c.: which may be due to the quality of the material or to the special properties of the acid colour employed. Materials of a firm, close texture, also the existence of a strong affinity between fibre and colouring matter, do not generally lend themselves to the dyeing of even colours, or to a satisfactory penetration of the material. Some acid colours dye even colours without any difficulty; others, however, do not. The addition of sodium sulphate to the dyebath exerts a restraining action; the dyeing therefore proceeds more slowly and regularly, and a more equal distribution and better absorption of. the colouring matter takes place. Other devices to obtain even colours are: the use of old dye-liquors, a diminished amount of acid, the employment of weaker acids, e.g. acetic or formic acid or ammonium acetate, and the entering of the material at a low temperature. oIn the application of so-called Alkali Blue the process of dyeing in an acid bath is impossible, owing to the insolubility of the colour-acid in an acid solution. Wool and silk, however, possess an affinity for the alkali salt of the colouring matter in neutral or alkaline solution, hence these fibres are dyed with the addition of about 5 %o borax; the material acquires only a pale colour, that of the alkali salt, in this dyebath, but by passing the washed material into a cold or tepid dilute solution of sulphuric acid a full bright blue colour is developed, due to the liberation of the colour-acid within the fibre. In the case of other acid colours, e.g. Chromotrope, Chrome Brown, Chromogen, Alizarin Yellow, &c., the dyeing in an acid bath is followed by a treatment with a boiling solution of bichromate of potash, alum, or chromium fluoride, whereby the colouring matter on the fibre is changed into insoluble oxidation products or colour-lakes. This operation of developing or fixing the colour is effected either in the same bath at the end of the dyeing peration, or in a separate bath. See also Artificial Mordant Colours. When dyeing with certain acid colours, e.g. Eosine, Phloxine and other allied bright pink colouring matters derived from resorcin, the use of sulphuric acid as an assistant must be avoided, since the colours would thereby be rendered paler and duller, and only acetic acid must be employed. The properties of the dyes obtained with the acid colours are extremely varied. Many are fugitive to light; on the other hand, many are satisfactorily fast, some even being very fast in this respect. As a rule, they do not withstand the operations of milling and scouring very well, hence acid colours are generally unsuitable for tweed yarns or for loose wool. They are largely employed, however, in dyeing other varieties of woollen yarn, silk yarn, union fabrics, dress materials, leather, &c. Previous to the discovery of the coal-tar colours very few acid colours were known, the most important one being Indigo Extract. Prussian Blue as applied to wool may also be regarded as belonging to this class, also the purple dyestuff known as Orchil or Cudbear: The following list includes some of the more important acid colours now in use, arranged according to the colour they yield in dyeing: Red.—Wool scarlet, brilliant scarlet, erythrine, croceIn scarlet, brilliant CroceIn, violamine G, scarlet 3R, crystal scarlet, new coccine, chromotrope 2R, azo acid magenta, Victoria scarlet, xylidine scarlet, Palatine scarlet, Biebrich scarlet, pyrotine, orchil red, Bordeaux B, milling red, azo carmine, acid magenta, fast acid violet A 2R, naphthylamine red, fast red, claret red, eosine, erythrosine, rose Bengale, phloxine, cyanosine, cloth red, lanafuchsine, rosinduline, erio carmine. Orange.—Diphenylamine orange, methyl orange, naphthol orange, crocein orange, brilliant orange, orange G, orange N, mandarin G R. Yellow.—Picric acid, naphthol yellow S, fast yellow, brilliant yellow S, azoflavine, metanil yellow, resorcine yellow, tartrazine, quinoline yellow, milling yellow, azo yellow, Victoria yellow, brilliant yellow S, citronine, Indian yellow. Green.—Acid green, guinea green, fast green, patent green, cyanol green, erio green, brilliant acid green 6 G. Blue.—Alkali blue, soluble blue, opal blue, methyl blue, HOchst new blue, patent blue, ketone blue, cyanine, thiocarmine, fast blue, induline, violamine 3 B, azo acid blue, wool blue, indigo extract, erio glaucine, erio cyanine, erio blue, lanacyl blue, sulphon-azurine, sulphon-cyanine. Violet.—Acid violet, red violet, regina violet, formyl violet, violamine B, fast violet, azo acid violet, erio violet, lanacyl violet. Brown: Fast brown, naphthylamine brown, acid brown, resorcine brown, azo brown, chrome brown, chromogene. Block: Naphthol black, azo black, wool black, naphthylamine black, jet black, anthracite black, Victoria black, azo acid black, brilliant black, union black, brilliant black B. Basic CoLouRs.