ralBBi Hanoi n BfiHfl HHtWB wmfflfPS ■ §§93 HI BB BBE Bl ral Bs B II H mw Eg BBBb ■b H| Bra B BB HiBfi& BB SfifiBti BBBBflB BBBBbB y «~^|i,' BoH UBMb BBBBl mHx HBBBB H»ni B I o*^BBHB»Hffi Bra HP* ■ m ®1tf 8. M. Htll Eibranj North (Carolina &iatj> HnitierBitg TP930 n* D8 1 TEX. LIB. This book is due on the date indicated below and is subject to an overdue fine as posted at the Circulation Desk. Digitized by the Internet Archive in 2010 with funding from NCSU Libraries http://www.archive.org/details/bleachingcalicopOOduer BLEACHING AND CALICO-PRINTING. s STANDARD WORKS. MANUAL OF DYEING: FOR THE USE OF PRACTICAL DYERS, MANUFACTURERS, AND STUDENTS. BY E. KNECHT, Ph.D., F.I.C., CHE. RA.WSON, F.I.C., F.C.S., And RICHARD LOEWENTHAL, Ph.D. In Two Large 8vo Vols., 920 pp., with a Supplementary Volume, containing Specimens of Dyed Fabrics. Handsome Cloth. 45s., Post-free. " This host valuable work . . . will he widely appreciated." — Chemical News. " This authoritative and exhaustive work . . . the most complete we have yet seen on the subject." — Textile Manufacturer. " The MOST EXHAUSTIVE and complete work on the subject extant." — Textile Recorder. " The distinguished authors have placed in the hands of those daily engaged in the dye- house or laboratory a work of extreme value and undoubted utility. . . . appeals quickly to the technologist, colour chemist, dyer, and more particularly to the rising dyer of the present generation. A book which it is refreshing to meet with." — American Textile Record. Companion Volume to MM. Knecht and Rawson's " Dyeing." TEXTILE PRINTING: A PRACTICAL MANUAL. Including the Proa sses used in tic Printing of Cotton, Woollen, and Silk Fabrics. By C. F. SEYMOUR ROTHWELL, F.C.S., Mem. Soe. of Chemical Industry, late Lecturer at the Municipal Technical School, Manchester. In Large 8to, with Illustrations in the Text and Specimens of Printed Patterns. O- _A_ IR, HVL" IE H>T T DYEING AND CLEANING: A PRACTICAL BOOK FOR PRACTICAL MEN. By GEO. H. HURST, F.C.S., Soe. t'l ■ in. Industry : Lecturer, Municipal Technical School, Manchester. With numerous Illustrations, 4s. Gel., Post-free. "An OR-TO-DATE handbook has long hern wanted, and Mr. Hurst, who has produced several admirable works, lias done nothing more complete than this. An important work, the more so that several of tin- branches of the craft here treated upon are almost entirely without English manuals for the guidance of workers. The price brings it within the reach of all."— Dyer mi'! i alico-Printer. " Mr. Hurst's work DECIDEDLY FILLS A WANT . . . ought to he in the hands of EVERY garment DYBB and cleaner in the Kingdom.; '— Te.rt{U>i.]^ercniiij.r-S: LONDON: CHARLES GRIFFIN & CO., LIMITED, EXETER STREET, STRAND. BLEACHING CALICO-PRINTING A PRACTICAL MANUAL. GEORGE DUERR, DIRECTOR OF THE BLEACHING, DYEING, AND PRINTING DEPARTMENT AT THE ACCRINGTON AND BACUP TECHNICAL SCHOOLS ; CHEMIST AND COLOURIST AT THE IRWELL PRINT WORKS. ASSISTED BY WILLIAM TURNBULL (OF TURNBULL AND STOCKDALE, LTD.) tClitb 2>ta Mg It Mn "Hg iiiN "O vP iK ivSi 'Na vis iv Sll vV "Zn Symbol Weight. 27-4 122 75 137 11 SO 112 40 12 35-5 52 63 19 1 127 56 207 24 55 200 14 16 31 39 28 23 32 118 51 65 25 BLEACHING AND CALICO-PRINTING. Compounds. — Compound substances are represented by means of formula 1 . The formula of a compound should contain the symbols of all the elements of which the compound is composed : thus, common salt is composed of the elements sodium and chlorine, its formula is, therefore, made up of the symbols Na and CI. NaCl is the formula of common salt, and this formula tells us how much sodium and chlorine common salt contains — viz., 23 parts of sodium and 35 '5 parts of chlorine, by weight, in every 58*5 parts of common salt. The salt called stannous chloride, or, as dyers generally call it, "tin salt"' or "tin crystals,"' is composed of the elements tin and chlorine; the formula of this salt will be made up of the symbols Sn and CI. Now we know that Sn stands for 118 parts of tin and CI for 35 - 5 parts of chlorine, but as stannous chloride is known to contain 118 parts of tin combined with 71 parts (twice 35*5) of chlorine, the formula of this salt will contain only 1 Sn to 2 CI, which could be written SnClCl or SnCl., ; the latter is the usual way of writing it. It will be noticed that each of the symbols for the thirty elements is marked on the left side with a .Roman numeral ; these numbers indicate what is called the combining power or valency of each of the elements : thus, oxygen, O, is marked with two dashes, whilst hydrogen, H, has only one dash ; this indicates that one is equal in value to two H, and when these elements combine to form water, they do so in the proportion of one O to two H, so that the formula of water is OH.,, or 16 parts of oxygen to 2 parts of hydrogen by