MINERAL 

CoLouRs.—Those include Chrome Yellow, Iron Buff, Prussian Blue and Manganese Brown . Chrome Yellow is only useful in cotton-dyeing as a self-colour, or for conversion into chrome orange, or, in conjunction with indigo, for the production of fast green colours . The cotton is first impregnated with a solution of lead acetate or nitrate, squeezed, and then passed through a solution of sodium sulphate or lime water to fix the lead on the fibre as sulphate or oxide of lead . The 752 material is then passed through a solution of bichromate of potash . The colour is changed to a rich orange by a short, rapid passage through boiling milk of lime, and at once washing with water, a basic chromate of lead being thus produced . The colour is fast to light, but has the defect of being blackened by sulphuretted hydrogen . Iron Buff is produced by impregnating the cotton with a solution of ferrous sulphate, squeezing, passing into sodium hydrate or carbonate solution, and finally exposing to air, or passing through a dilute solution of bleaching powder . The colour obtained, which is virtually oxide of iron, or iron-rust, is fast to light and washing, but is readily removed by acids . Prussian Blue is applicable to wool, cotton and silk, but since the introduction of coal-tar blues its employment has been very much restricted . The colour is obtained on cotton by first dyeing an iron buff, according to the method just described, and then passing the dyed cotton into an acidified solution of potassium ferrocyanide, when the blue is at once developed . A similar method is employed for silk . Wool is dyed by heating it in a solution containing potassium ferricyanide and sulphuric acid .

The colour is developed gradually as the temperature rises; it may be rendered brighter by the addition of stannous chloride . On wool and silk Prussian blue is very fast to light, but alkalis turn it brown (ferric oxide) . Manganese brown or

bronze is applied in wool, silk and cotton dyeing . The animal fibres are readily dyed by boiling with a solution of potassium permanganate, which, being at first absorbed by the fibre, is readily reduced to insoluble brown manganic hydrate . Since caustic potash is generated from the permanganate and is liable to act detrimentally on the fibre, it is advisable to add some magnesium sulphate to the permanganate bath in order to counter-act this effect . Irritation furs are dyed in this manner on wool-plush, the tips or other parts of the fibres being bleached by the application of sulphurous acid . Cotton is dyed by first impregnating it with a solution of manganous chloride, then dyeing and passing into a hot solution of caustic soda . There is thus precipitated on the fibre manganous hydrate, which by a short passage into a cold dilute solution of bleaching powder is oxidized and converted into the brown manganic hydrate . This manganese bronze or brown colour is very susceptible to, and readily bleached by, reducing agents; hence when exposed to the action of an atmosphere in which gas is freely burnt, the colour is liable to be discharged, especially where the fabric is most exposed . In other respects manganese bronze is a very fast colour . Dyeing on a large Scale.—It is not possible to give here more than a bare outline of the methods which are used on the large scale for dyeing textile fibres, yarns and fabrics . In principle, dyeing is effected by allowing an aqueous'. solution of the dye-stuff, with or without additions (alkalis, acids, salts, &c.), to act, usually at an elevated temperature, on the material to be dyed .

During the

process it is necessary, in order to ensure the uniform distribution of the dyestuff in the material, that the latter should either be moved more or less continuously in the dye liquor or that the dye liquor should be circulated through the material . The former mode of operation is in general use for hank, warp and piece dyeing, but for textile fibres in the loose condition or in the form of " slubbing," " sliver " or " cops " (see SPINNING) the latter method has, in consequence of the introduction of improved machinery, come more and more into vogue within recent years . Loose Material.—Cotton and wool are frequently dyed in the loose state, i.e. before being subjected to any mechanical treatment . The simplest method of effecting this is to treat the material in open vessels (boilers) which can be heated either by means of steam or direct fire . • Since, however, a certain amount of felting or matting of the fibres cannot be avoided, it is frequently found to be more advantageous to effect these treatments in specially constructed apparatus in which the dye liquors are circulated through the material . Yarn.—Yarn may be dyed either in the hank, in the warp or in the cop, i.e. in the form in which the yarn leaves the spinning frame . The dyeing in the hank is carried out in rectangular dye-vats constructed of wood or stone like that shown in fig.', in which the hanks are suspended from smooth wooden poles or rods resting on the sides, and are thus immersed almost entirely in the dye liquor . The heating of the vat is effected either by means of live steam, i.e. by blowing steam into the dye solution from a perforated pipe which runs along the bottom of the vat, ' . The term " dry dyeing," which is carried out only to a very limited extent, relates to the dyeing of fabrics with the dyestuff dissolved in liquids other than water, e.g. benzene, alcohol, &c.or by means of a steam coil similarly situated . In order to expose the hanks as uniformly as possible to the action of the dye liquor, they are turned by hand at regular intervals until the operation is finished . Washing off is effected in the same or in a similar vessel, after which excess of water is removed by wringing by hand, through squeezing rollers or, what is generally preferred, in a hydro-extractor (centrifugal machine) . The drying of the dyed and washed yarn is generally effected by suspending it on poles in steam-heated drying chambers .

