BLEACHING, DYEING, AND CALICO-PRINTING. ANNOUNCEMENT. TECHNOLOGICAL HANDBOOKS. THIS series has been designed to meet the wants of those who, 011 account of the high price of an encyclopaedia, are unwilling to purchase when they wish to consult but a small portion of it, and of others who seek for fuller infor- mation than can be found in works of such scope. It is hoped that these Handbooks will be of use both to the expert and the beginner. Each book will be complete in itself, embracing informa- tion on several collateral subjects, illustrations being intro- duced whenever they will be found of advantage in explain- ing the text. They will be issued in handy form, at a low price. The editing has been undertaken by Mr. John Gardner, who has had large experience in work of this kind, having been interested in the preparation of recent editions of " Cooley's Cyclopaedia." The first volume appeals to all interested in the Manu- facture and Trade of ALCOHOL COMPOUNDS. The second, now offered to the reader, treats of BLEACHING, DYEIXG, and CALICO-PRINTING. The third volume, which is in active preparation, will deal with ACETIC ACID and YINEGAR, AMMONIA, and ALUM. J. & A. CHURCHILL. [CHURCHILL'S TECHNOLOGICAL HANDBOOKS.] BLEACHING, DYEING, AND CALICO-FEINTING: Witfo JT G LONDON: 3. & A. CHUKCHILL, 11, NEW BURLINGTON STREET. 1884. QJ EDITOR'S PREFACE. ALTHOUGH the present volume claims to be little more than a summary of the arts of Bleaching, Dyeing, and Calico-printing, the Editor hopes it may, notwithstand- ing, be found a ready and serviceable manual for practical workers, and that in many cases, it may be instrumental in shortening the time and trouble, that would otherwise be expended in consulting the pages of larger and more elaborate 'works. The Editor has to tender his grateful acknowledgments to his friends, Air. J. F. HODGES, jun., of Belfast, and Mr. JAMES CHAD WICK, of Manchester ; the former for his valuable assistance in the compilation of the chapter on "Bleaching,'-' the latter for his no less valuable contributions to the sections on " Dyeing and Calico- printing." To Mr. CHAD WICK the Editor is indebted vi EDITORS PREFACE. for many of liis formulae, and additionally for a large amount of equally useful technical information. Lastly, the Editor has to acknowledge his indebted- ness to Mr. CKOOKES' " Practical Handbook of Dyeing and Calico-printing \ 3 URE'S " Dictionary of Arts, Manufactures, and Mines ;" WAGNER'S " Chemical Technology," edited by W. CROOKES, F.E.S. ; CALVERT'S "Dyeing and Calico-printing/'' edited by STENHOUSE and GROVES, F.K.S., and SPOX'S "Encyclopaedia of the Industrial Arts :" all of which works have been consulted in the preparation of this little volume. JOHX GARDNER, F.I.C., E.G. a LONDON, December, 1883. CONTENTS. CHAP. PAGE I. BLEACHING i II. DYEING 33 III. CALICO-PRIXTI-XCJ 61 IV. DYE STUFFS 133 APPENDIX 193 BLEACHING, DYEING, AND CALICO PRINTING. CHAPTER I. BLEACHING. BLEACHING is the process by which the colour of bodies, natural or acquired, is removed, and by which they are rendered white or colourless. It is more particularly applied to the decolorization of textile filaments, and of cloths made of them. Bleaching is a very ancient art, as passages referring to it in the earlier sacred and other writers fully testify. It had probably reached a high degree of excellence among the inhabitants of the first Assyrian empire, and was certainly practised in Egypt long before the commencement of written history. We may fairly assume that fine white linen formed part of the " raiment," which, together with " jewels of gold and jewels of silver and precious things," Abraham sent as presents to the beautiful Rebekah and her family, fully three centuries and a half before the Exodus. Subsequently, in Scripture, we have special mention of "fine linen, white and clean." Herodotus, the earliest Greek historian, tells us that the Babylonians wore " white cloaks ;" and in Athenseus we read of " shining fine linen," B 2 BLEACHING, DYEING, ETC. as opposed to that which was " raw" or unbleached. At this early period, and for many centuries afterwards, the operations of washing, fulling, and bleaching were not distinctly separated. The common system of washing, followed by drying in the sun, adopted by the ancients, is a process which of itself, by frequent repetition, decolorizes the raw materials of textile fabrics, and thus must inevitably have taught them the art of " natural bleaching" of a character similar to that practised in Europe up to a com- paratively very recent period. And this appears, according to the authority of ancient authors, to have been the case. Washing or steeping in alkaline and ammoniacal lyes, or in milk of lime, followed by exposure in the sun, formed the chief basis of their system ; whilst woollens, then as now, were treated with soap and fuller's earth, or with potter's clay, marl, limolian earth, or other like minerals. Urine was highly esteemed among them; and we are told that, in the time of the Emperor Vespasian, and undoubtedly long before, cloths were sulphured. Indeed, according to Pliny, sulphuring was often had recourse to in ordinary washing, as well as in the bleaching process. Bleaching continued to be practised with no essential change of its principles until the discovery of chlorine, to which we shall presently refer. Though the art of bleaching dates from the remotest ages, little or nothing was known of it in Great Britain as an art, until within a century, and it was then the custom to send the linen manufactured in Great Britian over to Holland, as the inhabitants of that country were at this period considered the most superior bleachers in Europe. An account of the method which the Dutch adopted at their great bleach works near Haarlem, is described by Mr. F. HODGES, jun., in his " Chemistry for Bleachers." It consisted in steeping the goods in a lixivium or lye made from the lye-ashes of Russia, and in which other cloth had been steeped ; after- BLEACHING. 3 wards they were steeped in a new lye of lye-ashes poured upon them boiling hot. In this solution they were left for some days, after which they were washed and pressed,, and then steeped in a sour made either by the fermentation of bran and water or buttermilk. The souring usually lasted from six to seven days ; after which the linen was washed, and then spread upon the grass to bleach by exposure to light, air, and moisture. The bleaching grounds were cut with canals in different places, from which the linen was watered with long narrow shovels made in the shape of a scythe ; the water of these canals came from the sand downs, and to the beneficial effects derived from it was mainly attributed the superior lustre of the Dutch cloth ; indeed, it was long a prejudice on the Continent that no water was so good for bleaching as sea water. This process usually required from six to seven months for its completion, and the goods bleached by it were sold under the name of Dutch cloth or Hollands. Another variety of linen bleached at Haarlem, which from its fineness was generally spread out on the better grass fields or lawns, received the title of lawn. Several authorities relate that in 1749 an Irishman named DUNLOP, who had learned something of the nature and art of bleaching, settled in the north of Scotland, and established works for the purpose of bleaching Scotch goods; and though for some years he failed to bleach the goods entrusted to him satisfactorily, in a few years he became an excellent practical bleacher, and from that time no more goods were sent to Holland for the purpose of being bleached. The art, when introduced into Great Britain by this enterprising Irishman, is described as not differing in the smallest degree from the method employed by the Dutch, from whom it was copied. It consisted of steepings and boilings in alkaline lyes, called bucking, then washing and exposing on grass, 'B 2 4 BLEACHING, DYEING, ETC. called crofting; these operations were repeated several times, reducing the strength of the lyes every time. The linen was then steeped in sour milk for some weeks, after which it was washed clean and crofted. This process was repeated as often as was required to produce a pure white. The first improvement in this tedious process occurred after the introduction of a new method for the manufacture of sulphuric acid by Dr. ROEBUCK, which greatly reduced the price of that acid. The improvement consisted in the substitution by Dr. FRANCIS HOME, of Edinburgh, of water acidulated with sulphuric acid, as a sour for the buttermilk hitherto employed ; this reduced the time required for souring from weeks to days, not to mention the absence of the risk with which the use of the milk was accom- panied, as sours of this description were very liable to corruption. Little further change took place in the art of bleaching until about the year 1787, when a most important improvement was effected in consequence of the discovery, in the year 1774, by SCHEELE, the celebrated Swedish chemist, of a substance which he called dephlogisticated marine air. The French chemist, BERTHOLLET, in 1785, repeated the experiments of SCHEELE on this new substance, and showed that it was a gas soluble in water, to which it gave a yellowish green colour, an astringent taste, and the peculiar smell by which it is distinguished. Owing to BERTHOLLET'S experiments, this body was known until the year 1810 as oxygenated muriatic acid, or oxy-muriatic acid, into which it was shortened ; but in that year Sir H. DAVY, adopting the idea of GAY-LUSSAC and THENARD, who had experimented with it, that it was an elementary substance, called it chlorine, owing to its peculiar colour, by which name it is known at the present day. BERTHOLLET'S ideas, and the result of some experiments which he made in bleaching linen BLEACHING. 5 with the gas, were mentioned by him in a paper which he read before the Academy of Sciences, at Paris, in April, 1795, and published in the Journal de Physique for May of the same year. He also published a paper in the number for August, 1 786, of the same journal, explaining the nature of the action of chlorine on vegetable colours, and showing how it could best be employed. PARKES, in his " Chemical Essays," relates how a Mr. COPLAND, Professor of Natural Philosophy in Aberdeen, while on a visit to Geneva, was shown by Professor de SAUSSURE of that town, the experiment of discharging vegetable colours by chlorine gas. The Aberdeen Professor, having been impressed with the importance of the experi- ment, communicated it on his return home to some eminent manufacturers, the Messrs. MILNES, of the firm of GORDON, BARRON & Co., of Aberdeen, who immediately entered upon a course of experiments in the preparation of the gas, and the best manner of employing it in bleaching, and obtained satisfactory results. PARKES states that this was about the end of July, 1787, and was, he believes, the first actual application of the then so-called oxy-muriatic acid in Great Britain. With this statement, however, other authorities on the subject do not agree, and it seems with some truth. Mr. F. HODGES, jun., in his " Chemistry for Bleachers," goes fully into the whole subject, and the weight of evidence which he brings to bear from numerous quarters goes far to prove that the distinguished engineer, JAMES WATT, if not the first, at least is entitled to the honour of having intro- duced it at as early a date as Professor COPLAND. WATT learnt the process of manufacturing and using chlorine from BERTHOLLET in 1786, and shortly afterwards introduced the process 011 a large scale into his father-in-law's (Mr. MAC GREGOR) bleach works at Glasgow. WATT laid the results of the employment of this gas in bleaching at Glasgow, before the Manchester manufacturers. In enforcing the importance 6 BLEACHING, DYEING, ETC. of the new substance and process on these gentlemen, he was ably followed and seconded by -Mr. THOMAS HENRY, F.R.S., of Manchester, and it is related how this gentleman and WATT unreservedly described to each other the result of their experiments. To Mr. HENRY we are indebted for the introduction of the new art into Lancashire. WATT made several improvements in the art, one of which was that instead of employing muriatic acid and manganese, as had been done by SCHEELE and BERTHOLLET for the production of the gas, he used a mixture of common salt, black oxide of manganese and sulphuric acid, which was much cheaper. He also invented a method of testing the strength of the water impregnated with chlorine, so as to estimate its bleaching power. This he did by taking a known quantity of infusion of cochi- neal, and ascertaining how much of the bleaching liquor was necessary to destroy the colour the larger the quantity necessary, the weaker obviously was the bleaching solution. Chlorine, when first introduced, was used in the state of gas, and one great drawback to it was its noxious odour, which is not only very disagreeable, but exceedingly injurious to health. To BERTHOLLET we owe the credit of being the first to remedy many of the defects of bleaching by chlorine, as, while visiting Javelle for the purpose of showing some bleachers the method of using the gas, he added a little potash to prevent the gas from impairing the goods. Not long after this, these bleachers announced in different journals that they had discovered a new bleaching liquor, which they called the " Lye" or " Eau de Javelle," and applied to the British Government to grant them the exclusive right to supply the public with it, but in this they were defeated, as it was shown that the same article had been in common use in Great Britain for some time, which fact prevented them from obtaining a patent, and BLEACHING. 7 consequently the liquor of Javelle, which thus became the property of the public, turned out to be nothing but a solu- tion of potash in water impregnated with chlorine, as was proved by BERTHOLLET shortly after its pretended discovery. After the failure of the foreigners to obtain a monopoly of the Lye of Javelle, other bleachers learnt to make it for them- selves, and continued to use it for some time. Though this bleaching liquor had some advantages over the solution of the gas in water, they were more than counterbalanced by the disadvantages, such as its being less economical than the solution of chlorine in water, and its not keeping any length of time without losing its bleaching properties. On account of these disadvantages, its use was not long continued. The next attempt to improve on this bleaching solution was made by Mr. HENRY, of .Manchester, to whom we have before referred, who is said to have first thought of the addition of lime, but owing to his manner of employing it, which was open to many objections, it did not come into use. Other attempts were made by different persons to improve on this process, but none succeeded till Mr. TENNANT, after long and laborious investigation, hit upon a method of making a saturated liquid, composed of chlorine and lime, for which he took out a patent in the year 1798. This patent was pronounced invalid, and unjustly so, as many authorities consider. But Mr. TENNANT was not so easily defeated, for in the following year, 1799, he took out another patent, which may be considered the completion of the new method. This patent consisted in impregnating quicklime in a dry state with chlorine.- As the originality of this invention was not disputed, and as its great supe- riority over all methods previously introduced was obvious, the demand for the product has gone on increasing, year by year, up to the present date. The " new or continuous process" of bleaching, as it is called, and that which is at 8 BLEACHING, DYEING, ETC. present in general use in all the chief bleach works of Lancashire, was introduced by Mr. DAVID BBXTLEY, of Pendleton, and patented by him in 1828. Bleaching is commonly said to be natural when exposure to light, air, and moisture forms the leading part of the pro- cess; and to be chemical when chlorine, or any of the hypochlorites, or sulphurous acid, or other like substances, are employed. In some cases, as with linen, the two pro- cesses are combined. The subject will be noticed under separate heads, depend- ing on the material operated on. I. Bleaching of Cotton. Cotton is more easily bleached, and appears to suffer less from th.e process, than most other textile substances. On the old plan it was first thoroughly washed in warm water to remove the weaver's paste or dressing; then bucked or "bowked" (boiled) in a weak alkaline lye, or in milk of lime, to remove colouring, fatty, and resinous matters insoluble in simple water ; and after being again well washed, was spread out upon the grass, or bleaching ground, and freely exposed to the joint action of light, air, and moisture (technically called " crofting"). The operation of " bucking" in an alkaline lye, washing, and exposure was repeated as often as necessary, when the goods were " soured" or immersed in water acidulated with sul- phuric acid, after which they received a final thorough washing in clean water, and were dried, .finished, and folded for the market. From the length of the exposure upon the bleaching-ground, this method is apt to injure the texture of the cloth ; and from the number of operations required is necessarily expensive and tedious. It is, therefore, now very generally superseded by the system of chemical bleach- ing, briefly described below. In the chemical system of bleaching, the goods are washed and " bucked" as on the old plan, then submitted to the action of a weak solution of BLEACHING. 