—These colouring matters are the salts of organic colour-bases, their name being derived from the fact that their dyeing power resides entirely in the basic part of the salt. In the free state the bases are colourless and insoluble, but in combinationwith acids they form salts which are coloured and for the most part soluble in water. They are usually sold in the form of powder or crystals, the latter exhibiting frequently a beautiful metallic lustre. Wool and silk are dyed in a neutral bath, i.e. without any addition, the material not requiring any previous preparation. During the dyeing operation the animal fibres appear to play the part of an acid, for they decompose the colouring matter and unite with the colour-base to form an insoluble coloured salt or lake, while the acid of the colouring matter is liberated and remains in solution. Although, as a rule, a neutral dyebath is employed in dyeing wool, a slight addition (2 %) of soap is sometimes made in order to give a brighter colour, while in other cases, e.g. with Victoria Blue, the dyebath must of necessity be made distinctly acid with acetic or sulphuric acid. Silk is usually dyed in a bath containing " boiled-off liquor " (i.e. the spent soap-liquor from the operation of scouring) neutralized or slightly acidified with acetic or tartaric acid. For a full colour use 2 or 3 % colouring matter, enter the wool at a low temperature, heat gradually to near the boiling point in the course of a hour, and continue dyeing fora hour. Owing to the slight solubility of many basic colours, it is important to take the pre-caution of filtering the colour solution into the dyebath through a flannel filter, also to neutralize the alkalinity of calcareous water with a little acetic acid, to prevent decomposition of the colouring matter and precipitation of the colour-base. Unlike the animal fibres, cotton has little or no affinity for the basic colours; hence the cotton dyer makes use of the fact that cotton has a natural attraction for tannic acid, and that the latter forms insoluble lakes with the bases of basic colours. Previous to dyeing, the cotton is prepared with tannic acid by steeping in a cold solution of the latter for several hours; cotton pieces are run at full width through a solution containing 2 to 6 oz. per gallon of tannic acid, and after being evenly squeezed are dried on steam cylinders. The cotton is then worked in a solution of tartar emetic or stannic chloride, so that the tannic acid absorbed by the fibre may be fixed upon it as insoluble tannate of antimony or tin. Although the tannic acid is thus united with metallic oxide, it still has the power of attracting the base of the colouring matter, and there is fixed upon the fibre an insoluble colour-lake, namely, a tannate of antimony and colour-base, which constitutes the dye. In this process the tannic acid is called the mordant, the tartar emetic acts as the fixing-agent for the tannic acid, and the cotton as finally prepared for dyeing is said to be mordanted. The proportions employed, reckoned on the weight of cotton, may vary from 2 to 10 % tannic acid, or the equivalent in a decoction of sumach, myrabolans, or other tannin matter, and Z to 3 % tartar emetic. After mordanting and fixing of the mordant, the cotton is well washed and dyed in the cold or at 6o° C. fora to I hour with the necessary colouring matter. Applied in this manner, basic colours are moderately fast to soap; but generally not to the action of light. Linen is dyed in the same manner as cotton. Jute is dyed without any previous preparation, since it behaves like a tannin-mordanted fibre, attracting the basic colours direct. The basic colours, to which class most of the earlier coal-tar colours belonged, are remarkable for their great colouring power, and in most cases for the brilliancy of the colours they yield. With the exception of certain dark colours, they are fugitive to light. It is interesting to note that only one vegetable colouring matter is at present recognized as belonging to this class, namely, the yellow dyestuff barberry bark and root (Berberis vulgaris) which contains the alkaloid berberine. The following is a list of the more important basic colours derived from coal-tar: Red.--Magenta, safranine, rhodamine, pyronine red, rhoduline red, •rosazein, induline scarlet. Orange.—ChrysoIdine, phosphine, acridine orange, tannin orange. Yellow.—Auramine, benzoflavine, thioflavine T, acridine yellow, homophosphine, rhoduline yellow. Green.—Malachite green, emerald green, imperial green, China green, brilliant green, Victoria green, diamond green, methylene green, Blue.—Methylene blue, new methylene blue, toluidine blue, thionine blue, indamine blue, Victoria blue, night blue, Nile blue, turquoise blue, marine blue, indoine blue, metamine blue, Capri blue, indazine, metaphenylene blue, paraphenylene blue, toluylene blue, indigene, indol blue, diphene blue, setopaline, setocyanine, setoglaucine, Helvetia blue. Violet.—Methyl violet, crystal violet, ethyl purple, methylene violet, mauve, paraphenylene violet, rhoduline violet, methylene heliotrope. Brown.—Bismarck brown. Black.—Diazine black. Grey.—Methylene grey, nigrisine, new grey.
End of Article: DYEING (0. Eng. dedgian, dealt ; Mid. Eng. deyen)
WILLIAM DYCE (1806–1864)
JOHN DYER (c. 1700-1758)

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