Yarn in the warp is dyed in vats or " boxes " like that shown in fig . 2, through which it is caused to pass continuously . The warps to be dyed pass slowly up and down over the loose rollers in the first

box B, then through squeezing rollers S into the next, and the same thing occurs in the second (also third and fourth in a four-box machine) box A, whence they are delivered through a second pair of squeezing rollers Sl into the wagon W . The boxes may contain the same or different liquors, according to the nature of the dyestuff employed . Washing is done in the same machine, while drying is effected on a cylinder drying machine like that shown in figs . 8 and q of BLEACHING . Latterly, machines have been introduced for dyeing warps on the beam, the dye liquor being caused to circulate through the material, and the system appears to be meeting with considerable success . Large quantities of yarn, especially cotton, are now dyed in the cop . When the dyed yarn is to be used as weft the main advantage of this method is at once apparent, inasmuch as the labour, time and waste of material incurred by reeling into hanks and then winding back into the compact form so as to fit into the shuttle are avoided . On the other hand the number of fast dyestuffs suitable for cop dyeing is very limited . In the original cop-dyeing machine constructed by Graemiger a thin tapering perforated metallic tube is inserted in the hollow of each cop . The cops are then attached to a perforated disk (which con- stitutes the lid of a chamber or box) by inserting the protruding ends of the tubes into the perforations .

The chamber is now immersed in the dye-bath and the hot liquor is

drawn through the cops by means of a centrifugal pump and returned continuously to the dye-bath . This principle, which is known as the skewer or spindle system, is the one on which most modern cop-dyeing machines are based . In the so-called " compact " system of cop dyeing the cops are packed as closely as possible in a box, the top and bottom (or the two opposite sides) of which are perforated, the interstices between the cops being filled up with loose cotton, ground cork or sand . The dye liquor is then drawn by suction or forced by pressure through the box, thus permeating and dyeing the cops . Pieces.—Plain shades are usually dyed in the piece, this being the most economical and at the same time the most expeditious means of obtaining the de- sired effect . The dyeing of piece goods may be effected by running them through the dye liquor either at full breadth or in rope form . The machine in most com- mon use for the first method is the Lancashire " jigger," which is simple in principle and is shown in section in fig . 3 . It consists essentially of a dye-vessel constructed of wood or cast iron and containing loose guide rollers, r and r, at the top and bottom . By coupling up the the pieces which are batched on A are drawn through the dye liquor and rolled on to B . A band brake (not shown in the figure) applied to the axis of A gives the pieces the required amount of tension in passing through the dye-bath . As soon as the whole of the pieces have passed through in this way from A to B, the machine is reversed, and roller A draws them back again through the bath in a similar way on to roller A .

This alternating process goes on until the dyeing is finished, when the goods are washed off, squeezed and dried . The jigger is especially useful in cotton piece dyeing, one

great advantage being that it is suited for what is known as a " short, bath," i.e. a bath containing a minimum amount of dye liquor, this being of great importance in the application of dyestuffs which do not exhaust well, like the direct colours and the sulphide colours . The padding machine is similar in principle to the jigger, the pieces running over loose guide rollers through the mordant or dye solution contained in a trough of suitable shape and size, but on leaving the machine they pass through a pair of squeezing rollers which uniformly express the excess of liquor and cause it to be returned to the bath . The padding machine is used more for preparing (mordanting, &c.) than for dyeing . For the dyeing of pieces in rope form a so-called "dye-beck " is used, which is a machine of larger dimensions than the jigger . Across the dye-bath is attached a winch W (see fig . 4), by means of which the pieces, sewn together at the ends so as to form an end- less band, are caused to circulate through the machine, being drawn up on the front side of the machine and allowed to drop back into the dye liquor on the other . This form of machine is particularly suited for the mordanting and dyeing of heavy goods . Washing off may be done in the same machine . The drying of piece goods is done on steam-heated cylinders like those used for the drying of bleached goods (see BLEACHING) . The operations which precede dyeing vary according to the material to be dyed and the effects which it is desired to produce . Loose wool, woollen and worsted yarn and piece goods of the same material are almost invariably scoured (see BLEACHING) before dyeing in order to remove the oily or greasy impurities which would otherwise interfere with the penetration of the dye solution .