9 chloride of lime, and afterwards passed through water soured with hydrochloric or sulphuric acid, and again thoroughly washed, then dried and finished. The aim of the old as well as the new process is to remove with the smallest amount of risk to the goods and at the lowest cost, as well as in the shortest time, the natural as well as the acquired impurities of the cotton. The nature of the former, which amount to only about i per cent., has been carefully studied by Dr. SCHUNCK, and they have been found by him to consist of fatty and waxy matters, brownish colouring substances, pectic acid, and albuminous matter. The acquired impuri- ties consist of all those foreign matters obtained either accidentally or intentionally during the process of manu- facture. Their amount varies enormously, often exceeding 30 per cent. They consist of the various matters, organic and inorganic, introduced during the sizing of the warps, such as china clay, magnesium chloride, zinc chloride, starch or flour, grease from the size, the machinery, and the hands of the workmen, and dust and dirt of all kinds. The new or continuous process, before referred to, is the method of chemical bleaching at present inmost general use; and, indeed, it has nearly superseded all other methods. In this system, the pieces previously tacked together endwise, so as to form a chain, are drawn by the motion of rollers in any direction, and any number of times through every solution to the action of which it is desired to expose them ; being at the same time entirely and completely under the control of the operator. Annexed is an outline of the several operations in the improved form of the continuous process as practised by Messrs. McNAUGHTON, BARTON & THOM, at Chorley, and in most other large bleach- works. i. Preliminary Operations:- a. The "pieces" are separately stamped to enable the bleacher to distinguish 10 BLEACHING, DYEING, ETC. between different lots of cloth, and to detect faults. The goods in the grey state are marked by any colour (usually black), which will sufficiently resist the bleaching process. Among the marking materials which are commonly employed, are gas-tar, pretty thick, alone or mixed with lamp-black ; a solution of nitrate of silver, boiled oils coloured with red lead or lamp-black ; and aniline black ; but this latter has many objections, such as a tendency to produce holes. In iinen bleaching, each piece is marked with letters made by red thread, which is found to stand the bleach better than any of the above agents. b. They are tacked together endwise, either by hand or a machine, so as to form one continuous piece of 300 to 350 yards in length, according to the weight of the cloth. c. The next operation is singeing, the object of which is to remove all the fine loose down from the surface of the cloth. This is accomplished either by passing the goods rapidly over revolving hot cylinders, by hot plate, by coke flame, or by gas flame. The plan most generally adopted is by the gas machine, invented by TALPIN, and improved "upon by Messrs. MATHER & PL ATT. d. i . After the singeing, the goods are washed ; either before or after washing, they are crushed into a rope-like form by drawing them through a smooth aperture, the surface of which is generally of glass or porcelain, the rope- form being given them to enable the water and other liquids to penetrate the goods more easily, and to allow them to be laid in loose coils in the kiers. ^ 2. The following process requires to be modified slightly, if a market bleach or madder-bleach is desired ; the latter is the name given by bleachers when the goods are required as white as possible, the former if the goods are to be sold in a white state, and not printed before going into the market. The goods are run through milk of lime, contained in the BLEACHING. 11 "linieing machine," direct into the kier, where they are bucked or boiled under pressure from twelve to fourteen hours, followed by rinsing or cleansing in the washing- machine. 3. They are soured in water acidulated with hydrochloric acid ; this process is known as the " lime sour" or " grey sour," after which they are again washed by the washing- machines. 4. They are now bucked or boiled for fifteen or sixteen hours in a solution of resinate of soda, and then washed as before. In some works they give the goods a light boil with soda ash, free from caustic, after the resin boil ; this is to remove any risk of resin remaining in the cloth. 5. They are chemicked by being laid in a wooden, stone, or slate cistern, when a solution of chloride of lime is pumped over them, so as to run through the goods into a vessel below, from which it is returned on them by continued pumping, so that the cloth lies in it for one or two hours. This operation requires great care, particularly in the preparation of the chloride of lime solution ; as Mr. F. HODGES, jun., has shown that if the smallest particle of undissolved bleaching powder is allowed to come into contact with the cloth it is liable to produce holes. The goods are again washed. 6. They are bucked or boiled for four or five hours in a solution of i Ib. of crystallized carbonate of soda, dis- solved in 5 gallons of water, to every 35 Ibs. of cloth, and washed. 7. They are again " chemicked" as before, and washed. 8. They are soured in very dilute hydrochloric acid, and then left on stillages for five or six hours. 9. They are finally thoroughly washed, well squeezed between rollers, dried over steam heated tin cylinders, starched or dressed, and finished. This is the usual process for good calicoes. Muslins, and other light goods, are 12 BLEACHING, DYEING, ETC. handled rather more carefully ; whilst for commoner goods the sixth and seventh operations are generally omitted. The entire process usually occupies five days ; but by using Mr. BARLOW'S high pressure steam-kiers it may be performed in two. PENDLEBURY'S kier, which is not unlike BARLOW'S, is generally used when working on a small scale. Yarns, as they contain a smaller percentage of artificial impurities than cloth, are bleached in a somewhat different manner. The skeins are first looped together, after which they are boiled in open kiers in soda lye, then in water, washed, chemicked, washed, soured and washed. According to the most reliable authorities, the strength of cotton fibre is not impaired by its being boiled for two hours in milk of lime, under ordinary pressure, out of con- tact with the air ; nor, according to the bleachers, even by sixteen hours, boiling at the strength of 40 Ibs. per 100 gallons. It is said that lime is less injurious than soda. Solution of caustic soda, sp. gr. 1*030, does not injure it, even by boiling under high pressure ; but, in practice, soda- ash, or carbonate of soda, is used, and this is only" in the second bucking, and in the third, if there be one. The strength now never exceeds 25 Ibs. of the crystals to the 100 gallons, and is usually less. Experiments have shown that immersion for eight hours in a solution of chloride of lime,* containing 3 Ibs. to the 100 gallons, followed by souring in sulphuric acid of the sp. gr. 1*067, * Since the introduction of bleaching powder many chemicals have been proposed as a substitute for this bleaching agent, but up to the present not one of them has met with any but a partial success. Among those brought before the public may be mentioned perman- ganate ; chlorozone, obtained by passing a mixed current of hypo- chlorous acid and air through a solution of caustic soda, this compound being considered by some to bleach better than the hypochlorites, the action of which in bleaching it resembles ; chloro- chromic acid, the chlorates, and peroxide of hydrogen. Perhaps the BLEACHING. 13 or for eighteen hours in acid of 1*035, does not injure it. By the improved method of previously treating the goods with lime or alkalies, little chloride of lime is required. Indeed, it is said that where 300 Ibs. were formerly em- ployed, 30 to 40 Ibs. only are now used. At the same time it is right to mention, that though a solution at ^ Twaddle is usually regarded as the best and safest strength, yet in some bleach works, particularly for inferior and less tender goods, this is greatly increased, even up to 5, the period of immersion being proportionally reduced, as it is not safe to expose the goods long to the action of such powerful solutions. With the higher strengths they are passed rapidly through the liquid with the callender, sufficient time only being allowed to soak them thoroughly, then immediately through the acid or souring, followed by washing as before. 2. Bleaching of Linen. Linen may be bleached in a similar way to " cotton," but the process is much more troublesome and tedious, owing to its greater affinity for the -1 colouring matter existing in it in the raw state. Under the old system several alternate buckings . with pearlash or pot- ash and lengthened exposure on the field, with one or two sourings, and a final scrubbing with a strong lather of soft soap, constituted the chief details of the process. In this way a high degree of whiteness, though not an absolutely pure or snow white, was ultimately produced. Grass- bleaching or crofting is still extensively used for linen ; but most novel plan proposed as a substitute for the chemickhig, is that invented by ENGLER, who bleaches with the vapours of chloroform, generated by means of a mixture of quicklime, chloride of lime, alcohol or acetic acid, sulphuric acid, and water. In Scotland and Ireland the washing is generally performed by wash- stocks, whilst in Lancashire dash-wheels or washing-machines with squeezers are almost always used for the purpose. Cotton loses about i-2oth of its weigh by bleaching. 14 BLEACHING, DYEING, ETC. it is more generally employed only for a limited time, and in combination with a modification of tlie system at present almost universally adopted for cotton goods ; whilst in some cases crofting is omitted altogether, and the bleaching con- ducted wholly by the latter process. Linen goods are bleached either in the form of yarn, thread or cloth. The following Tables exhibit the outlines of the new method as at present practised in Ireland and Scotland for linen bleaching. Table No. I. is that which is given as suitable for a parcel of light linens, by a well-known proprietor of an Irish bleach works, at a time when the now but little used fermentation process was in favour. No. II. is the outlines of the new system at present practised in Ireland and Scot- land for plain sheetings. TABLE No. I. 1. Steep for 24 hours, wash 15 minutes ; time 2 days. 2. Boil for 7 hours in lye and resin 2^, wash 15 minutes ; time 2 days. 3. Boil for 9 hours in lye 2-J, wash 30 minutes ; time i day. 4. Grass for 3 days ; time 3 days. 5. Boil for 10 hours in lye 3, wash 30 minutes; time i day. 6. Grass for 3 days; time 3 days. 7. Boil for 8 hours in lye 3, wash 30 minutes ; time i clay. 8. Grass for 3 days ; time 3 days. 9. Rough sour for 10 hours in vitriol 2,Vash 40 minutes ; time i day. 10. Scald for 4 hours in weak lye, wash 30 minutes ; time i day. n. Grass for 2 days ; time 2 days. BLEACHING. 15 12. Dip for 10 hours in alkali 40 to i strength, wash 30 minutes ; time i day. 13. Sour for 12 hours in vitriol ij, wash 45 minutes; time i day. 14. Scald for 4 hours in lye and soap, wash 20 minutes ; time i day. 15. Rub withbrowii soap, wash 35 minutes; time i day. 1 6. Grass for 2 days; time 2 days. 17. Dip for 10 hours in alkali 30 to i strength, wash 20 minutes; time i day. 1 8. Sour for 12 hours in vitriol i, wash 45 minutes; time i day. 19. Scald for 3 hours in soap and lye, wash 30 minutes ; time i day. 20. Dip for 10 hours in alkali 45 to i strength, wash ?o minutes; time i day. 21. Sour for 12 hours in vitriol i, wash 45 minutes; time i day. 22. Rub with soap. Time taken 3 1 days. The goods should now be white and ready for finishing. TABLE No. II. For plain sheetings : 1 . They are bucked for 12 or 1 5 hours in a lye made with about i Ib. of pearlash (or soda-ash) to every 56 Ibs. of cloth, and washed. 2 . Crofted for about 2 days. 3. Bucked in milk of lime. 4. Turned, and the bucking continued, some fresh lime and water being added, and washed. 5. Soured in dilute sulphuric acid at 2 Twaddle. 6. Bucked with soda-ash for about 10 hours, and washed. 7. Crofted, as before. 1 6 BLEACHING, DYEING, ETC. 8. Bucked again with soda-ash, as before. 9. Crofted for about 3 days. 10. Examined, the white ones taken out, and the others again bucked and crofted. T i . Scalded or simmered in a lye of soda-ash of about only 2-3rds the former strength, and washed. 12. Chemicked, for 2 hours, at J Twaddle, washed, and scalded. 13. Again chemicked, as before. 14. Soured for 4 hours, as in No. 5 ; washed, and finished. This occupies 13 to 15 days, according to the weather. b. For shirtings, &c. : As the preceding, but with some- what weaker solutions. c. For goods to be subsequently printed : 1. Bucked in milk of lime for 10 or 12 hours. 2. Soured in dilute hydrochloric acid of 2 Twaddle, for 3 to 5 hours, and washed. 3. Bucked with resinate of soda for about 12 hours. 4. Goods turned, reboiled as before, and washed] 5. Chemicked at | Twaddle, for 4 hours. 6. Soured at 2 Twaddle, for 2 hours, and washed. 7. Bucked with soda-ash for about 10 hours, and washed. 8. Chemicked as in No. 5. 9. Soured, as at No. 6, for 3 hours ; washed, and dried.* The chief difficulty in bleaching linen arises from the fact that it contains a much larger proportion of natural impurities than cotton. To thoroughly understand the nature of these impurities it would be necessary to study the various processes through which the flax plant passes before being manufactured into linen, this our space will * The strengths of the solutions, when not otherwise stated, are about the same as those given under Cotton. BLEACHING. 17 not permit ; it will be sufficient to mention that after the retting process, which Professor HODGES has shown removes from the fibre up wards of 41 'i per cent, of the nitrogenized and other constituents of the plant, there are to be seen numerous brilliant scales of a resinous appearance and light amber hue which are deepened in colour by alkalies, in which also they can be entirely dissolved. The nature of these scales is not as yet clearly understood. The consti- tuents of dressed and undressed flax have been carefully studied by HODGES, sen., and HODGES, jun. ; to the investi- gations of the former we are principally indebted for infor- mation as to the nature of these bodies. HODGES, sen., upwards of thirty years ago, gave not only analyses of the gases evolved in the steeping process, but investigated the nature of the constituents of dressed flax, showing that the latter consisted of wax,volatile oil and acid resinous matter, sugar and colouring matters, gum, pectin, nitrogenized compounds, inorganic matters and cellular fibre. HODGES, jun., has lately thoroughly investigated the nature and chemical constitution of these bodies, and finds that the wax is a complex body closely resembling in composition palmitic ceryl ether. To remove these impurities, and to produce a pure white cellulose, is the object of all the bleaching processes described ; the machinery which is used to accomplish this in linen bleaching differs greatly from that used by the cotton bleacher. Space will not permit us to enter fully into a description, but the following sketch may be serviceable to those unacquainted with this part of the subject. WASH MILLS. These machines which are used in Ireland for washing linen are there called wash mill feet or stocks. They are made by suspending from a strong frame two large blocks of wood, weighing about 534 Ibs. each ; by means of the water supply, these blocks are made to rise c 1 8 BLEA CHING, D YE ING, E TC. and fall alternately, in this way the goods are first soaked with water and then squeezed free from it. Though the appearance of these machines is far from ornamental, yet they have been found to work more satisfactorily than any other plan. The dash- wheel is a cylindrical box revolving upon its axis, and divided into four compartments, these have openings into which two or more pieces are introduced ; Avater is admitted through the hollow axis and the wheel is set in motion, causing the goods to pass from side to side. Many other washing machines have been proposed, but as yet have met with only very partial success. RUBBING MACHINE. This machine is a special feature in linen bleaching. The object of the process called " rubbing" is to give the goods a thorough soaping, to neutralize any in- jurious acids or alkalies they may contain, and to remove the yellowish brown specks known as sprits. At the foot of this machine there is a trough containing a strong solution of soap kept constantly boiling by steam, the goods are first passed through this trough, then between two square flat pieces of wood or marble, toothed transversely. The upper piece is made to move lengthwise over the goods, which are pulled through by the drawing engine. A description of the yarn and linen drying and finishing machinery would be alto- gether out of place in a notice such as this, and we shall have to content ourselves with a short account of the .several chemical processes described, such as the Steep, the Boil, the Sour, the Scald, and the Dip. Linen goods con- tain about 33 per cent, of impurities, consisting of those before mentioned ; together with these it contains a dressing employed by the weaver, this dressing is used to make the linen smooth and cover bad work, and is made usually from flour in the form of paste ; but just as the cotton bleacher has to contend with a numerous list of articles used as a size or as dressing, so has the linen bleacher ; among those used by the BLEACHING. 