Silk is subjected to the process of discharging or boiling off (see BLEACHING) in order to remove the silk

gum or sericine . Cotton which is to be dyed in dark shades does not require any preparatory treatment, but for light or very bright shades it is bleached before dyeing . Wool and silk are seldom bleached before dyeing . Cotton, wool and union (cotton warp and worsted weft) fabrics are frequently singed (see BLEACHING) before dyeing . Worsted yarn, especially two-fold yarn, is very liable to curl and become entangled when scoured, and in order to avoid this it is necessary to stretch and " set " it . To this end it is stretched tight on a specially constructed frame, placed in boiling water, and then cooled . Similarly, union fabrics are liable to " cockle " when wetted, and although this defect may be put right in finishing, spots of water or raindrops will give an uneven appearance of a permanent character to the goods, To avoid this, the pieces are subjected previous to dyeing to the so-called " crabbing " process, in which they are drawn under great tension through boiling water and wound on to perforated hollow cylinders . Steam is then blown through the goods and they are allowed to cool . With respect to the question of colour, we meet with two kinds of substances in nature, those which possess colour and those which do not . Why this difference ? The physicist says the former are bodies which reflect all the coloured dyeory of dyeing . rays of the spectrum composing white light—if opaque, they appear white; if transparent, they are colourless .

The latter are bodies which absorb some of the spectrum rays only, reflecting the

remainder, and these together produce the impression of colour . A black substance is one which absorbs all the spectrum rays . The fundamental reason, however, of this difference of action on the part of substances towards light remains still unknown . All substances which possess colour are not necessarily dyestuffs, and the question may .be again asked, Why ? It is a remarkable circumstance that most of the dyestuffs at present employed occur among the so-called aromatic or benzene compounds derived from coal-tar, and a careful study of these has furnished a general explanation of the point in question, which briefly is, that the dyeing property of a substance depends upon its chemical constitution . Speaking generally, those colouring matters which have the simplest constitution are yellow, and as the molecular weight increases their colour passes into orange, red, violet and blue . In recent years chemists have begun to regard the constitution of nearly all dyestuffs as similar to that of Quinone, and some even believe that all coloured organic compounds have a quinonoid structure . According to O . N . Witt, a colourless hydrocarbon, e.g. benzene, becomes coloured by the introduction of one or more special groups of atoms, which he terms the colour-bearing or chromophorous groups, e.g . NO2, – N:N –, &c . Benzene, for example, is colourless, whereas nitro-benzene and azo-benzene are yellow .

Such compounds containing chromophorous groups are termed chromogens, because, although not dyestuffs themselves, they are capable of generating such by the further introduction of

salt-forming atomic groups, e.g . OH, NH2 . These Witt terms auxochromous groups . In this way the chromogen tri-nitrobenzene, C6H3(NO2)3, becomes the dyestuff tri-nitro-phenol (picric acid), C6H2(NO2)3(OH), and the chromogen azo-benzene, C6HS•N N•C6H5, is changed into the dyestuff amido-azo-benzene (Fast Yellow), C6H5•N : N•CSH4(NH2) . These two dyestuffs are typical of a large number which possess either an acid or a basic character according as they contain hydroxyl (OH) or amido (NH2) groups, and correspond to the Acid Colours and Basic Colours to which reference has already been made . Other important atomic groups which frequently occur, in addition to the above, are the carboxyl (COOH) and the sulphonic acid (HSO3) groups; these either increase the solubility of the colouring matter or assist in causing it to be attracted by the fibre, &c . In many cases the free colour-acid or free colour-base has little colour, this being only developed in the salt . The free base rosaniline, for example, is colourless, whereas the salt magenta (rosaniline hydrochloride) has a deep crimson colour in solution . The free acid Alizarin is orange, while its alumina-salt is bright red . It may be here stated that the scientific classification of colouring matters into Nitro-colours, Azo-colours, &c., already alluded to, is based on their chemical constitution, or the chromophorous groups they contain, whereas the classification according to their mode of application is dependent upon the character and arrangement of the auxochromous groups . The question of the mordant-dyeing property of certain colouring matters containing (OH) and (COOH) groups has already been explained under the head of Artificial Mordant Colours . The peculiar property characteristic of dyestuffs, as distinguished from mere colouring matters, namely, that of being readily attracted by the textile fibres, notably the animal fibres, appears then to be due to their more or less marked acid or basic character .