19 linen weaver may be mentioned mashed potatoes allowed to sour, a mixture of glue, sago, and tallow boiled together, Irish moss, and soap. These are either used alone or mixed with numerous substances, such as chloride of calcium or mag- nesium, gum, glycerine, \vax, etc. The object of the steep or boil is to remove all these matters, arid the success of the bleach in great part depends upon whether this has been successfully accomplished. The now little used steeping process was carried out in a kieve or box made of wood, stone, or cement, containing water at a temperature of 120 to 150 Fahr. (49 to 65-5 C.), in which the goods were immersed from one to two days, and fermentation was promoted either by pipe clay, resin, bran, in- fusion of malt, or yeast. When the goods had been sufficiently long in the steep they were washed, and then boiled under pressure, first in old soda lye, then again washed and again boiled in lye cleaner than that at first used, yet not quite pure. The number of boils and their length depended not only on the class of goods to be bleached, but upon the ideas of the bleacher. Lime is now used in most of the Irish bleach- greens for boiling, and though some of the older bleachers do not care for it, yet for many classes of goods it has been found to produce a better result than soda lye for the first boils. It is most important that the goods after boiling in soda lye be not allowed to lie exposed to the air too long without being washed, as the carbonate of soda is apt to crystallize within the fibres, which are burst during the formation of the crystals. The loss of weight by the boiling in lime and caustic or carbonated alkalies, varies according to the class of yarn and its former treatment, from 14 to 37 per cent. The larger the number of boils the greater will be the quantity of the brownish colouring matter of the fibre which will be removed, and after a time the goods will only retain a light grey shade which is without difficulty removed c 2 20 BLEACHING, DYEING, ETC. by steeping in a weak solution of a hypochlorite ; care must, however, be taken that the hypochlorite be not used until the brownish colour has been removed, as it will be " set" or fastened by the hypochlorite. Steeping in a solution of a , hypochlorite is technically called the DIP. The hypochlorite principally used in Ireland for the dip, is for linen, hypo- chlorite of soda, commonly called chloride of soda ; this the bleacher usually makes for himself by adding to a clear solution of bleaching powder or hypochlorite of lime, a solution of soda ash or carbonate of soda, allowing the mix- ture to settle and drawing* off the clear solution, which is the chloride of soda. For yarns and threads the bleaching agents used are hypochlorites of lime or magnesia. THE SOUR. Souring consists in immersing the goods from four to eight hours in a bath of dilute sulphuric acid and then washing. It is called a rough sour if the goods are soured after coming from the grass and before they have had a dip. THE SCALD. Scalding is a light boil of from two to three hours in a clean and weak lye containing some soap, together with the soap left in the goods after the rubbing process. The above is an outline of the process and machinery at present employed in Ireland for linen bleaching, and with the excep- tion of the machinery, which has been greatly improved, little or no change has taken place in the method since the introduction of chlorine. Though many plans have been proposed to shorten the process by doing away with the grassing, none so far as linen is concerned have succeeded ; the latest and perhaps the most novel plan suggested is that lately patented by Messrs. J. J. DOBBIE & J. HUTCHESOX, who generate chlorine by the electrolysis of dilute hydro- chloric acid. Their process consists in steeping the cloth to be bleached in sea-water, and passing the fabric between a series of carbon rollers, the upper row of which is connected BLEACHING. 21 with one pole, the lower row with the other pole of a battery. The rollers are caused to rotate slowly, and thus pass the fabric from one end to the other. Hypochlorite is formed, and on subsequent immersion in acid the fabric is effectually bleached. For yarn and thread bleaching the process which has been found most successful is that of HODGES, jun., which is known in Ireland as the " Chemico-Mechamcal Process," so called from the patentee turning to account the advantages derivable from the employment of mechanical contrivances driven by steam, combined with the introduction of a new method of obtaining the hitherto little used hypochlorite of magnesia. This process may be said to date from the discovery of the substance known as Kieserite (native sulphate of magnesia), which occurs as an essential constituent of the Abraum salts of Stassfurt. For some time after the introduction of this substance into the market, it was considered of little value except for the production of Epsom salts ; but Mr. HODGES, in the course of some investigations in bleaching jute, having had occasion to employ large quantities of hypo- chlorite of magnesia, it occurred to him that kieserite might be substituted for the more expensive crude sulphate of magnesia ; and the importation into Ireland of the sample for this purpose, was the first that was ever sent into that country for the manufacture of a bleaching liquor, or, in- deed, for any other use. Mr. HODGES, on experimenting with the kieserite, found that it not only supplied the place of the crude sulphate, but acted as a better precipitant for the lime of the bleaching powder, which is employed in the production of the hypochlorite of magnesia; and that it also produced a stronger and clearer solution. Without entering into a minute description of the process, the fol- lowing outline will be sufficient to show the nature of the methods adopted. The kieserite, which is imported from 22 BLEACHING, DYEING, ETC. Germany in square blocks, on arriving at the works, is conveyed to a house, on the ground-floor of which it is stacked until required, when it is ground to a fine powder, placed in barrels, and drawn up by means of a crane to a room at the top of the building, at one end of which is a row of three tanks furnished with water taps, agitators, and false bottoms. In one of the end tanks a definite quantity of the kieserite powder (varying according to its strength, ascertained by analysis) is placed and dissolved in a given quantity of water, the solution being assisted by agitators, and on settling, the clear liquor is siphoned over into the middle tank. In the third tank, bleaching powder (hypochlorite of lime), varying in quantity according to the strength of the kieserite solution, is placed. The bleaching powder after being agitated with water is allowed to settle, and the clear solution is siphoned over into the middle tank containing the clear kieserite solution, the agitator being kept in motion, not only during the mixing of the liquids, but for some time after. The mixed liquids are then allowed to remain undisturbed all night, after which the clear hypo- chlorite of magnesia solution is siphoned into a large settling tank, which is situated in the room below. From this vessel it is conducted through wooden pipes (which are so contrived that they can be opened and cleansed at will), into a large cistern standing in the bleaching-house. This cistern is fitted with a ball-cock, by which arrangement the liquid can be drawn off by a system of wooden pipes as re- quired. The bleaching-house in which the cistern is situa- ted is fitted up in an original manner, and covers something more than an acre of ground; whilst the reeling-shed, which is the only part of the works our limits will permit us to describe, is 240 feet long by 24 feet broad, and con- tains ten steeps and twelve reel boxes. Each box is pro- vided with water, a solution of the bleaching agent, and BLEACHING. 23 steam pipes, and is capable of reeling at a time about 500 Ibs. of yarn. Above the box is. a line of rails on pillars. A travelling crane runs along the rails, and carries the reels from one box to another. Attached to this crane is a newly invented hydraulic pump, by means of which the reels with the yarn on them can be lifted in a few seconds from one box to another. After the yarn has been boiled,washed, and passed through the squeezers in the usual manner, it is put on a waggon, in which it is carried, by means of a line of rails, clown to the first reel box. Here it is placed 011 the reels, which are made to revolve by means of steam first in one direc- tion and then in another, through a solution of carbonate of soda, previously heated by means of the steam-pipes before mentioned. The yarn having been sufficiently scalded and so saturated with soda, the reels to which it is attached are raised by the hydraulic pump out of the box, and the yarn allowed to drain for a few minutes, after which the travel- ling crane carries it on to the next box. Into this box the yarn is again lowered by the pump and made to revolve as before, but this time through a solution of the bleaching agent, which immediately re-acting 011 the carbonate of soda with which the yarn is charged, renders this bleaching agent free from the danger which attends the employment of chlorine, or the ordinary bleaching powder used in the older methods of bleaching. After the yarns have been brought to the desired shade in the solution of HODGES' bleaching agent, they are either removed as before to a new box, and there washed before being soured, or they are thrown into one of the steeps filled with water for the night. These operations are repeated with weaker solutions in the remaining reel boxes, either once or twice according to the shade required. Mr. HODGES claims as the chief features of his invention, UNIVERSITY 24 BLEACHING, DYEING, ETC. that it consists, first, in the employment of a bleaching agent which has not hitherto been practically employed, and a cheap method for its production ; second, in the pre- paration of the yarn prior to its being submitted to the action of the bleaching agent, this preparation setting free not only the imprisoned chlorine of the hypochlorite, but also another powerful bleaching agent, oxygen; third, in new and improved machinery, by which the work of bleaching the yarn is greatly shortened ; fourth, in doing away with the tedious and expensive operation of exposing the yarn on the grass. If this last were the only feature in Mr. HODGES' invention, the patentee would have greatly im- proved the process of bleaching ; not only, however, does the new process supplant the old long and tedious one, but a great economy of time is additionally gained in other parts of the process ; added to these advantages it is stated that a superior finish is given to the yarns, and that in conse- quence a much greater demand for them has arisen. Mr. HODGES contends that the absence of caustic lime from his new bleaching compound gives it great "advan- tages over the old bleaching powder, particularly in its application to finely woven fabrics, such as muslins, 3 " Mix well and strain. 5. MADDER PURPLE (dark). Water 10 gallons. Iron liquor, at 24 Twaddle . . ij Purple fixing liquor (No. i ) . . 2 pints. Fine flour 1 5 \ Ibs. Thoroughly incorporate and boil as madder black. CALICO-PRINTING. 97 6. MADDER PURPLE (medium). Water 14 gallons. Iron liquor, at 24 Twaddle . . i| Purple fixing liquor (No. i ) . . 12 pints. Fine flour 18 Ibs. Treat as dark madder purple. 7. MADDER PURPLE (light). Gum water (farina dark) ... 9 gallons. Iron liquor, 24 Twaddle ... i quart. Purple fixing liquor .... 4 pints. 8. STANDARD BROWN. Water 50 gallons. Catechu 200 Ibs. Boil for six hours ; then add Acetic acid 4^ gallons. Water to make up 50 ,, Let the whole stand for two days and decant ; after heating this to 130 Fahr. (54*4 Cent.) add Sal ammoniac 96 Ibs. Dissolve, and let it stand for forty-eight hours. Decant, and to the clear liquid, add gum Senegal in the proportion of 4 Ibs. to the gallon. 9. BROWN. For Machine Work. Standard Brown (No. 8) . . . 4 gallons. Acetate of copper* -J ,, * The acetate of copper is prepared as follows : Sulphate of copper 4 Ibs. Lead acetate 4 Ibs. Hot water i gallon. Dissolve, let settle, and dilute the clear liquid to 16 Twaddle with water. n 98 BLEACHING, DYEING, ETC. Acetic acid 2 quarts. Gum Senegal water (4 Ibs. to the gallon) 2 10. MEDIUM BROWN. No. 9 2 gallons. Gum water 2 Acetate of copper i gill. 11. MADDER BROWN TO RESIST HEAVY COVERS OF PURPLE. Catechu Jib. Sal ammoniac \ Ib. Lime-juice at 8 Twaddle . . . i quart. Nitrate of copper at 80 Twaddle 2\ oz. Acetate of copper ij Gum Senegal . .' i Ib. 12. CHOCOLATE. For Machine Work (dark). Iron liquor at 12 Twaddle . . 3 gallons. Red at 1 2 Twaddle . . 9 Flour 24 Ibs. Oil i pint. Mix. 13. CHOCOLATE (redder). Iron liquor at 1 2 Twaddle . . i gallon. Red at 1 2 Twaddle .... 6 Flour 14 Ibs. Oil i gill. Mix. 14. DRAB. For Machine Work. Standard No. 8 4 gallons. Protochloride of iron at 84 Twaddle 2 pints. CALICO-PRINTING. 99 Solution of acetate of copper . 2<| pints. Gum water substitute (4 Ibs. to the gallon) i gallon. 15. FARINA GUM WATER (dark). Water 5 gallons. Dark coloured farina . . . .30 Ibs. Boil well together. 1 6. FAWNS. These may be produced by reducing the drab of formula 14 with gum water to suit shade required. 17. No. 20 PADDING PURPLE. Water 18 gallons. Purple fixing liquor .... 2 Iron liquor at 24 Twaddle . . i Logwood liquor at 4 Twaddle . | Flour (boiled as usual) . . .24 Ibs. P.S. If a gum colour is required instead of a paste one, as the above is, then take 18 gallons of gum water (dark farina), instead of the water, and keep out the flour. Of course avoid boiling. 1 8. DARK RED. For Machine Work. Red liquor,* 9 to 10 Twaddle, but not to exceed 12 Twaddle 6 gallons. Flour . 12 Ibs. * The red liquor of commerce which is always used for dark reds (but not for pinks) is generally made by the manufacturing chemist, from crude acetate of lime and alum cake, and afterwards freed from iron with ferrocyanide of potassium. H 2 ioo BLEACHING, DYEING, ETC. 19. STANDARD RED LIQUOR. Alum 20 Ibs. White sugar of lead . . . . i2-J Boiling water 5 gallons. Stir until dissolved, let the mixture settle, and decant. 20. PALE BED. For Machine Work. Standard red liquor, No. 19 . i gallon. Gum substitute water (30 Ibs. gum substitute in i o gallons of water) 3 gallons. 21. RED RESIST (dark). For Machine Work. Hesist red liquor at 18 Twaddle 12 gallons. Flour 24 Ibs. Boil well, and when nearly cold, add Tin crystals 12 ,, Used as a resist for a chocolate colour. 22. RESIST RED LIQUOR. Acetate of lime liquor at 24 Twaddle 90 gallons. Sulphate of alumina . . . .272 Ibs. Ground chalk 34 22 a. RESIST RED LIQUOR. Water i gallon. Alum 5 Ibs. Acetate of lead 2 J Soda crystals \ 23. RESIST (dark red). For Machine Work. Resist red liquor at 1 8 Twaddle 6 gallons Flour 12 Ibs. Treat as in No. 21, and add Tin crystals 3 This is used as a resist for a purple colour. CALICO-PRINTING. 101 MORDANTS, DISCHARGES, RESERVES, COVERS, &c. 1. ALKALINE RED MORDANT. Potash Alum 10 Ibs. Boiling "Water 5 gallons. Dissolve and add Soda lye at 70 Twaddle. . . f Make up to 12 gallons with cold water, let the precipi- tate settle, then wash it by decantation till the washings are tasteless. Filter, remove the precipitate from the filter, and dissolve it in 5 pints of soda lye at 70 Twaddle. Boil, make up to 3 gallons with water ; stir in 9 Ibs. of dark gum substitute, and finally boil again. 2. LIGHT RED ALKALINE MORDANT. Alkaline red mordant, No. i . . i gallon. Dark gum substitute water . . 9 Ibs. 3. ALKALINE PINK MORDANT. Potash lye at 54 Twaddle ... 40 gallons. Sulphate of alumina (patent or cake-alum) 140 Ibs. Heat the lye in an iron boiler, and add the sulphate of alumina gradually, frequently stirring. The above pro- portions yield about 45 gallons at 34 Twaddle. It is to be thickened with dark gum substitute. 4. ALKALINE LIGHT PINK MORDANT. Potash lye at 41 Twaddle , .25 gallons. Potash alum 90 Ibs. Dissolve as in No. 3. 102 BLEACHING, DYEING, ETC. 5. "Acic" (LIME-JUICE MIXTURE). Lime-juice at 8 to 16 Twaddle i gallon. Starch i Ib. Boil, keeping it stirred till the starch is dissolved. 6. "AciD." Lime-juice at 20 Twaddle . . i gallon. Starch i Ib. 7. a Acnx" Lime-juice at 30 Twaddle . . i gallon. Starch i Ib. These acids are sometimes thickened with gum substitute. 8. ACID DISCHARGE. Lime-juice at 22 Twaddle . . i gallon. Bisulphate of potash . . . i Ib. Decant the clear liquor, filter, and thicken with. Starch i Ib. 9. ACID DISCHARGE. Lime-juice at 28 Twaddle . . i gallon. Bisulphate of potash ... 2 Ibs. Decant and filter the clear liquor, and thicken with Dark British gum .... 5 Ibs. 10. GALL LIQUOR. Gall nuts, ground 28 Ibs. Acetic acid 2 gallons. Water 12 Let stand for two days, with occasional stirring, and then filter. CALICO-PRINTING. 103 1 1 . BUFF STANDARD. Water 2 gallons. Copperas 10 Ibs. Brown acetate lead 2j White 1-1 12. ANOTHER BUFF. Water 5 gallons. Copperas 20 Ibs. Brown sugar lead 10 Dissolve, and let settle, decant the clear liquid, and reduce it to the desired shade with gum Senegal water. 13. SULPHATE OF CHROME STANDARD. Water 6 gallons. Bichromate of potash . . . .24 Ibs. Dissolve by means of heat, and place in a pan made of stoneware ; then add Sulphuric acid, at 170 Twaddle 6J pints. Cold water 3 gallons. Then gradually add Sugar 6 Ibs. When the violent reaction and frothing cease, boil down to 3 gallons. 14. CHLORIDE OF CHROME STANDARD. Bichromate of potash .... 8 Ibs. Boiling water 2 gallons. Dissolve, and add Hydrochloric acid, at 32 Twaddle, i gallon 3^ pints. Then add gradually Sugar 3^ Ibs. 104 BLEACHING, DYEING, ETC. 15. ARSENIATE OF CHROME STANDARD. Bichromate of potash . . . .10 Ibs. Arsenious acid 14 Hydrochloric acid, at 3 2 Twaddle 1 4 pints. Water . . , 2 gallons. Heat the mixture until the liquid becomes of a pure green colour, without an olive tint. Sometimes, to obtain this result, more acid has to be used. When the reduction is completed, the liquid must be concentrated to 95 Twaddle. Care is necessary in the preparation of the chrome standards ; should they not be perfectly uniform and smooth, they must be reheated, and more acid added if requisite. The best thickener for them is tragacanth gum. Under Style 2, Reserves, will be found a variety of colours. 1 6. FAST BLUE STANDARD. Ground-wet indigo .... 8 Ibs. Soda lye at 70 Twaddle . . . ij gallons. Water i Feathered tin an excess. Boil in an iron pan until a few drops placed 011 a piece of window glass appear perfectly yellow. 17. FAST BLUE FOR BLOCK WORK. Fast blue Standard liquid (No. 1 6) i quart. Tin crystals 12 ounces. Lime-juice, at 60 Fahr.(i5'5C.) 12 Gum Senegal water (6 Ibs. to the gallon) 3 quarts. 1 8. FAST GREEN. Fast blue Standard liquid (No. 1 6) 2 1 pints. Lead gum (see No. 19) . . . 2 quarts. Tin crystals 8 ounces. CALICO-PRINTING. 105 19. LEAD GUM. White sugar of lead .... 8 Ibs. Nitrate of lead 4 Hot water i gallon. Gum Senegal water (6 Ibs. to the gallon) i 20. DRAB. Sulphate of chrome, Standard No. 13 5 quarts. Gum tragacanth water (J Ib. to the gallon) 10 Cochineal liquor, at 4 Twaddle i| pints. Bark liquor, at 8 Twaddle . . i| 21. FAWN. Sulphate of chrome, Standard No. 13 i gallon. Gum tragacanth water ?(J Ib. to the gallon) 2 Brown standard, No. 5 ... \ gallon. 22. PALE SAGE. Sulphate of chrome, Standard No. 13 i gallon. Gum tragacanth water (| Ib. to the gallon) i 3. Garancine Style. Most of the styles that can be carried out with madder can also be worked with garanciiie, but with this latter the resulting colours are generally not so clear. As a rule they are fuller, but less transparent, even when they have been equally well soaped and treated in the same manner after dyeing as the madders. The dis- covery and introduction of garancine was a great boon to io6 BLEACHING, DYEING, ETC. the calico-printer, since it not only enabled him to produce beautiful fast reds, purples, and other colours, cheaper than by the use of madder alone, but also chocolates, blacks, browns, drabs, &c., in conjunction with reds results he was unable to get with madder. Furthermore, garancine and garanceux, can be used with peach-wood, yellow-wood, and Persian berry extract, and thus produce a fast print with red, yellow, brown, drab, chocolate, and black in combination ; effects which can only be obtained with considerable diffi- culty and expense by the use of the madder-bath. Garancines thus dyed are scarcely so fast as madder colours, nor will they tolerate soaping, but this operation is not so necessary as with madder dyed fabrics, for two reasons. In the first place the colours as they come out of the beck are generally brighter ; and in the second, the whites or grounds are less tinged with the dye. The bright- ening of the colours and the clearing of the whites are effected by merely passing the dyed goods through what is called the " chlor" machine, or " chemicking" them. The " chlor" apparatus is a simple padding machine, immediately behind which is fixed a steam-box or iron chest, fitted with five copper rollers, and two perforated steam-pipes, also of copper. The trough of the padding machine contains solu- tion of chloride of lime at from J to i Twaddle. The goods are passed through the trough and padding machine, and then immediately carried through a small aperture into the steam-box, and over and under the copper rollers ; after which they pass through another aperture situated on the opposite side of the box, jets of steam being projected upon them during their passage. As they leave the steam-box, the pieces fall into a cistern of water, and then pass on to the squeezers. They are afterwards dried and finished. From tin's it will be seen that the processes for dyeing and cleansing garancined goods are simpler and less expen- CALICO-PRINTING. 107 sive than those followed in madder dyeing. Garancine mordants also for reds, pinks, purples, and chocolates are used in a more dilute form than those for madder. The same care, however, in drying the aluminous mor- dants after printing, is as necessary for garancine as for madder goods. Formula for a dyed garancine print composed of black, red, brown, and drab, ivith chocolate ground. BLACK. Same as IsTo. 3, page 95. RED. Same as JSTo. 18, page 99. BROWN. Same as JSTo. 8, page 97. CHOCOLATE. Same as No. 13, page 98. DRAB. Same as No. 14, page 98. 4. Padding Style. This style, as formerly practised, is now little used, being mostly confined to producing mourning effects, such as black and white, and black and lavender. The mordants employed in this style are the acetates of alumina and iron, the former giving with madder, garancine or alizarin reds ; the latter, browns or blacks with log- wood, and purples with madder and garancine. By mixing the two mordants, and separately using for the tinctorial correspondents, logwood, quercitron bark, sumach and peach- wood, all the colours from clarets to olive can be obtained. The goods are dunged as for madders or garancines, and dyed and cleared mostly as garancines. 5. Indigo Style. For Formula?, see pages 89-90. 6. China Blue Style. For Formulas, see page 90. 7. Indigo Discharge Style. The goods are dyed plain indigo, then soured, washed, dried, and afterwards printed. This very beautiful and permanent style, as more particularly exemplified in its chintz form, is of comparatively recent date. Instead of printing a reserve as in Style 5, and loS BLEACHING, DYEING, ETC. afterwards dyeing and preparing, and finally blocking in the desired illuminating colours by block printing, the goods are first dyed (technically termed " dipped") plain, and afterwards printed with such compounds as discharge the indigo and leave the desired colours in the discharged parts. The application of chromic acid as the discharging agent used for this purpose, was first proposed by Mr. MERCER. The goods, after being dyed indigo and dried for printing, are previously padded through a solution, consisting of 8 to 1 2 oz. of bichromate of potash in a gallon of water, dried through a hot-air stove and excluded from light. They are then printed with a solution of oxalic and sulphuric acids, thickened with coloured starch (known to the calico-printer as "dark British gum"). After this, they are dried for printing in the usual way. They are then washed in water, drained, and again dried. There are other methods of conducting this process, but they are impracticable and more costly. We are indebted for the annexed formulae, to Mr. JAMES CHADWICK of the firm of Messrs. CHADDERTON, CHADWICK & Co., of Manchester, who assures us their em- ployment will be attended with complete success. The colours obtained by these formulas, not only the white, but also yellow, orange, red, green, and, in short, almost all compound colours occurring as pigments, may be fixed. We may further state that this interesting style requires the observance of the two conditions of chemical and mechanical printing or fixing, to ensure the desired results, for whilst in the colours printed the chromic acid necessary for the discharge of the indigo must be present, they must also contain the coagulurns or agglutinants necessary to fix the pigments, consequently it is necessary that the chromic acid and colour compounds should be as nearly as possible neutral. After the goods are printed they are passed through the padding machine, before which is fixed a box containing five CALICO-PRINTING. 109 copper rollers, three at bottom and two at top. The fabric passes over and under these rollers, and then immediately after, through the padding machine, which causes the greater part of the solution with which the box and padding machine have been charged, to be squeezed out. The solution is com- posed of sulphuric acid at 12 Twaddle, containing in each gallon 8 oz. of oxalic acid. The temperature at w T hich the solu- tion must be maintained during the passage of the goods should be from 110 to 120 Fahr. (43 to 49 C.). After the goods or the piece passes from the padding machine, it should pass over one or two rollers so as to allow the gas to escape before the piece falls down in folds. At the expiration of a minute or two, the piece passes into the washing machine, and is lastly washed, dried and finished. i. WHITE DISCHARGE FOR INDIGOES. Water 2 gallons. Bichromate of potash .... 3 Ibs. Dissolve, Dark British gum 5 to 6 Ibs. Boil and work hot. 2 a. OXALATE AND CHROMATE STANDARD. Blood albumen solution (6 Ibs. per gallon) 2 gallons. Neutral chromate of potash . . 8 Ibs. Neutral oxalate of potash . . if Dissolve perfectly cold ; strain. 1. ORANGE FOR INDIGO DISCHARGE STYLE. Orange pigment i quart. Oxalate and chromate standard .2 ,, Mix thoroughly and strain. 2. YELLOW DITTO. Yellow pigment i quart. I io BLEACHING, DYEING, ETC. Oxalate and chrbmate standard . i J quarts. Albumen thickening (6 Ibs. per gallon) 1 Mix thoroughly and strain. 3. GREEN DITTO. Pigment green 4 quarts. Oxalate and chromate standard . 4 Mix thoroughly and strain. 4. RED DITTO. Vermilion powder 8 Ibs. Oxalate and chromate standard . 4 quarts. Mix till thoroughly incorporated, and afterwards strain well. 5. BUFF (CHAMOIS). Orange pigment 2 quarts. Albumen thickening (6 Ibs. per gallon) 12 Oxalate and chromate standard .6 Mix thoroughly and strain. 6. OLIVE DITTO. Olive pigment 3 quarts. Oxalate and chromate standard .6 Mix thoroughly. 7. BROWN DITTO. Brown pigments 4 quarts. Oxalate and chromate standard .8 Mix thoroughly and strain. 8. LIGHT OLIVE DITTO. Olive pigment ij quarts. Oxalate and chromate standard . 4^- Mix thoroughly and strain. CALICO-PRINTING. in 9. LIGHT BROWN DITTO. Pigment brown 2 quarts. Oxalate and chromate standard .6 Albumen thickening ( 6 Ibs. per gallon) 2 Mix thoroughly and strain. 10. SALMON, OR FLESH COLOUR, DITTO. Vermilion 4 Ibs. Pigment brown i quart. Oxalate and chromate standard .5 Mix thoroughly and strain. n. BLUE, DITTO (Light Blue.) Neutral Prussian blue paste . . 2 quarts. Oxalate and chromate standard .4 Mix thoroughly and strain. N.B. The broAvn and olive pigments are those usually sold for printing purposes. They are ground in water only, and must be perfectly neutral and insoluble. The ordinary green, is a borate of chromium. Any pigment colour may be used that does not coagulate the albumen, which is mixed with it, and which will withstand the action of the sulphuric and oxalic acids when developing the design. 8. Steam Style. FOR COTTON, AND COTTON AND WOOL. (MIXED GOODS.) Preparation (before printing). If the fabric consist of cotton only, the goods after being bleached and dried, are padded through a machine charged with stannate of sodium at 12 Twaddle, then immediately through sulphuric acid at 1 1 to 2 Twaddle. This precipitates upon the fabric the tin oxide, which then becomes the mordant. The goods are next well and carefully washed, to free them from all traces of sulphuric acid ; after which they are drained either by means of squeezers or the hydro-extractor. They are then dried for printing. ii2 BLEACHING, DYEING, ETC. If the fabric is mixed wool and cotton (mousseline de laine), after the good pieces have been scoured or "crabbed," theyare prepared as before described, but after being drained by means of the squeezer or the hydro-extractor, and before being dried, they are again padded through the padding-machine charged with sulpho-muriate of tin at 6 or 8 Twaddle, and allowed to remain so saturated from i to 1 1 hours. They are then passed through a cistern charged with chloride of lime at from | to J Twaddle. The cistern being supplied at top and bottom with rollers, the cloth passes over and under these ; the cistern must have such a capacity that the cloth in its transit through it shall occupy from 30 to 50 seconds, during which time it is exposed to the action of the evolved chlorine. Directly the cloth leaves the chlorine cistern, it falls into water and thence passes on to the washing-machine, after which it is drained as usual, and dried. Sulpho-muriate of tin is prepared as follows : Sulphuric acid, 170 Twaddle . 2 gallons. Water 8 Stir till cool, then in 8 gallons of water dissolve, cold, protochloride of tin crystals 25 Ibs. Afterwards mix all together, and reduce with cold water to 8 Twaddle. COLOURS FOB STEAM STYLES. RED (wood red). Sapanwood liquor at 8 Twaddle 3^ gallons. Ground alum 3 Ibs. Chlorate of potash 6 ozs. Nitrate of alumina 3 pints. Bark liquor, at 8 Twaddle . . 5 CALICO-PRINTING. 1 1 3 Water ........ 8 pints. Crystal starch ...... yi Ibs, Boil, cool, and strain. 2. NITRATE OF ALUMINA. Hot water ....... 32 gallons. In which dissolve Nitrate of lead ..... 96 Ibs. Alum ........ 96 Common soda (carbonate) . .12 When dissolved allow to subside and use the clear liquor. 3. PINK (cochineal) STANDARD. Boiling water ...... i gallon. In which dissolve Bitartrate of potash (cream of tartar) ....... ij Ibs. Ground alum ...... i| And then add Cochineal liquor at 8 Twaddle 3 gallons. 4. PINK (cochineal) MEDIUM. Gum (foreign) water (4 Ibs. to 6 Ibs. per gallon) .... 3 gallons. Cochineal pink standard (3) . 2 5. PINK (cochineal) PALE OR ROSE. Gum (foreign) water (5 Ibs. per gallon) ....... 3 gallons. Cochineal pink standard (3) . i 6. PINK (magenta aniline) DARK. Gum (foreign) water .... 4 quarts. Magenta crystals ..... 4 ozs. Dissolved in Acetic acid at 8 Twaddle . . i quart. Tannic acid dissolved . ... 12 ozs. H4 BLEACHING, DYEING, ETC. 7. MEDIUM PINK. Foreign gum water .... 4 quarts. Magenta crystals 2 oz. Acetic acid at 8 Twaddle . . i quart. Tannic acid dissolved ... 8 ozs. 8. PALE or LIGHT PINK. Foreign gum water .... 4 quarts. Magenta crystals i oz. Acetic acid i quart. Tannic acid dissolved ... 6 ozs. Steam Styles known as " best prepared Steams, not Anilines." 9. CHOCOLATE STEAM STYLES. Sapanwood liquor at 12 Twaddle 6 gallons. Logwood . 3 Acetate of alumina 18 . 4 Bark liquor 12 ,, . 2 Starch 24 Ibs. British gum (terrified starch) . 4 Alum ......... 5j Chlorate of potash i| Sal ammoniac 2 Acetate of copper .... i gill (2 J noggins) Boil, cool, and strain. 10. DARK BLUE (Royal). Water 6 gallons. Starch 12 Ibs. Sal ammoniac 2 When boiled add Prussiate of tin pulp (cyanide of tin) 6 gallons. Thoroughly incorporate and add Yellow prussiate of potash (ferro- cyanide of potassium) . . . 12 Ibs. CALICO-PRINTING. 115 Red prussiate of potash (ferrid- cyanide of potassium) ... 6 Ibs. Tartaric acid 18 Stir till quite dissolved ; then add Oxalic acid, which has previously been dissolved in 3 pints of water i| Ibs. Mix and strain. 11. MEDIUM BLUE. Gum substitute water .... 3 gallons. Dark royal blue 2 12. PALE BLUE. Gum substitute water .... 7 gallons. Dark royal blue I gallon. Any further reduced shades in the same way to pale sky. 13. GREEN, (Dark Royal). Bark liquor at 12 Twaddle . . 6 gallons. Starch 10 Ibs. Boil and add Protochloride of tin crystals . 1 2 ounces. Prussiate of tin pulp . . . . i gallon. Yellow prussiate of potash . .14 Ibs. Tartaric acid 13 Extract of indigo (of commerce) 2 pints. 14. PRUSSIATE OF TIN PULP (Ferrocyanide of tin). Take 1 2 gallons of hot water, in which dissolve 12 Ibs. of yellow prussiate of potash ; add gradually to the solution 6 quarts protochloride of tin at 120 Twaddle. Then fill up the vessel with cold water ; wash the preci- i 2 n6 BLEACHING, DYEING, ETC. pitate several times, and afterwards filter for use ; using of course the precipitate. 15. MEDIUM GREEN. Persian berry liquor (yellow berries) at 12 Twaddle . . 8 gallons. Yellow prussiate of potash . .16 Ibs. Alum 8 Oxalic acid 2 Protochloride of tin at 120 Tw. 2 ,, Acetic acid at 8 Twaddle . . i gallon. Foreign gum water (8 Ibs. per gallon) 6 gallons. 1 6. PALE GREEN. Gum (foreign) water .... 5 gallons. Medium green 2 17. YELLOW. Persian berry liquor at 8 Tw. . 4 gallons. Starch 4 Ibs. Gum substitute i Alum 2 ,, Boil and add Protoxide of tin 4 pints. Protoxide of tin is made as follows : 2\ Ibs. protochloride of tin crystals are dissolved in i gallon of water, and 2 J Ibs. of common soda in another gallon, then both solutions are gradually mixed, and afterwards the precipitate washed twice and filtered. 1 8. DEEP YELLOW. Bark liquor at 12 Twaddle . . 4 gallons. Starch 6 Ibs. Boil and add the following basic tin compound : CALICO-PRINTING. 117 Basic Tin Compound. 2 1 Ibs. of common soda are put into an earthenware vessel, which is then placed in a hot-water bath, and kept there till the heat from the water-bath causes the soda to lose its crystalline state, and to become liquid, when there is immediately added to it 3 Ibs. of proto- chloride of tin crystals ; the mixture must be briskly stirred, and when the whole has become semi-fluid, it is added to the colour. 19. RED (Wood Red) better than No. i. Sapanwood liquor at 12 Twaddle 8 quarts. Bark liquor at 12 Twaddle . . 2^ Nitrate of alumina 2 Water 4 Oxalic acid i Ib. Alum 12 oz. Chlorate of potash 4 Starch 6J Ibs. Boil, cool, and strain. 20. MEDIUM BROWN. Bark standard 14 pints Sapan 3 Blue ij Black i Gum substitute water .... 3 21. BARK STANDARD (A). Bark liquor at 12 Twaddle . . 3 gallons. Alum 3 Ibs. 22. SAPAN STANDARD (B). Sapanwood liquor at 12 Twaddle 2 gallons Chlorate of potash 4 oz. ii8 BLEACHING, DYEING, ETC. Alum ......... i| Ibs. Gum substitute ...... 8 Ibs. Boil and cool. 23. BLUE STANDARD (c). Water . . ....... 2 gallons. In which dissolve Red prussiate of potash ... 2 Ibs. Alum ......... i 24. BLACK STANDARD (D). Logwood liquor at 1 2 Twaddle . 2 gallons. Gum substitute ...... 6 Ibs. Boil and add Red prussiate of potash . . . 2 Ibs. Alum ......... i^ Ibs. Dissolve and cool. 25. RED BROWN. Bark standard (A) ..... 8 quarts. Sapan (B) ..... 2 Black (D) ..... i Gum substitute water .... 6 26. FAWN or MEDIUM (CHAMOIS). Bark standard (A) ..... 16 pints. Sapan (B) ..... 2 Black (D) ..... 2 Gum substitute water . . . .16 gallons. N.B. From the four standards A, B, c, and D, every tone and shade of colour may be obtained, from a dark brown to a light fawn (including Chestnut Cuir, Chamois, Cinnamon and all kindred compound colours), by varying their proportions. 27. BUFF or PALE NANKEEN STANDARD (A). Persian berry liquor at 12 Twaddle 3 gallons. CALICO-PRINTING. 119 Cochineal liquor at 6 Twaddle i Alum 3 Bitartrate of potash (cream of tartar) i| gallon. Ibs. 28. MEDIUM BUFF. Gum substitute water ... 3 gallons. Buff standard (A) ...... 2 29. PALE BUFF. Gum substitute water . . .10 gallons. Buff standard (A) ..... i 30. BLUE STANDARD FOR SHADES. "Water ......... 4 gallons. In which dissolve Oxalic acid . . ..... i Ib. Alum ......... 4 Yellow prussiate of potash . . 8 31. SLATE STANDARD. Logwood liquor at 12 Twaddle 2 gallons. Blue Standard for shades . . i| Medium green ..... 3 quarts. Tartaric acid .... 32. MEDIUM SLATE. Gum substitute water Slate standard, No. 3 1 33. PALE SLATE. Gum substitute water Slate standard 34. SILVER DRAB STANDARD. Slate standard Buff or pale nankeen standard Pink (cochineal) standard (3) Ib. 4 quarts. 10 gallons. i 4 gallons. 3 i 120 BLEACHING, DYEING, ETC. 35. MEDIUM SILVER DRAB. Gum substitute water .... 3 gallons. Silver drab standard . . . . i 36. PALE SILVER DRAB. Gum substitute water . . .10 gallons. Silver drab standard . . . . i IST.B. From the foregoing formulae every shade and tone of compound colours can be obtained : Stones, Drabs, Lavenders, Slates, Pearls, &c. &c., all of which are known as " best prepared steam styles." FORMULAE FOR MIXED GOODS. COTTON AND WOOLLEN (MOUSSELINE DE LAINE), &c. On prepared goods. 1. BED. Cochineal liquor, at 12 Twaddle 4 gallons. Starch 8 Ibs. Gum substitute i Boil and add Protochloride of tin crystals . . i| Oxalic acid ...,.,. i| Dissolve and strain. 2. CRIMSON. Ammoniacal cochineal standard . 4 gallons. Bitartrate of potash (cream of tartar) 3 Ibs. Alum (dissolved) 3 Foreign gum 16 Stir till dissolved. 3. ROSE or PINK. Foreign gum water .... 3 gallons. Crimson, No. 2 i CALICO-PRINTING. 1 2 1 4. AMMONIACAL COCHINEAL STANDARD. 