Intimately connected with this is the fact that these fibres also exhibit partly basic and partly acid characters, due to the presence of carboxyl and amido groups . The behaviour of magenta is typical of the Basic Colours . As already indicated, rosaniline, the base of magenta, is colourless, and only becomes coloured by its union with an acid, and yet wool and silk can be as readily dyed with the colourless rosaniline (base) as with the magenta (salt) . The explanation is that the base rosaniline has

united with the fibre, which here plays the part of an acid, to form a coloured salt . It has also been proved that in dyeing the animal fibres with magenta (rosaniline hydrochloride), the fibre unites with the rosaniline only, and liberates the hydrochloric acid . Further, magenta will not dye cotton unless the fibre is previously prepared, e.g. with the mordant tannic acid, with which the base rosaniline unites to form an insoluble salt . In dyeing wool it is the fibre itself which acts as the mordant . In the case of the Acid Colours the explanation is similar . In many of these the free colour-acid has quite a different colour from that of the alkali-salt, and yet on dyeing wool or silk with the free colour-add, the fibre exhibits the colour of the alkali-salt and not of the colour-acid . In this case the fibre evidently plays the part of a base . Another fact in favour of the view that the union between fibre and colouring matter is of a chemical nature, is that by altering the chemical constitution of the fibre its dyeing properties are also altered; oxycellulose and nitrocellulose, for example, have a greater attraction for Basic Colours than cellulose . Such facts and considerations as these have helped to establish the view that in the case of dyeing animal fibres with many colouring matters the operation is a chemical process, and not merely a mechanical absorption of the dyestuff .

A similar explanation does not suffice, however, in the case of dyeing cotton with the Direct Colours . These are attracted by cotton from their solutions as alkali salts, apparently without decomposition . The

affinity existing between the fibre and colouring matter is somewhat feeble, for the latter can be removed from the dyed fibre by merely boiling with water . The depth of colour obtained in dyeing varies with the concentration of the colour solution, or with the amount of some neutral salt, e.g. sodium chloride, added as an assistant to the dye-bath; moreover, the dye-bath is not exhausted . The colouring matter is submitted to the action of two forces, the solvent power of the water and the affinity of the fibre, and divides itself between the fibre and the water . After dyeing for some time, a state of equilibrium is attained in which the colouring matter is divided between the fibre and the water in a given ratio, and prolonged dyeing does not intensify the dyed colour . Some investigators hold the view that in some cases the fibres exert a purely physical attraction towards colouring matters, and that the latter are held in an unchanged state by the fibre . The phenomenon is regarded as one of purely mechanical surface-attraction, and is compared with that exercised by animal char-coal when employed in decolourizing a solution of some colouring matter . Some consider such direct dyeing as mere diffusion ofthe colouring matter into the fibre, and others that the colouring matter is in a state of " solid solution " in the fibre, similar to the solution of a metallic oxide in coloured glass . According to this latter view, the cause of the dyeing of textile fibres is similar to the attraction or solvent action exerted by ether when it with-draws colouring matter from an aqueous solution by agitation . Latterly the view has been advanced that dyeing is due to precipitation of the colloid dyestuffs by the colloid substance of the fibre . In the case of colours which are dyed on mordants, the question is merely transferred to the nature of the attraction which exists between the fibre and the mordant, for it has been conclusively established that the union between the colouring matter and the mordant is essentially chemical in character .