8 Ibs. Cochineal, steeped for 12 hours in a covered vessel (not copper) with 2 gallons cold water, and 1 liquid ammonia ; afterwards add 2 ,, more water ; boil in water-bath for 2 hours, afterwards sieve off the liquor, which ought to measure 4 gallons; should it not do so, add sufficient water to make up to that quantity. 5. DARK BLUE. Same as royal blue for cottons. 6. LIGHT BLUE. Same as pale blue for cottons. 7. YELLOW or AMBER. Persian berry liquor, at 12 Twaddle 4 gallons. Foreign gum 16 Ibs. Protochloride of tin crystals . . 2 8. GREEN MEDIUM. Persian berry liquor, at 12 Twaddle 4 gallons. Alum 3 Ibs. Oxalic acid i ,, Tin crystals (protochloride) . . i Yellow prussiate of potash . . 6 Foreign gum water (6 Ibs. per gallon) 4 gallons. Extract of indigo 3 pints. 9. CHOCOLATE. Sapanwood liquor, at 12 Twad- dle 6 gallons. Logwood liquor, at 12 Twaddle 3 122 BLEACHING, DYEING, ETC. Bark liquor, at 1 2 Twaddle . . i gallon. Starch 16 Ibs. Gum substitute 4 ? Boil and add Alum 7i Chlorate of potash 10 ozs. Bed prussiate of potash . . . 4! Ibs. Most of these colours are now superseded by the aniline colours. 9. Spirit Styles. 1. BLACK. Logwood liquor at 8^ Twaddle . 6 gallons. Starch 9 Ibs. Gum substitute 4 Boil and add Nitrate of iron at 84 Twaddle . 4 pints. Mix thoroughly and strain. 2. PURPLE or LILAC. Logwood liquor at 8 Twaddle . 8 gallons. Starch 16 Ibs. Boil and add Yellow prussiate of potash . . i| Nitrate of iron at 84 Twaddle . 3^ pints. Starch paste (i Ib. per gallon) . 4 gallons. Perchloride of tin 120 Twaddle i Mix and Strain. 3. PINK. Use Sapanwood, with tin. 4. BLUE. Use Prussian blue, with tin. And so on. 10. Bronze Style.* The goods are padded through a * During the last three years there has been more demand for prints produced by this style, than for the previous forty years. CALICO-PRINTING. \ 23 padding machine, charged with a solution of protochloride of manganese at from 24 to 36 Twaddle, and dried through a hot-air stove, care being taken to avoid their coming into contact with the iron of the stove. They are then passed through the soda cistern, as quickly as possible after being dried, since the protochloride of manganese being deli- quescent, the fabric otherwise becomes damp, to the detri- ment of the bronze colour. The soda cistern is fitted with twelve rollers, six at top and six at bottom, over and under which the cloth is passed. The cistern is charged with caustic soda at from 20 to 24 Twaddle. In passing through this solution, the manganese is precipitated upon the fabric, in an almost colourless condition, in the state of a protoxide. The fabric is then carried over wooden rollers, a process which, by exposing it to the air, effects the partial oxidation of the manganese. It is then well washed and afterwards winched for five or ten minutes in chloride of lime at 4 to 6 Twaddle, which converts the manganese protoxide into peroxide, which is of a dark bronze colour, and which gives its name to the style. After the pieces are printed with the colours, for which the formulae are now given, they are steamed in the usual way in an ordinary steam-chest at about one to two pressures for twenty-five minutes. They are afterwards washed, drained on a hydro-extractor, and dried. COLOURS FOE BRONZE STYLES. i. WHITE DISCHARGE ON BRONZE. Water 2 gallons. Wheat en starch 5 Ibs. Boil and, when half cold, add Protochloride of tin crystals . . 12 Stir till thoroughly dissolved, and afterwards strain. 124 BLEACHING, DYEING, ETC, 2. YELLOW DITTO. Bark liquor, at 12 Twaddle . . 2 gallons. Starch 5 Ibs. Boil and add when half cold Protochloride of tin crystals . . 12 Dissolve and strain. 3. RED DITTO. Sapan or Brazil wood liquor, at 12 Twaddle 2 gallons. Starch 5 Ibs. Boil and, when half cold, add Protochloride of tin crystals. .12 Dissolve and strain. 4. MAUVE or VIOLET DISCHARGE ON BRONZE. 4 B Violet 2 quarts. Water 4 gallons. Starch n Ibs. Boil and, when half cold, add Protochloride of tin crystals . . 20 Dissolve and strain. 5. BLUE DITTO. Prussian blue paste .... 2 quarts. Water 2 gallons. Starch 6 Ibs. Boil and, when half cold, add Protochloride of tin crystals . . 12 Dissolve and strain. 6. GREEN DITTO. Mix yellow No. 2 and blue No. 5, say, 2 of the former, i j of the latter, or any other proportions to produce the shade of green required. CALICO-PRINTING. 125 From the foregoing formulae, it will be seen that proto- chloride of tin is the active agent which discharges the peroxide of manganese, and at the same time becomes the mordant for the various colouring matters. Any colouring matter therefore to which the protochloride of tin acts as a mordant, and which will bear the quantities given of it as before, can be used for bronze discharges. Beautiful styles are now being worked with bronze effects. ii. Pigment Style. The theory and practice are described at page 93. Sometimes, however, to obtain bright blues, the goods instead of being steamed are passed through a cistern charged with boiling milk of lime. The hot lime-water, by instantly coagulating the egg albumen, renders the blue brighter. Sometimes after fixation of the pigments, they are slightly soaped with the object of removing the unpleasant odour. PIGMENT COLOURS. 1. GREEN (Best). Green pigment 8 Ibs. Blood albumen water (5 Ibs. per gallon) i gallon. Mix well and strain. 2. GREEN (Generally Used). Green pigment 4 Ibs. Gum tragacanth water . . . i quart. Blood albumen water (5 Ibs. per gallon) 3 3. BROWN PIGMENT COLOUR. Brown pigment 4 Ibs. Gum tragacanth water. . . . i gallon. Blood albumen water . i 126 BLEACHING, DYEING, ETC. 4. BUFF PIGMENT COLOUR. Buff pigment 4 Ibs. Gum tragacanth water . . . 2 quarts. Blood albumen water .... 2 5. BLACK PIGMENT COLOUR. Pigment black 6 Ibs. Gum tragacanth water ... 2 quarts. Blood albumen 4 J? 6. OLIVE PIGMENT COLOUR. Pigment green colour . . . . i| pints. Buff pigment . . . . i| Black . . . . 2 Blood albumen water .... 2 . Gum tragacanth water ... 2 7. TAN PIGMENT COLOUR. Blue pigment standard ... i| pints. Brown colour .' . . . ij Black . . . . ij Blood albumen water .... 2 ,, Gum tragacanth water ... 2 8. GREY PIGMENT COLOUR. Black pigment colour .... 2 pints. Albumen water i Gum tragacanth water .... i 9. SLATE PIGMENT COLOUR. Black pigment colour .... 3 pints. Blue standard . . .12 Blood albumen water . . . . 7 Gum tragacanth water .... 7 CA LI CO -PR IN TING. \ 27 10. PIGMENT BLUE STANDARD. Ultramarine 2 Ibs. Gum tragacanth water ... 3 quarts. Blood albumen water . . . . i The best pigment blues are made with egg albumen, not with blood albumen. 12. Extract Style. Some years ago, before the adoption of artificial alizarin by the dyer and calico-printer, an ex- tract of madder was introduced into the trade. It is from this fact that the present style takes its name. By the extract style, thanks to the discovery of artificial alizarin and other coal-tar colours, effects are obtained that were previously practically impossible. The old method was to print on the fabric the mordants for the madder colours, and afterwards to dye it, the printing in of the illuminating colours being performed by hand. In extract printing, this clumsy method, which generally effaced the integrity of the design, is avoided, with immense advantage to the resulting pattern, of delicacy and fidelity of outline, as well as of richness and purity of colour. The discovery and application of the coal-tar colours have given an unpre- cedented impetus to this amongst other branches of calico- printing, not only by increasing the number and variety of tinctorial agents possessing purer tints, but because the raw material for manufacturing them lies around us. At the present day when the printer requires pale chintzes, it is not necessary for him to ransack the two hemispheres for the red, yellow, blue, green, and violet dye-stuffs, as it was not many years back. COTTON. FORMULAE FOR EXTRACT STYLES. After the goods are bleached as for madder styles, they are prepared by padding through an emulsion of oleine, or 128 BLEACHING, DYEING, ETC. saponified castor oil, made by mixing i part of oleine to 15 of water; or i of oleine to 20 of water: this latter being the strength generally used. The goods are after- wards dried, and are then ready for printing. After printing, the goods are aged and then steamed for 1 1 hours at a pressure of from i to 2 Ibs. per square inch. Then, provided the prints contain no mordant of which tannic acid is an ingredient, as is the case with the coal-tar colours, they are washed and afterwards soaped as in madder work, but for not quite so long a time, or at so high a tempera- ture ; afterwards they are washed, cleared, drained, and dried. If, however, the mordants used for any of the colours contain tannic acid, the goods must be passed through a solution of tartrate of antimony (2 oz. to the gallon). This is done before washing and soaping, and of course after they have been steamed. 1. EXTRACT, RED. Acetic acid at 8 Twaddle . . 9 pints. Water 14 Olive oil 4 Starch 7 Ibs. Boil, and when nearly cold, add Acetic acid at 8 Twaddle . . 2 pints. Acetate of alumina at 18 Tw. . 2j ,, Nitrate of alumina i| ,, Sulphocyanide of alumina ... 2 Acetate of lime (at 2 Ibs. per gal.) 5 Artificial alizarin (at 20 per cent.) 13 Ibs. 2. DARK PURPLE (Extract Work). Water 2 gallons. Acetic acid at 8 Twaddle . . 2^ quarts. Starch 6 Ibs. CALICO-PRINTING. 129 Boil and add Acetate of iron (4 and 4)* . . 2 pints. Acetate of lime (2 Ibs. per gal.) 4 Artificial alizarin (20 per cent.) 10 ,, 3. BLACK (Chromium). Logwood liquor at 12 Twaddle . 6| gallons. Bark ,, .6 quarts. Acetic acid at 8 Twaddle ... 5 Water 2 Dark British gum . . . .36 Ibs. Starch ...*.... 9 Boil and add Chlorate of potash i And when cold add Nitro-acetate of chrome . . . i gallon. 4. NlTRO-ACETATE OF CHROME. A. 6 Ibs. bichromate of potash, 3 gallons of hot water ; dissolve, then add yi- Ibs. sulphuric acid at 170 Twaddle, diluted with 2 quarts of cold water ; then add gradually 1 1 Ibs. raw sugar. B. 9f Ibs. nitrate of lead, 9! acetate of lead dissolved in 2 quarts of hot w^ater ; then add to solution A. Mix well, allow to subside, and use the clear liquor. * The acetate of iron is made as follows: Sulphate of iron (copperas) 4 Ibs., hot water 2 quarts, dissolve ; acetate of lead 4 Ibs., hot water 2 quarts, dissolve. Mix the solutions and stir well ; let the precipitate settle, and keep the clear liquid for use. K 130 BLEACHING, DYEING, ETC. 5. MAUVE (Fast) for Extract Work. Acetic acid ...... 2 quarts. "Water 2 Yiolet crystals (6 B violet.) . 4 ozs. Starch i Ib. Boil and add Tannic acid 8 ozs. Dissolve arid strain. 6. MAUVE (Fast). Hed liquor at 18 Twaddle . . 3 gallons. "Water i Gum tragacanth water (8 ozs. per gallon) i gallon. Starch 5 Ibs. Boil and add Alum i Ib. Violet crystals i ,, Dissolve and, when cold, add Glycerin standard i J quarts. Mix \vell and strain. 7. GLYCERIN STANDARD. Brown glycerin 2 gallons. Arsenic . 8 Ibs. Boil i hour ; allow to stand, and use the clear liquor. P.S. When boiling the arsenic and glycerin, avoid inhaling the steam, which contains a dangerous gas. K.B. By following Methods 5 and 6 all the ani- line violets, mauves, magentas, most of the blues, choco- lates, and other aniline colours can be fixed for printing ; when desired for dark shades and neat patterns, starch may be used as the thickening, and gums for medium or light shades. CALICO-PRINTING. 131 8. CERULEAN BLUE (most beautiful colour.) Red liquor at 18 Twaddle . . 3 gallons. Water i Jt Gum tragacanth water (8 ozs. per gallon) i Starch 5 Ibs. Boil and add Ground alum i lb. Dissolve and, when quite cold, add, Glycerin standard 3 pints. And Cerulean blue (ROBERTS, DALE, and Co.) 5 Ibs. 9. METHYL GREEN. Acetic acid 7,} quarts. Sumach extract 7^ Tartaric acid i lb. Starch 5 ,, Boil and, when cold, add Methyl green crystals . . . i Alum 8 ounces. Dissolved in Persian berry liquor or extract, at 48 Twaddle 4 pints. jo. METHYLINE BLUE. Acetic acid at 8 Twaddle . . \ gallon. Water i Methyline blue crystals ... 3 ounces. Starch i lb. Boil and add Tamiic acid 8 ounces. Dissolve. K 2 132 BLEACHING, DYEING, ETC. IT. PINK or ROSE. Is made by reducing Extract Bed, formula (i), either with gum water or starch paste. 12. PINK. Gum water (4 Ibs. per gallon) . 3 gallons,. Extract Keel (i) i 13. PALE PURPLE. Gum water (4 Ibs. per gallon) . 3 gallons^ ^Extract Purple (2) . . . . i CHAPTER IV. BYE STUFFS. Aloes. An extract of aloes when treated with nitric acid, gives rise to various beautiful coloured products, which, by the aid of mordants, can be fixed to silken and woollen goods. Aloin, the colour-giving principle of aloes, is a body soluble both in water and alcohol, and when exposed to the air, it absorbs atmospheric oxygen, and assumes an intense red colour. Aloes are seldom employed for dyeing purposes. Annotta. Syn. ANOTTO, ANNATTO, ANNATA, ARNATTO, ARXOTTO. A colouring matter obtained from the seeds of the Bixa, orellana (LiNN.), an exogenous evergreen tree, common in Cayenne, and some other parts of tropical America. Annotta is usually obtained by macerating the crushed seeds or seed-pods of the plant in water for several weeks, ultimately allowing the pulp to subside, then boiling it in coppers to a stiff paste, and drying it in the shade. Some- times a little oil is added when the paste is made into cakes or lumps. A better method is that proposed by LEBLOXD, in which the crushed seeds are simply exhausted by washing them in water (alkalized ?), from which the colouring matter is afterwards precipitated by means of vinegar or lemon- juice ; the precipitate being subsequently collected, and either boiled up in the ordinary manner, or drained in bags and dried, as is in the preparation of indigo. Annotta so prepared is said to be four times as valuable as that made by the former process. 134 BLEACHING, DYEING, ETC. The term annotta is frequently indiscriminately applied to the commercial article, and to the colouring principle contained in it. This latter is a resinous substance possess- ing strong tinctorial properties, to which the name bixin* has been given. It may be prepared by digesting commercial annotta in an alkaline lye, and by neutralizing the filtered liquid with sulphuric acid, when the bixin is precipitated. Bixin is of an orange colour, scarcely soluble in water, but freely so in alcohol, ether, oils, and fats, to each of which substances it imparts a beautiful orange tint. It is also soluble in alkaline solutions, to which it imparts a deep red colour. Genuine commercial annotta contains about 28 per cent of the resinous substance (bixin), and 20 per cent, of extractive matter. In analyzing a sample, it is only necessary to determine the quantity of ash and of colouring matter it contains, the nearer of course the amount of the latter approaches that given above, the greater will be its trade value. Dr. BLYTH gives the following as the composition of a fair commercial sample. The sample was in the form of a paste, colour deep red, odour peculiar, but not disagreeable :. "Water 24-2 Resinous colouring matter . . . . 2 8 '8 Ash 22*5 Starch and extractive matter . . . 24-5 lOO'O The following is an analysis of an adulterated specimen.. The sample was in a hard cake of a brown colour, with the * Annotto also contains another and less important colouring bocty,. which lias been denominated orellin. DYE STUFFS. 135 maker's name stamped upon it, and marked " patent" ; tex- ture hard and leathery, odour disagreeable : Water 13-4 Resin . iro Ash, consisting of iron, chalk, salt, alumina, silica 48*3 Extractive matter 27-3 lOO'O Thus, in the one the resin was 28 per cent., the ash 22 per cent. ; in the other the resin was only n per cent., the ash no less than 48 per cent. Annotta is very frequently extensively adulterated. The most usual sophisticants are meal, flour, or farina of some description, chalk, plaster of Paris, pearlash, soap, turmeric, Venetian red, red ochre, orange chrome and common salt. Red lead and sulphate of copper have occasionally been detected in it. Dr. H ASS ALL states that out of thirty-four 'different specimens, two only were genuine. Since genuine commercial amiotta exhibits but few evidences of structure, any of the above vegetable adulterants may be easily detected by means of the microscope. Annotta is used as a pigment for painting velvets and transparencies, and as a dye-stuff for cotton, wool and silk, to the latter of which it imparts a beautiful orange yellow hue, the shade of which may be varied from " aurora" to deep orange, by using different proportions of pearlash with the water in which it is dissolved ; or by applying different mordants before adding the amiotta to the dye- beck. The tints thus imparted are, however, more or less f ugitiv e . Archil. Syn. ARCIIEL, ORCHIL. This is a violet-red, purple or blue colouring matter or dye-stuff, obtained from 136 BLEACHING, DYEING, ETC. several species of lichens, but of finest quality from Rocclla tinctoria, and next from Rocellafusiformis. The archil of commerce is met with as a liquid paste, or as a thin liquid dye of more or less intensity of shade. Blue archil, is prepared by steeping in the cold in closely covered wooden vessels, the coarsely ground lichen in a mixture of lime or milk of lime, in stale urine or bone spirit, or in any similar ammoniacal solution ; the process being repeated till all the colour is extracted. The carbonate of ammonia resulting from the decaying urine acts upon the peculiar acids, the lecanoric, alpha and beta orcellio, erythrinic, gyrophoric, evernic, usninic, &c., contained in the lichens, and converts them into orcine. By taking up nitrogen and oxygen, orcine is converted into orceine, which constitutes the essential colouring principle of archil. In the preparation of red or crimson archil, the same materials are used as for the production of the blue ; the only difference being that a smaller quantity of milk of lime is used, and the steeping is generally performed in an earthen jar placed in a room heated by steam, and technically called a stove. The two varieties differ only in the degree of their red or violet tint, the addition of a small quantity of lime or alkali to the one, or of acid to the other, immediately bringing them to the same shade of colour. The hues given by archil to silk and wool possess an exquisite lustre, but they are far from permanent, and since the introduction of the coal-tar colours, their use has diminished considerably. If archil is employed at all, it is in combination with other dye stuffs, or as a finishing bath to give a bloom to silk or woollen goods dyed with some permanent colour. Barwood. A red dye-wood imported from Angola and other parts of Africa. It closely resembles camwood and sanders wood in its colouring matter being of a resinous nature, and scarcely soluble in water. In dyeing, this dim- DYE STUFFS. 137 culty is obviated by taking advantage of the strong affinity existing between it and the protosalts of tin and iron. Thus, by strongly impregnating the goods with protochloride of tin, either with or without the addition of sumach, according to the shade of red desired, and then putting them into a boiling bath containing the rasped wood, the colour is rapidly given out and taken up, until the whole of the tin in the fibres of the cloth is saturated, and the goods become of a rich bright hue. In like manner the dark red of bandana handkerchiefs is commonly given by a mordant of acetate of iron followed by a boiling bath of this dye- stuff. Previous to the introduction of artificial alizarin " Barwood Reds " were extensively used, and they ranked next in permanency to madder reds. The dark barwood red, however, possessed one great defect : if exposed for some time to the air, it darkened, and became dull. The change is supposed to be due to the absorption of ammonia. Catechu. Syn. CASHEW, CUTCH, GAMBIR. An extract obtained from the wood of the Acacia catechu, or from the leaf of Uncaria gambir. There are several varieties of catechu known in commerce, of which the principal are I- BOMBAY CATECHU. This occurs as a firm, brittle extract, of a dark-brown colour, of uniform texture, and of a glossy, semi-resinous and uneven fracture. Sp.gr. i'39 Richness in catechu tannin 52 per cent. MALABAR CATECHU. Resembles the last in appearance, but is more brittle and gritty. Richness in catechu tannin 45*5 per cent. The amount of catechu tannic acid may be determined in catechu as follows : i. Exhaust a weighed and finely pulverized sample of the catechu with ether, and evaporate by the heat of a water-bath; the product, which is catechu-tannin, must then be accurately weighed. 138 BLEACHING, DYEING, ETC. 2. Reduce the sample to powder, dissolve in hot water, let cool out of contact with the air, filter and add solution of gelatine as long as a precipitate falls. The precipitate, after being washed and dried at a steam heat, should contain 40 per cent, of catechu-tannin. When used for dyeing purposes catechu forms a great variety of browns. Alum mordants are mostly emplo}-ed in dyeing with it. With the salts of copper, and sal ammoniac,* catechu gives a fast bronze colour ; with protochloride of tin, a brownish yellow ; with perchloride of tin and nitrate of copper, a deep bronze; with acetate of alumina, a reddish brown; with nitrate of copper a reddish olive grey, and with nitrate of iron, a deep brown grey. Acetate of alumina and tin nitrates make but weak mordants for catechu, sulphate and acetate of copper the best. The iron mordants also act satisfactorily, although they give darker and duller colours than the copper ones. Hence it is that the iron mordants are rarely ever used alone with catechu, but in conjunction with copper ones, by which means the browns are converted into drabs. Some beautiful colours are now obtained by mixing varying quantities of magenta with the catechu and copper. Such colours are fairly fast. Brazil Wood. Syn. CAMWOOD. This dye-stuff is furnished by several species of trees belonging to the genus Ccesalpinia, and was formerly much employed in producing . various shades of red. The best kind of Brazil wood is that known as Pernambuco or Fernambuco wood, the source of which is the Ccesalpinia brasiliensis s. crista. This variety is a heavy and rather hard wood, externally * The sal ammoniac acts chiefly by absorbing moisture, and by thus expediting the oxidation of the metals employed, aids in the fixation of the catechu. DYE STUFFS. 139 of a yellowish brown, and internally of a bright red colour. It occurs in commerce in chips and large logs. Inferior but closely allied varieties of the wood are i. Sapan woody derived from Ccesalpinia Sapan, and Lima or Nicaragua, wood. The colouring matter of all these woods is brezilin, which when isolated occurs in small orange-coloured needles, solu- ble both in water and alcohol. Alkalies turn it violet, acids yellow. These woods give brilliant but unstable colours. Coal-tar Colours. See p. 160. Cinchonine. If cinchonine (one of the products left after the extraction of the quinine from cinchona bark),, be submitted to distillation with caustic soda in excess,, there passes over into the receiver a crude kind of oil,, called chinoline oil, one of the principal constituents of which is a base called Lepidine,. When this chinoline oil is heated with amyl iodide, and the product treated with caustic soda solution, a very bril- liant blue pigment known as Cyanine, Lzpidine Blue, or Chinoline Blue is obtained. Cinchonine has a very limited application in dyeing. Cochineal. Syn. Coccus CACTI. This insect is found upon several species of Cacti, more particularly on the ISTopal plant, and on the Cactus opuntia. The chief seats of the cochineal culture are Mexico,Central America, Java, Algeria,, the Canary Islands and the Cape. The insect sickens and dies out if the cactus plant is grown too near the sea, or exposed to damp winds. The female insect, which only possesses value as a dye, is wingless the male, on the contrary, is winged. The females- are collected twice a year after they have laid their eggs. They are first brushed off the plant, and then killed, some- times by exposure to the vapour of boiling water, but more frequently by the heat of an oven. HO BLEACHING, DYEING, ETC. The two chief varieties of cochineal are known in commerce as the " silver grey" and the " black," another kind is dark grey mottled with red. The best kind comes from Honduras. An inferior quality is collected from wild cactus plants. The silver grey specimens are covered with a white dust, which microscopical examination has proved to be the insect's ex- crement. The white dust is frequently imitated by shaking the insects in a bag with French chalk, or white lead. Herr DURWELL. a German chemist, states that he found a sample adulterated with oxide of zinc. Sulphate of baryta and powdered bone dust have also been used as sophisticants. The object of the adulterations is of course to increase the weight. Genuine cochineal has the specific gravity 1*25. A peculiar kind of acid, which has been named carminic acid, has been discovered in cochineal. "When acted upon by very dilute sulphuric acid and other reagents, carminic acid splits up into carmine red (or carmine) and glucose. Artifi- cally prepared carmine is obtained by exhausting cochineal with boiling water, adding alum to the clear supernatant liquid, and allowing the carmine to deposit. Since the intro- duction of the coal-tar colours, cochineal is in much less demand by the dyer. To ascertain the colorific value of a sample of cochineal, the dyer generally makes a dyeing experiment 011 a small scale. He impregnates a piece of mordanted wool, cotton, or silk, with a decoction of the specimen under examination, and then compares the colour with that of a piece of similar tissue dyed with a standard decoction of cochineal. By this means, he is enabled to form an opinion as to the strength, purity of colour, &c., of his specimen. Cudbear. Syn. PERSIO. This dye-stuff is obtained from Lecanora tartarea, and other lichens, by a process nearly similar to that used in making archil. The lichen is watered with stale urine or some other ammoniacal liquid, DYE STUFFS. 141 and kept in a state of fermentation for three or four weeks, after which the mixture is transferred to a flat vessel, and exposed to the air until the urinous smell has disappeared, and it has become of a violet colour. The residue is then ground to powder. Its use is limited to a few cases of silk dyeing, where it is employed to impart shades of ruby and maroon. It dyes wool of a deep red tint. The colours given by it are very fugitive; there are two varieties of cudbear, the blue and the red. Fustic. Two distinct dye-stuffs are met with under this name, the " old" and the " young" fustic. Old Fiistic, called also " yellow wood" is the hard wood of the Madura tinctoria, a tree growing in Cuba, Hayti, and St. Domingo. The tinctorial properties of the wood are due to a colourless crystalline substance, called marine, and to a peculiar acid, the moritannic, to which the name madurin has been given. Under the combined influence of alkalies and the air, morine becomes yellow. It dyes woollens different shades of yellow according to the mordant. These colours are very permanent. A commercial extract of the wood is sent into the market under the name of Cuba extract. Young Fustic is the wood of the lihus cotinus or Venice sumach, a shrub belonging to Southern Europe. It derives its name of young fustic from the circumstance of its branches being much smaller than those of the old fustic. The colouring principles of this wood are tannic acid, and a substance termed fustine, which, it appears, yields by decom- position quercetin, one of the decomposition products of quercitrin, the pigment of quercitron bark. Young fustic dyes greenish yellow, but the colours are not very permanent. Indigo. This blue dye-stuff is extracted from several plants growing in the East and West Indies, Central and Southern America, Egypt and other countries. 142 BLEACHING, DYEING, ETC. The Indigofera tinctoria, Indigofera anil, Indigofera dispenna, Indigofera jiseudotinctoria, and Indigofera argentea are the chief varieties of the plant, from which commer- cial indigo is obtained. The Nerium tinctorium is the source of the East India indigo. Indigo does not exist as such in the plant, but is the result of the action of atmospheric oxygen upon the freshly expressed juice. The method of its manufacture consists in steeping the branches, twigs and leaves of the plant in tanks filled with water until fermentation sets in. The clear liquid, which then assumes a yellow or golden colour, is drawn off from the deposited vegetable matter, and agitated and beaten with bamboo poles for about two hours to bring it into contact with the air. By this treatment the indigo forms and settles down as a blue precipitate,which in its fluid state is run into a caul- dron, in which it is boiled for about fifteen or twenty minutes to prevent its undergoing a second fermentation, which would render it useless. After standing over night, the magma in the cauldron is again boiled for three or four hours, after which it is placed on filters, composed of bamboo mats and canoes. The thick nearly black paste which is left on the filters, is subjected to pressure in boxes,whereby the greater portion of the water is removed, and the paste becomes of a more solid consistence. The cakes of indigo thus formed are dried by artificial heat, packed in wooden boxes and so sent into the market. Commercial indigo contains indigo blue, or indigotin (its most important constituent), indigo red, indigo brown, &c. The amount of indigo blue or indi- gotiii varies in different samples of commercial indigo from 20 to 75 or 80 per cent., and averages from 40 to 50 per cent. The indigo plant, according to SCHUNCK, contains a glucoside, which he terms indican ; when indican is decom- posed by fermentation, or acted upon by strong acids, it is DYE STUFFS. 143 converted into indigo' blue or indigotin, and a peculiar kind of sugar, indiglucin, according to the following formulae : Indican. Indigo blue. Indiglucin. The best indigo is that which has the deepest purple colour, and which assumes, when rubbed with the nail, a bright coppery hue. Its fracture should be homogeneous, compact, fine-grained, and coppery. When reduced to powder it should possess an intense blue colour, and should be so light as to float on water. Indigo should leave only a fine streak when rubbed on a piece of paper. In general, when indigo is in hard dry lumps of a dark colour, or in the form of dust or small pieces, it is frequently adulterated with sand, pul- verized slate, and other earthy substances, which fall to the bottom of the vessel when the indigo containing them is thrown on to water. Good indigo leaves only a small quantity of ash on ignition, and when suddenly heated gives off its indigotin in the form of a purplish coloured vapour. A simple and approximative test for indigo consists in drying the sample at 212 Fahr. ( 1 00 C.), the loss giving the quantity of hygroscopic water, which should not exceed from 3 to 7 per cent. The dried indigo is next incinerated for the purpose of ascertaining its yield of ash, which in good indigo should not be more than from 7 to 9*5 per cent. Four pounds of Bengal are equal to five pounds of Guatemala indigo. There are two methods of preparing solutions of indigo for dyeing : i. By deoxidizing it, and then dissolving it in alkaline menstrua. 2. By dissolving it in sulphuric acid. The former method is used in preparing the ordinary indigo vat of the dyers. i. a. (CoLD VAT). Take of indigo, in fine powder, i Ib. ; green copperas (clean cryst.), 2 J to 3 Ibs. ; newly slaked lime, 144 BLEACHING, DYEING, ETC. 3 J to 4 Ibs. ; triturate the powdered indigo with a little water or an alkaline lye, then mix it with some hot water, add the lime, and again well mix, after which stir in the solution of copperas, and agitate the whole thoroughly at intervals for twenty-four hours. A little caustic potassa or soda is frequently added, and a corresponding portion of lime omitted. For use, a portion of this " preparation vat" is ladled into the " dyeing vat," as wanted. After being employed for some time, the vat must be refreshed with a little more copperas and freshly slaked lime, when the sediment must be well stirred up, and the whole thoroughly mixed together. This is the common vat for cotton. b. (POTASH VAT). Take indigo, in fine powder, 12 Ibs.; madder, 8 Ibs. ; bran, 9 Ibs. ; potash, 24 Ibs. ; water at 125 Fahr. (51*5 C.), 120 cubic feet; mix well; at the end of about thirty-six hours add 14 Ibs. more potash, and after ten or twelve hours longer, further add 10 Ibs. of potash, and rouse the whole up well ; as soon as the fermentation and reduction of the indigo are well developed, which generally takes place in about seventy-two hours, add a little freshly slaked lime. This vat dyes very quickly, and the goods lose less of their colour in alkaline and soapy solutions than when dyed in the common vat. It is well adapted for woollen goods. It is worked hot. c. (Wo AD VAT). As the last, but employing woad instead of madder; the vat is "set" at 160 Fahr. (71 C.), and kept at that temperature until the deoxidation and solution of the indigo has commenced. The last two are also called the " warm vat." d. (PASTEL VAT). This is " set " with a variety of woad whfch grows in France, and which is richer in colouring matter than the plant commonly known as " woad." e. (SCHUTZEXBERGER and DE LALANDE'S VAT). It is known that the low stage of oxidation of sulphur obtained DYE STUFFS. 145 on the reduction of sulphurous acid by zinc, dissolves indigo. On this reaction the following proceedings for dyeing and printing with indigo are founded : To prepare the reducing liquid, a solution of bisulphite of soda at 35 B.is brought into contact with sheet zinc in a closed vessel, of which the liquid should occupy only one-fourth. After the lapse of an hour the zinc is precipitated from the clear liquid by means of milk of lime. It is then diluted or decanted, or filtered with exclusion of air. The clear liquid is then poured upon the ground indigo, with the addition of the needful soda and lime. One kilo of indigo yields in this manner a very concentrated vat of from 10 to 15 litres. Cotton is dyed cold, and wool with the aid of heat. A vat is filled with water, and a suitable quantity of the above indigo mixture introduced, when the dyeing can be performed at once. The excess of the low sulphur acid dissolves the froth which appears upon the surface. During the process of dyeing, further quantities of indigo can be added as required. Cotton can be rapidly and easily dyed in this manner ; and in the case of wool, the dyer escapes the many disadvantages of the hot vat and obtains brighter and clearer shades. To print a fast blue the alkah'ne solution of the reduced indigo is printed on with an excess of the reducing agent, aged for twelve to twenty- four hours, washed and soaped. In comparison with the old process there is a saving of indigo to the extent of 50 to 60 per cent. ; the shades are richer and the impressions sharper. The colour requires no subsequent treatment, and can there- fore be printed on simultaneously with most other colours. f. (GERMAN VAT). To 2,000 gallons of water heated to 130 Fahr. (54*4 C.), are to be added 20 Ibs. of crystals of common carbonate of soda, 2^ pecks of bran, and 12 Ibs. of indigo, the mixture being well stirred. In twelve hours fermentation sets in, bubbles of gas rise, L 146 ' BLEACHING, DYEING, ETC. the liquid acquires a sweet smell, and a green colour ; 2 Ibs. of slaked lime are next added, with diligent stirring ; the vat is again heated and covered over for twelve hours, when a similar quantity of bran, indigo, and soda, with some lime are added. In about forty-eight hours the vat may be worked ; but as the reducing powers of the bran are somewhat feeble, 6 Ibs. of molasses are added. Should the fermentation be too energetic, it must be repressed by the addition of lime : if too sluggish, it must be stimulated by the addition of bran and molasses. It is worked hot. Sulphate of Indigo. Syn. SULPHINDYLIC ACID, SUL- PHINDIGOTTC AdD, SAXONY BLUE, SOLUBLE INDIGO. This is generally prepared by adding indigo in fine powder i part, to Nordhausen sulphuric acid 5 parts, or oil of vitriol 8 parts, contained in a stoneware vessel placed in a tub of very cold water, to prevent the mixture heating. The ingredients are stirred together with a glass rod at short intervals, until the solution is complete, after which the whole is allowed to repose for about forty-eight hours, by which time it becomes a homogeneous pasty mass of an intense blue colour, which in a dull light appears nearly black. The above preparation, diluted with about twice its weight of soft water, is converted into " Saxony blue." Wool, silk, linen, and cotton, may each be dyed blue in the indigo vat. The goods after being passed through a weak alkaline solution, are subjected to the action of the vat for about fifteen minutes ; they are then freely exposed to the air ; the immersion in the vat and the exposure are repeated until the colour becomes sufficiently deep. Woad and madder improve the richness of the dye. Other deoxi- dizing substances, besides those above mentioned, may be used to effect the solution of the indigo ; thus a mixture of caustic soda, grape sugar, indigo, and water, is often em- DYE STUFFS. 