From our present knowledge it will be seen that we are unable to give a final

answer to the question of whether the dyeing process is to be regarded as a chemical or a mechanical process . There are arguments and facts which favour both views; but in the case of wool and silk dyeing, the prevailing opinion in most cases is in favour of the chemical theory, whereas in cotton-dyeing, the mechanical theory is widely accepted . Probably no single theory can explain satisfactorily the fundamental cause of attraction in all cases of dyeing, and further investigation is needed to answer fully this very difficult and abstruse question . The poisonous nature or otherwise of the coal-tar dyes has been frequently discussed, and the popular opinion, no doubt dating from the time when magenta and its derivatives were contaminated with arsenic, seems to be that they are con for the most part really poisonous, and ought to be ciuson. avoided for colouring materials worn next the skin, for articles of food, &c . It is satisfactory to know that most of the colours are not poisonous, but some few are—namely, Picric acid, Victoria Orange, Aurantia, Coralline, Metanil Yellow, Orange II. and Safranine . Many coal-tar colours have, indeed, been recommended as antiseptics or as medicinal remedies, e.g . Methyl Violet, Auramine and Methylene Blue, because of their special physiological action . In histology and bacteriology many coal-tar colours have rendered excellent service in staining microscopic preparations, and have enabled the investigator to detect differences of structure, &c., previously unsuspected . In photography many of the more fugitive colouring matters, e.g . Cyanine, Eosine, Quinoline Red, &c., are employed in the manufacture of ortho-chromatic plates, by means of which the colours of natural objects can be photographed in the same degrees of light and shade as they appear to the eye—blue, for example, appearing a darker grey, yellow, a lighter grey, in the printed photograph . Since the year 1856, in which the first coal-tar colour, mauve, was discovered, the art of dyeing has made enormous advances, mainly in consequence of the continued introduction of coal-tar colours having the most varied properties and suitable for nearly every requirement . The old idea that the vegetable dyestuffs are superior in fastness to light is gradually being given up, and, if one may judge from the past, it seems evident that in the future there will come a time when all our dyestuffs will be prepared by artificial means .

AuTxoxrrIas.—Macquer, Hellot and le Pileur d'Apligny, The Art of Dyeing Wool, Silk and Cotton (

London, 1789) ; Bancroft, Philosophy of Permanent Colours (2 vols., London, 1813) ; Berthollet-Ure, Elements of the Art of Dyeing (2 vois., London, 1824) ; Chevreul, Recherches chimiques sur la teinture (Paris, 1835–1861) ; O'Neill, The Chemistry of Calico Printing, Dyeing and Bleaching (Manchester, 186o) ; Dictionary of Calico Printing and Dyeing (London, 1862) ; Schutzenberger, Trite des matieres colorantes (2 vols., Paris, 1867) ; Bolley, Die Spinnfasern and die im Pflanzen- and Thierkorper vorkommenden Farbstoffe (1867) ; Crookes, A Practical Handbook of Dyeing and Calico-Printing (London, 1874) ; Jarmain, Wool-Dyeing (1876) ; rO'Neill, Textile Colourist (4 vols., Manchester, 1876) ; Calvert, Dyeing and Calico Printing (Manchester, 1876); Moyret, Traite de la teinture des soies (Lyon, 1877); O'Neill, The Practice and Principles of Calico Printing, Bleaching and Dyeing (Manchester, 1878) ; Girardin, Matieres textiles et matieres tinctoriales (Paris, 188o)'; Hummel, The Dyeing of Textile Fabrics (London, 1885) ; Sansone, Dyeing (Manchester, 1888) ; Witt, Chemische Technologie der Gespinnstfasern (Brunswick, 1888) ; Benedikt and Knecht, The Chemistry of the Coal-Tar Colours (London, 1889) ; Hurst, Silk Dyeing, Printing and Finishing (London, 1892) ; Noelting and Lehne, Anilinschwarz (Berlin, 1892); Knecht, Rawson and Loewenthal, Manual of Dyeing (London, 19o8); Steinbeck, Bleichen and Farben der Seide and Halbseide (Berlin, 1895) ; Gardner, Wool-Dyeing (Manchester, 1896) ; Rawson, Gardner and Laycock, A Dictionary of Dyes, Mordants, &c . (London, 1901); Gros-Renaud, Les Mordants en teinture et en impression (Paris, 1898) ; Georgievics, The Chemical Technology of Textile Fabrics (London, 1902) ; Paterson, The Science of Colour Mixing (London, 1900); Paterson, Colour Matching on Textiles (London, 1901) ; Beech, The Dyeing of Cotton Fabrics (London, 1901) ; Beech, The Dyeing of Woollen Fabrics (London, 19o2); The Journal of the Society of Dyers and Colourists (Bradford, 1885–1908) and the publications of the colour manufacturers . (J . J . H.; E .