147 ployed on the Continent for this purpose ; and orpiment, lime, and pearlash are also occasionally used. When pro- perly prepared, the indigo vat may be kept in action for several months by the addition of one or other of its con- stituents, as required. An excess of either copperas or lime should be avoided. 1. Solution of sulphate of indigo is added to water, as required, and the goods, previously boiled with alum, are then immersed in it, and the boiling and immersion are repeated until the wool becomes sufficiently dyed. With this, every shade of blue may be dyed, but it is most commonly employed to give a ground to logwood blues. The colouring matter has affinity for wool and silk with or without mordant, but none for cotton. A solution of soluble indigo (sulphindylate of potassa or soda), in water made very slightly acid with sulphuric acid, imparts a very fine blue to cloth, superior in tint to that given by the simple sulphate. 2. Give the goods a mordant of alum, or of acetate of alumina (" red liquor,") then rinse them well, and boil them in a bath of logwood, to which a small quantity of blue vitriol has been added ; lastly, rinse and dry. 3. Boil the goods for a short time in a bath of logwood , then add to the liquor tartar and verdigris, in the proportion of i oz. of each to every Ib. of logwood employed ; and again boil for a short time. Kermes. Syn. Kermes Grain, Alkermes. The dried bodies of the Coccus ilicis (LiXN.), a small insect which nourishes on the Ilex oak or Quercus cocciferce, a tree growing in the South of France, Spain, Italy, and the Greek Islands. Kermes now only finds use in Spain, Morocco, and Turkey, where it is used for dyeing leather and woollens. The colouring matter yielded by it is nearly the same as that existing in cochineal, but is not so brilliant. It is unacted upon by soap or alkalies. L 2 148 BLEACHING, DYEING, ETC. Lac. Syn. Lac lake, Indian cochineal. The source of this dye, the colouring matter of which is very similar to that found in cochineal, is a species of Coccus the Coccus laccce, a native of India. The insect punctures the branches of certain species of the fig, more especially the Ficus religiosa indica, the juice exuding from which in consequence, whilst becoming inspissated, encloses the creature, and at last hardens into a resinous mass around it, which becomes tinged with the colouring principle contained in the insect. By treating this resinous substance, known as stick lac, with a weak alkaline solution, and then adding to this a solution of alum, the pigment separates in the form of a lac lake. Lac dye is only suited for woollen or silk goods. It gives scarlet colours like those obtained from cochineal, but of a less brilliant character. The physical tests of a good lac-dye are that it should be tolerably easily broken by the fingers ; that the fracture should exhibit a deep red colour ; that it should not have a shining resinous appearance, and that it should evolve a pronounced and peculiar odour. The harder it" -is, the larger is the amount of shellac, and the smaller the quantity of colouring matter it contains. It may be tested by putting 5 grains of each sample in a phial, and covering with about 2 fluid drachms of scarlet finishing spirit, and setting aside all the specimens so treated for an hour, after which about an ounce of water is added to each phial, all the phials being then exposed for another hour to a moderate heat. They are then examined as to their respective depths of colour. This examination is all that is necessary when the lacs are used for printing, or for dyeing wool or woollen fabrics. When used, however, for woollen goods that require to be subsequently hot pressed, the amount of resin contained in the lac must be first ascertained ; for if this resin is in DYE STUFFS. 149 excess, the pressing papers will adhere to it in patches, and consequently spoil the goods. To ascertain the amount of resin in a lac, take equal weights of the samples reduced to powder, and place them in small flasks, pouring upon each sample an equal measure of alcohol. The flasks are then loosely stoppered and exposed to a gentle heat, after which the clear solutions are decanted off into capsules, the tares of which have been previously taken. The contents of the capsules are then evaporated to dry ness and weighed. The difference in the tare of each capsule will of course represent the amount of shellac in each sample. A great variety of brands of lac lake are upon the market? but the trade mark is no evidence of excellence. Messrs. BROOKE, SIMPSON, & SPILLER prepare a lac dye which is said to be superior to that which comes from India. They obtain a lac-lake by dissolving stick lac in weak ammonia, and then adding to the solution chloride of tin. The colouring matter of stick lac, although not identical with that of cochineal, bears a considerable resemblance to it in its properties. La Kao. The Rhamnus chloropJiorus and Rkamnus utilis yield a green dye much used by the Chinese, and formerly by the English dyer, who has latterly abandoned it for the aniline greens. Logwood. Syn. CAMPEACHY WOOD. This is the heart- wood of Hcematoxylon campechianum, a native of the coast of Campeachy, and cultivated in India and the West Indies. Hcematoxylin, the colouring principle of logwood, occurs in brilliant reddish-white or straw-yellow crystals. When dissolved in water, hcematoxylin forms a colourless solution, which is rendered purple-red by the smallest addi- tion of ammonia. An extract of logwood is very frequently used in dyeing, instead of the wood. In common with other dye extracts, it should be prepared in vacuum pans, and ISO BLEACHING, DYEING, ETC. with exclusion, as far as possible, of air, the presence of which acts detrimentally on the colouring matter. Madder. The Rubia tinctorium, the roots of which yield the madder dye, is a perennial plant growing in the Southern, Central, and Western parts of Europe. Another variety, the Rubia peregrina, is largely cultivated in the Levant, and a third, the Rubiam mimgista or mungeet, in India and Japan. The Levant, Indian, and Japanese madders are also some- times found in the wild state. All the varieties are peren- nial. The dye-stuff imported under the name of " mungeet" from India, is the reedy stem of a species of rubia, and is inferior in tinctorial power to the two other varieties. Large quantities of mungeet are used in Thibet for dyeing the apparel worn by the Llamas. Madder root varies from 4 to 10 inches in length, and is about the thickness of an ordinary goose quill. Deprived of its external brown bark, it presents a yellowish red appearance, and with the excep- tion of the Avignon madder, has a strong smell. The Zealand or Holland madders are distinguished for their marked odour. The best kind of madder is that grown in the Levant, which occurs in commerce under the name of lizari or alizari* The roots of the Levant madder are rather thicker than those of the other varieties, which is due to their being allowed to attain a growth of four or five years, whereas the othe'r roots are used when they are from two to three years old. Madder is sent into the market under the forms of root and powder, the latter being always kept in strong oaken casks, so as to protect it from the action of air and light. European madder root when in powder is technically known as ratine. * By these terms is understood the entire root of the madder. The term madder is applied to the root when pulverized. DYE STUFFS. 151 Besides Dutch madder, that from Alsace and Avignon is rather, before the extensive employment of the, arti- ficial alizarin and purpurin, was in very large demand, and had a high reputation. Alsatian madder is sent into the market in the state of a very fine powder ; and in order to extract its tinctorial principle, it requires boiling a much longer time than the Levant madder. It has a penetrating smell and a bitter taste, and readily absorbs moisture by exposure. It is in best condition after being kept for two years. Avignon madder possesses an agreeable and rather pungent odour. It is met with in the condition of a very fine powder. It absorbs moisture less readily than the other species. That which has been kept in casks for a year is to be preferred for use. It keeps well and undergoes little if any fermentation. The finest quality of ground madder is called crop, or grappe; next come ombro and gamene. and lastly mull, which consists of the refuse and dust from the madder grinding rooms. Flowers of madder, orfleur de garance, as the preparation is called by the French dyers, is obtained by infusing i part of madder in fine powder in 8 or i o parts water, and setting- up fermentation in the liquid, whereby the large amount of sugar* which the root contains is removed. The residue is then thoroughly washed with warm and afterwards with cold water. The residue being next freed from water by means of hydraulic pressure, is carefully dried, and after being again reduced to powder is ready for use. It is used in the same manner as madder, except that in the dye-beck it is subjected to a lower temperature. By the above treat- ment the pectous substances of the madder root, which * The fermented liquid, being submitted to distillation, yields a spirit, which is employed for technical purposes. 152 BLEACHING, DYEING, ETC. would otherwise become insoluble during the process of dyeing, are eliminated. Garancine is obtained by first moistening madder root, re- duced to fine powder, with water, and next adding | part of sulphuric acid, diluted with double as much water. The mixture is next heated by steam for an hour, and the acid removed from the magma by well washing this latter in water. The resulting garancine, next submitted to hydraulic pressure, whereby the water is removed, is then dried and finally ground to a very fine powder, which amounts to about 2 5 per cent, of the madder root operated upon. The sulphuric acid destroys much of the woody fibre and other substances which interfere with the dyeing properties of the madder. The tinctorial value of garancine is three or four times that of madder. When the fluids of the beck left after dyeing with madder root, are strained from the solid residue, and this is treated with half its weight of sulphuric acid, and the resulting mass* in a manner similar to that followed in preparing garancine, a product is obtained, which after drying, goes by the name of garanceux. Garanceux is mostly used for pro- ducing sad colours. It is inferior in tinctorial power to garancine. Madder Extracts are made by treating madder root with boiling water, collecting the precipitates which form as the infusion cools, mixing them with gum or starch, and then adding acetate of alumina or iron. Extracts so prepared form mordanted dyes, which are available for direct applica- tion in calico printing. The consumption of madder, and the various tinctorial pre- parations obtained from it, have, owing to the recent intro- duction of artificial alizarin and purpurin, greatly declined in England. Madder root contains several distinct principles, such DYE STUFFS. 153 as madder red or alizarin, madder purple or purpurin,* madder orange or rubiacin, madder yellow or xanthin. The researches of SCHUNCK have shown that alizarin, the colouring principle of madder root, is derived from a glucoside which he terms rubian, which, under the influence of acids and alkalies, and of a peculiar nitrogenized ferment known as erythrozym, splits up into alizarin and other colouring matter, and a fermentable sugar. The following equation, according to GERHARDT, represents the reaction that takes place : Eubian. Alizarin. Glucose. The chief mordants used in madder dyeing and calico- printing, are the acetates or pyrolignites of ^alumina and iron, the first known as " red liquor ;" the second as " black" or " iron liquor." Formulae for Bed Liquor : 1. URE. Standard Red Liquor. Alum ......... 20 Ibs. Sugar of lead ...... 12^ ,, Boiling water ...... 5 gallons. Stir till dissolved ; let settle and draw of the clear. 2. KCECHLIN. Alum ......... ii kilos. Acetate of lead ...... 82 -5 grammes. Boiling water ...... 32 litres. According to KCECHLIN, this mordant produces the deepest tints with nearly all tinctorial substances. * Purpurin occurs in crystalline red needles, insoluble in cold, but soluble in hot water, and in alcohol, ether, and solutions of the alka- lies. Its formula is C S H 6 8 . 154 BLEACHING, DYEING, ETC. 3. Five-fourths Mordant. Alum 625 grammes. Acetate of lead 450 Boiling water 2 litres. The following, which are French formulae for red liquor, have a high reputation : 4. A. B. c. Alum ... 1 6 kilos. ... 80 kilos. ... 10 kilos. Acetate of lead 12 ... 8*5 ... 10 Boiling water 62 ... 6o~o ... 20 Extract of Lima ) wood at 20 2 ' 4 ' ( at 3 ) 30 Twaddle. 4 Twaddle. Baume . . . / It is customary with English dyers to make up the above without the peachwood liquor, and to add it when the colour is being prepared for printing. 5. For Garancine (MUSPRATT). At 11 Baume = 1-083 S P- g r - = I 5 Twaddle. Alum 25 kilos. ' Acetate of lead 19 Water 80 litres. 6. Strong Mordant. At ] i Baume. Alum 2\ kilos. Acetate of lead 2 Water 6'3 litres. The German dyers frequently prepare their red liquor from basic alum, which they dissolve in acetic acid, the basic alum being first obtained by treating alum with carbonate of soda. Acetate of lime being a cheaper commodity than lead acetate, is frequently substituted for it. The chlorides of ammonium, sodium, and zinc are added to red liquor, since DYE STUFFS. 155 they prevent the too rapid drying of the acetate on the fibre. Tartrate of alumina, which is formed when cream of tartar is mixed with alum, is found to be superior to the acetate for dyeing woollen goods. "Iron liquor" or " black liquor" is made as follows : 1. Copperas, 300 Ibs., dissolved in 175 gallons of hot water; to the solution is added 5 7 gallons of acetate of lime liquor at 1 6 Twaddle. 2. Copperas 32 Ibs.; pyroligneous acid at 7 Twaddle; acetate of lime liquor, at 24 Twaddle, 10 gallons. Iron liquor at about 6 Twaddle, when properly thickened, gives black with madder. From 4 Twaddle downwards to a very diluted state, it gives various shades of purple or lilac ; mixed with red liquor, it gives chocolates. The purified pyroligneous acid should be employed in the preparation of these mordants, as the tarry matters contained in the crude acid act injuriously. Starch is the best thickener for iron liquor. Madder is adulterated with powdered brick, ochre, yellow sand, yellow clay, oak sawdust, mahogany sawdust, fustic, and various dye woods. The presence of any foreign mineral matter may be detected by the amount of ash yielded on incineration. Good madder should yield from 9 to 1 1 per cent, of ash. The best method of estimating the tinctorial value of a sample of madder is to compare its dyeing power with a specimen of known good quality, which is carried out by the following process, given by Dr. CALVERT : Place 1 2 grains of each sample in pans of copper or block-tin with a quart of water. The pans are placed in a water-bath, heated by means of a jet of steam. A piece of calico, mordanted with red, purple, and chocolate mordants, which cover about three-fourths of the surface of the cloth, is placed in each pan. It is important that each strip taken should be about 156 BLEACHING, DYEING, ETC. 3 inches in breadth, and its length equal to one-half the breadth of the calico (26 inches). The swatches are placed in the pans whilst cold, steam is then turned on, and the tem- perature is gradually raised during an hour and a half to 1 80 Fahr. (82 0.), and then for half an hour kept as near the boiling-point as possible. During the whole time of the operation the pieces should be constantly and carefully lifted out of the dyeing liquor, either with a glass-rod, or better still, by a mechanical arrangement. When the dyeing is completed, the pieces are thoroughly washed with pure water, and the brilliancy and intensity of shade carefully compared. If the samples under trial are found to be weaker than the standard, the dyeing operation is repeated, adding such a quantity of the inferior madder as will bring up the colour to the same intensity as the standard. The values are in inverse ratio to the quanti- ties taken. A further trial is, however, necessary to arrive at a correct conclusion as to the value. The dyed pieces are divided into two parts, one of which is kept for com- parison, whilst the other is submitted to a light soaping ; three or four grains of soap to a quart of water being suffi- cient for the surfaces above given. They are carefully heated in this solution for a quarter of an hour, the tem- perature being kept at 180 Fahr. (82 C.). They are then washed and dried, and the tints again compared. The first operation gives the total amount of colour, the second removes any colouring matter of the dye woods which may have been used for the purposes of adulteration. Murexid. Syn. PURPURATE OF AMMONIA. By adding to a solution of alloxan and alloxantin a solution of carbonate of ammonia, magnificent iridescent crystals of a beautiful reddish purple by transmitted, and of an equally beautiful green colour by reflected, light are obtained. Some years back this substance, known as " murexid," was extensively used in DYE STUFFS. 157 dyeing, but it is now almost, if not entirely, superseded by the coal-tar colours. Peachwood. Syn. ST. MARTHA'S WOOD. The source of this dye-stuff is the Ctescdpinia echinata. The best is imported from Nicaragua, and an inferior kind from Sierra Nevada. Peachwood, sapanwood, and Lima wood, all give very similar shades of colour. Persian Berries. Syn. YELLOW BERRIES. FRENCH BERRIES. AVIGNON BERRIES. BERRIES. The berries or fruit of different species of Rhamnus, growing in Persia, the Levant, Southern France, and Hungary. The Persian berries, which are the most valuable, are stated to be the product of the Rhamnus ainygdalinus. Two varieties of these berries are met with in commerce -the larger, a bright olive-coloured berry, which is gathered before being ripe, and a smaller, shrivelled, deep brown kind, which are not removed from the branches until some time after they have reached maturity. The yellow colouring matter of these berries is chryso-rhamnin which occurs in golden yellow crystals. These, when boiled in water, are resolved into xantho-r/iamnin, a substance of an olive yellow colour. According to BOLLEY, chryso-rluimnin is identical with quercetin. Persian berries are chiefly used for dyeing morocco leather, yellow. Cloth, previously mordanted with alum, tartar, or protochloride of tin is also dyed yellow, whilst with sulphate of copper they give an olive, and with sulphate of iron an olive-green colour. Purree. Syn. INDIAN YELLOW. This yellow dye-stuff, imported from China and India, is of doubtful origin, and is more largely vised by artists than by dyers. Some writers suppose it to be derived from an animal source. According to the researches of STENHOUSE and E RDM ANN, purree chiefly consists of purreic acid, a strongly tinctorial substance, com- bined with magnesium. rue UNIVERSITY 158 BLEACHING, DYEING, ETC. Quercitron Bark. Syn. BARK. This yellow dye material is the inner bark of the Quercus tinctoria, Quercus nigra, or Quercus citrina, a species of oak, a native of America, grow- ing more particularly in Pennsylvania, Carolina and Georgia. Quercitrin, the pigment of quercitron bark, is a neutral substance which, when treated with dilute acids, yields quercetin, a substance of a lemon-yellow colour, which occurs in commerce under the name of flavine. "With picric acid, quercitron bark affords a magnificent yellow dye. Rhubarb. The root of common rhubarb contains a yellow colouring principle, termed rhein or chrysophanic acid) which is soluble in boiling achohol and ether, from which it crystallizes in golden yellow crystals of a metallic appear- ance. With alkalies it produces a reddish-brown coloured liquid. Sandal Wood. This is the wood of the Pterocarpus santalinus, an Indian tree. It is imported in logs, which are of a deep red colour externally, and a bright red internally. The colouring principle of sandal wood resides in a resinoid body named santalin, which appears to be the oxidation product of a colourless body named santal. Santalin is also found in barwood, the source of which is Baphia nitida, an African tree. According to BANCROFT, if wool be mordanted with alum and tartar, and then dyed in a bath of sandal wood and sumach, it takes a reddish-yellow colour. Safflower. Syn. BASTARD SAFFRON. DYERS' SAFFRON. The dye-stuff to which this name is given, consists of the dried florets of Carthamus tinctorius, a thistle-like plant, cultivated in Spain, Egypt, the Levant, and in some parts of Germany. Safflower contains two colouring principles a yellow and a red one. The latter, which is the tinctorial agent of the plant, is called carthamin. The yellow is removed by water and is rejected. The red is easily dis- DYE STUFFS. 159 solved out from the florets by weak solutions of the carbonated alkalies, and is again precipitated on the addition of an acid. Safflower is employed for dyeing silk, to which it imparts a brilliant but very fugitive colour. Saffron. Saffron is the prepared stigmata or stigmas of the Crocus sativus, or saffron crocus. There are two principal varieties of saffron known in commerce : hay saffron, and cake saffron. Hay saffron consists of the stigmas with part of the styles, carefully separated from the other part of the flowers, and then dried by a very gentle heat. Cake saffron is the last kind compressed into a cake, after it has been softened by the fire and afterwards dried. Saffron is very largely and constantly adulterated. The chief sophisticants are safflower, marigold, and carbonate of lime. Saffron owes its colour to crocin, a glucoside. Turmeric. This dye-stuff is the dried rhizome or under- ground stem of the Curcuma longa,&nd the Curcuma rotunda, a plant growing in India, Java, and Ceylon. The finest kinds come from the latter island. Curcumin, the colour- ing principle of turmeric occurs as a brownish yellow mass. It dyes cotton without a mordant. It gives a golden yellow to wool, and an orange tinge to scarlet. It is, however, a very fugitive dye. Weld. Weld consists of the dried herbs and stems of the Reseda luteola, a native of the South of France. Luteolin, the colouring matter of weld, is a substance of considerable durability, and when sublimed condenses in yellow needles. The decoction of weld imparts a rich yellow to goods mordanted with aliim, tartar, or chloride of tin. Woad. Syn. DYER'S WOAD ; PASTEL, Fr. The Isatis tinctoria. To prepare them for the dyer, the leaves of the plant are partially dried and ground to a paste, which is made into balls ; these are placed in heaps, and occasionally sprinkled with water, to promote the fermentation ; when 160 BLEACHING, DYEING, ETC. this is finished, the woad is allowed to fall down into lumps, which are afterwards reground and made into cakes for sale. The woad thus prepared is mixed with boiling water, and allowed to stand for some hours in a closed vessel, about i-2oth its weight of newly slaked lime being added to it. The mixture is then digested at a moderate temperature, and stirred every three or four hours, when a new fermentation begins ; a blue froth rises to the surface, and the liquor, though it appears itself of a reddish colour, dyes woollens of a green which, like the green from indigo, changes in the air to a blue. It is said this process does not succeed well on the small scale. Woad is now mostly used in combination with indigo. Fifty Ibs. of woad are reckoned equal to i Ib. of indigo. By increasing the proportion of alum or red-liquor, the colour verges on purple ; and by employing a little acetate of iron, or green copperas, the darker shades of blue are pro- duced. Verdigris, blue vitriol, and alkalies, turn it more on the blue ; whilst a mordant of tin imparts a violet cast. Coal- Tar Colours. The old synonym of . aniline colours is hardly now applicable, as these only form a portion of the colours obtained from TAR. Coal-tar consists of the oily fluid obtained in the destructive distillation of coal, during the manufacture of ordinary illuminating gas, and collected in a tank from the hydraulic main and con- densers. The composition of coal-tar is highly complex, the most important constituents, being, however, benzol, toluol, naphthalene, anthracene and carbolic acid. Naphtha, which is one of a series of homologous hydrocarbons obtained by distilling coal-tar, yields, by rectification, between 180 and 250 Fahr. (82 and 121 C.), an almost colourless liquid, the benzol of commerce. By the action of a mixture of nitric and sulphuric acids on benzol, nitro-benzol, a heavy oily liquid with an odour of oil of bitter almonds, is obtained. In commerce DYE STUFFS. 161 this substance is made in large cast-iron pots, fitted with tight covers, and provided with sfcirrers worked /by steam power. By means of pipes the reagents are admitted, and the nitrous fumes are carried off, while the nitro-benzol and the spent reagents are drawn off from the bottom. The entire charge of benzol is first placed in the vessels, and the mixed .acids are, as the reaction is very energetic, cautiously run in, the whole being well stirred throughout. When finished, the contents are drawn off, and the nitro-benzol collected, washed with water, and finally washed with a weak solution of soda. Nitro-benzol is converted into aniline in a similar apparatus, only provided with the means of admitting a current of superheated steam, and condensing the aniline as it distils over. In the vessel iron borings are placed, and acetic acid and nitro-benzol cautiously run in as the reduction is violent, stirring well all the time. A current of superheated steam is passed through, and the aniline collected as it distils over, as a pale, sherry-coloured, oily liquid, boiling at 360 Fahr. (182 Cent.), and of sp. gr. 1-02. Aniline. C G H 7 xsf. Syn. PHENYLAMINE. A peculiar vola- tile organic base first noticed by UXVERDORBEN in empy- reumatic bone-oil, and afterwards obtained by RUXGE from coal-tar, and by FRITZSCHE, ZININ, A. W. HOFMAXN, and others, as a product of various reactions, processes, and decompositions, particularly those attending the destructive distillation of nitrogenous organic bodies. Aniline is now invariably obtained, on the large scale, indirectly from coal-tar, from the naphtha, or, more correctly, from the nitro-benzol, of which this is the source. The following are the leading commercial and experimental processes : i . From COAL-TAR. The aniline present in coal-tar may be obtained by washing the crude naphtha with dilute hydro- chloric acid, the clear portion of the liquid (containing the hydrochlorates of the bases present) is then decanted and 1 62 BLEACHING, DYEING, ETC. carefully evaporated over an open fire until acrid fumes begin to be disengaged, when it is again decanted or filtered ; the clear liquor, or filtrate, is next treated with caustic soda or milk of line in excess, by which the bases are liberated under the form of a brownish oil ; the whole of the resulting mixture is now submitted to distillation, the portion which passes over at or about 360 Fahr. (182 Cent.)., and which consists chiefly of 'crude aniline, being collected separately ; the product is purified by rectification at the same temperature, and, lastly, by fresh treatment with hydrochloric acid, and careful distillation with excess of soda, or milk of lime, as before. 2. From NITRO-BENZOL : a. (ZiNix.) An alcoholic solu- tion of nitro-benzol, after saturation with ammonia, is treated "with sulphuretted hydrogen, until, after some hours, a pre- cipitation of sulphur takes place ; the brown liquid is then repeatedly saturated with fresh sulphuretted hydrogen^ until no more sulphur separates, the reaction being aided by occasionally heating or distilling the mixture ; an excess of acid is next added, and, after filtering the liquid, . and the removal of the alcohol and unaltered nitro-benzol by ebulli- tion or distillation, the residue is lastly distilled with caustic potash, in excess. The aniline found in the receiver may be rendered pure by forming it into oxalate of aniline, repeat- edly crystallizing the salt from alcohol, and finally distilling it with excess of caustic soda as before. The following is a cheaper and more convenient process,. and is the only method used on a large scale : b. (M. BECHAMPS). From NITRO-BENZOL by distillation with a mixture of iron-filings and acetic acid (the acetic acid is now more economically replaced by hydrochloric acid or a solution of chloride of iron). The liquor found in the receiver consists of aniline and water, from which the first, forming the lower portion, is DYE STUFFS. 163 obtained, after sufficient repose in a separator. A very spa- cious retort must be employed in the process, as the mass swells up violently ; and it must be connected with the receiver, by means of a condenser, kept in good action by a sufficient flow of cold water. The apparatus for carrying out BECIIAMP'S method was devised by NICHOLSON, and is exhibited in the subjoined plate. " It consists essentially of a cast-iron cylinder (A) of 10 hectolitres (220 gallons) cubic capacity. A stout iron tube is FIG, 5. fitted to this vessel, reaching nearly to the bottom of the cylinder. The upper part of this tube is connected with the machinery G, while the surface of the tube is fitted with steel projections. The tube serves to admit steam, as well as acting as a stirring apparatus. Sometimes, instead of this tube, a solid iron axle is employed, and in this case there is a separate stearnpipe, D. Through the opening at K M 2 164 BLEACHING, DYEING, ETC. the materials for making aniline are put into the apparatus, while the volatile products are carried off through E. H ser- ves for emptying and cleaning the apparatus. The S-shaped tube connected with the vessel B acts as a safety valve. "When it is intended to work with this apparatus there is poured into it through K, 10 kilos of acetic acid at 8 B. (sp. gr. ro6o), previously diluted with six times its weight of water ; next there are added 30 kilos of iron filings, or cast iron borings, and 125 kilos of nitro-benzol, and immediately after the stirring apparatus is set in motion. The reaction ensues directly, and is attended by a considerable evolution of heat and vapours. Gradually more iron is added until the quantity amounts to 180 kilos. The escaping vapours are condensed in F, and the liquid condensed in R is from time to time poured back into the cylinder A. The reduction is finished after a few hours."* 3. From INDIGO. Powdered indigo is added to a boiling and highly concentrated solution of caustic potash, as long as it dissolves and hydrogen is liberated, the resulting brownish-red liquid is evaporated to dryness, and 'the resi- duum is submitted to destructive distillation in a retort. Prod. 1 8 to 20 per cent, of the indigo employed. 4. By fusing, with proper precautions, a mixture of isa- tin and hydrate of potassium (both in powder). A retort connected with a well-cooled receiver, is employed as the apparatus. The interest attaching to these two methods arises from the fact that the aniline thus obtained is abso- lutely free from toluidine, which is always present in that prepared from coal-tar benzol. 5. From anthranilic acid mixed with powdered glass or sand, and rapidly heated in a retort. * WAGNER'S "Chemical Technology," edited by W. CKOOKES, F.R.S. DYE STUFFS. 165 6. By treating an alcoholic solution of benzine with a little zinc and hydrochloric acid. 7. By heating pheiiyl- alcohol with ammonia in sealed tubes. Many other reducing agents have been proposed for the conversion of nitro-beiizol into aniline, such as arsenite of sodium, powdered zinc, &c., but on the large scale they have all been found inferior to the process of BECHA:,IP. KREMER'S process consists in heating one part of nitro-benzol in a pro- per apparatus with five of water and two and a half of zinc dust. When the reaction is completed, the aniline, amounting to about 65 per cent, of the weight of the benzol, is distilled off in a current of steam. Aniline is a thin, oily, colourless liquid, with a faintly vinous odour, and a hot and aromatic taste, miscible in all proportions with alcohol and ether, very slightly soluble in water, neutral to ordinary test-paper, but exhibiting an alka- line reaction to dahlia-petal infusion and paper. It dissolves camphor, sulphur, and phosphorus, and coagulates albumen, possesses a high refractive power, and precipitates the oxides of iron, zinc, and alumina, from solutions of their salts, and neutralizes the acids like ammonia. With the acids it forms numerous crystallizable compounds of great beauty, which are easily formed, and are precisely analogous to the corresponding salts of ammonia. These, on exposure to the air, acquire a rose colour, in many cases gradually passing into brown. Tests. i. Chromic acid gives a deep greenish or bluish- black precipitate with aniline and its salts. 2. Hypo- chlorite of lime strikes an extremely beautiful violet colour, which is soon destroyed. 3. The addition of two or three drops of nitric acid to anhydrous aniline produces a fine blue colour, which, on the application, of heat, passes into yellow, and a violent reaction ensues, sometimes followed by explo- 1 66 BLEACHING, DYEING, ETC. sion. 4. With bichloride of platinum it yields a double salt, the platino-chloride of aniline, corresponding to the corresponding salt of ammonia. These reactions distinguish it from all other substances. Commercial aniline is a mixture consisting in great part of aniline, paratoluidine, and orthotoluidine in variable proportions. In addition it contains small amounts of metatoluidine, nitro-benzol, odorine, &c., but for all practical purposes it may be regarded as a mixture of aniline and toluidine. As it is obtained from a portion of the light naphtha, boiling between certain temperatures, it will vary according to the naphtha from which it is made. In order to distinguish between various samples of com- mercial aniline, BEIMANN submits them to fractional distilla- tion and compares the results. He places 100 c.c. of the sample to be tested in a retort fitted with a thermometer and heated by means of an oil-bath. The liquid, as it distils, is received in a narrow graduated cylinder, and the amount that passes over between every 5 Cent. (41 Fahr.) is noted. In order to obtain standards for comparison he first dis- tilled a sample of light aniline, then one of heavy aniline ; CENTIGRADE. Light 100 Heavy 90 10 85 15 80 20 75 25 60 40 3 '774 4 '029 2 4 | '199 44 438 64 796 5 "036 25 -210 45 '453 6< 8.9 6 044 26 ! '221 46 468 66 846 7 5 2 '27 < -231 47 483 67 872 8 060 28 ! '242 48 498 68 897 9 067 29 ; '253 49 5i4 69 921 70 '075 3 ! ' 2U 4 5 '530 70 946 J I 083 3* '27S 5' 546 7i '974 12 OQI 32 -286 52 '5<>3 72 2'OCO 13 '100 33 '297 53 580 73 2 '03 I 14 108 34 '39 54 '597 74 2'059 15 116 35 '320 55 6i< 1 6 ' I2 5 3 6 -332 56 ^34 i? 134 37 '345 57 652 18 -I 43 38 '3*7 58 6 7 r 19 "152 59 '3?o 59 691 /Specific Gravities corresponding to Degrees of BAUME'S Hydrometer. For Liquids lighter than Water (FBANCCEUR). Degrees. Specific Gravity. Degrees. Specific Gravity. Degrees. Specific Gravity. "srccs. ] 5S1* 10 I "000 23 0-918 36 0-849 49 o'789 it o'993 24 0-913 37 0-844 50 0-785 12 0*986 25 0-907 38 0-839 51 0-781 13 0-980 26 0-901 39 0834 52 0-777 14 '973 27 0*896 40 0*8 ;o 53 0-773 i5 0-967 28 0*890 41 \ 0-825 54 0*708 16 0*960 29 0-885 42 i o'820 55 0-764 i7 '954 30 o'88o 43 0*816 56 0-760 18 0-948 31 0-874 44 o*8i t 57 o'7S7 !9 0-942 32 0*869 45 0-807 58 o'7S3 20 0-936 33 0-864 46 0-802 59 0-749 21 0-930 34 O"8