weight. Classification. — Substances may be divided into three classes, viz. : — 1st, Basic or positive substances ; 2nd, acid or negative sub- stances ; and 3rd, salts or neutral bodies. A base is a metal, or a combination of a metal with oxygen; an acid is a non-metal, or a com- bination of a non-metal with oxygen or hydrogen; a salt or neutral substance is formed when a basic or positive substance combines with a negative or acid substance. Thus, the neutral substance Glauber's salt or sulphate of soda, Na^OSC.,, is made up of the positive or basic substance soda, Ka.,0, and the negative or acid substance sulphuric anhydride, SO... The following is a list of the salts most interesting to the bleacher, dyer, and printer, showing their basic and acid con- stituents : — COMPOUNDS. 29 Name of Salt. Positive or Basic part. Negative or Acid part. Aluminium sulphate, Sodium ,, Calcium ,, Lead , , Ferrous , , Zinc ,, Copper ,, Magnesium , , Aluminium acetate, Chromium ,, Ferrous . , Calcium , , Lead , , Stannous ,, Stannic ,, Calcium chloride, Stannous ,, Manganese ., Sodium bichi-omate Sodium chromate, Lead ,, Sodium phosphate, ,, silicate, ,, carbonate, ,, chloride, ,, stannate, , , chlorate, Aluminium sulpho-cyani Stannic chloride Copper nitrate, Lead , , Copper sulphide, Barium sulpho-cyani Sodium-hydrogen su Potassium ferro-cya ide, lphite nide ferri-cyanide, le, Al 2 O a Na 2 CaO PbO FeO ZnO CuO MgO ALOo Cr 2 3 FeO CaO PbO SnO Sn0 2 Ca Sn Mn Na 2 NaoO PbO H(Na 2 0) (Na 2 0) 2 Na 2 Na Na 2 Na 2 Al 2 Sn CuO PbO Cu Ba NaHO K 4 K 3 (S0 3 ) 3 (H 2 0) 18 S0 3 S0 3 so 3 S0 3 (H 2 0) r S0 3 (H 2 0) 7 S0 3 (H 2 0).-, S0 3 (H 2 0) r (C 4 H G 3 ) 3 (C 4 H 6 3 ) 3 C4H G 3 C 4 H 6 ?> C 4 H 6 3 (H 2 0) 3 C 4 H 6 3 (C 4 H fi 3 ) 2 Cl 2 C1 2 (H 2 0) 2 C1 2 (H 2 0) 4 (Cr0 3 ) 2 Cr0 3 CrO s P0 3 (H 2 0) 12 Si0 2 CO 2 (H 2 O) 10 CI SnOo C1 2 5 (CNS)c Cl 4 N 2 5 N0O5 S (CNS) 2 S0 2 Fe"(CN) c (H 2 0) 3 Fe'"(CN) Weight of Molecule. GG7 142 13G 303 278 287 249 246 409 458 174 158 379 236 354 111 225 19S 262 162 323 358 184 286 5S5 212 213 403 260 187 331 95 253 104 422 329 Sometimes these salts combine with one another, and with water, to form very complex and crystalline salts; this is the case with aluminium sulphate and potassium sulphate, which crystallise together and with water to form common alum, the composition of which is indicated by the formula — Al 2 3 (S0 3 ) 3 K 2 OS0 3 ( tl 2 0) 24 . From this formula we see that alum is made up of 103 parts of the base alumina. 94 ,, !> potash. 320 ,, ,, acid sulphuric anhydride. 432 ,, water in 949 parts of alum by weight. Mordants. —This complex salt, alum, was one of the first sub- stances used as a mordant for fixing colouring matters ; but it is only 30 BLEACHING ANI> CALICO-PRINTING. its base alumina which is useful for this purpose ; this base combines with the acid colouring matters to form insoluble salts. Alum would seem to be a rather expensive source of alumina, seeing that it only con- tains about 11 per cent, of that base. Anhydrous sulphate of alumina, ALO^SOo^, is a cheaper source of alumina, as it contains about 30 per cent, of the base. The pure alumina itself cannot be used as a mordant, because it is not soluble in water ; for, in order to get a substance to combine with cotton, we must first make a solution of it, in order that it may enter the pores of the fibre ; the substance must then be ren- dered insoluble, so that it cannot get out of the fibre again. However, alum and sulphate of alumina are not the best substances to use for the purpose of supplying alumina to the cotton fibre ; the acetate of alumina being a far better substance for this juirpose, especially if we desire to print a pattern in alumina mordant, which is to be after- wards dyed up with one of the acid colouring matters. The acetate Of alumina or "red liquor," as it is called, is very largely used by dyers and calico-printers, and is generally prepared in one of the following ways : — 1st. By dissolving alumina in acetic acid. 2nd. By mixing together solutions of lime acetate and alumina sulphate. 3rd. By mixing lead acetate with alum or sulphate of alumina. These three methods of preparing acetate of alumina can be repre- sented by chemical equations as follows :— Alumina. Acetic Acid. Alumina Acetate. Water. 1st method— A1 2 3 + 3H 2 OC 4 H 6 3 = A] 2 03(C 4 H 6 03) S + 3H 2 0. Lime Acetate. Alumina Sulpliate. Alumina Acetate. Lime Sulphate. 2nd method— 3CaOC 4 H 6 3 + A1 2 3 (S0 3 )3 = A1 2 3 (C 4 H G 3 ) 3 + 3CaOS0 3 . By this method insoluble lime sulphate is formed; this is allowed to settle to the bottom, and is thrown away as it is of no use ; the clear solution only being the "red liquor." Lead Acetate. Alum. 3rd method-3PbOC 4 H G 3 (H 2 0) 3 + Al 2 3 (S0 3 )3K 2 OS0 3 (H 2 0) 24 Alumina Acetate. Potash Sulphate. Lead Sulphate. Water. = A1 2 3 (C 4 H G 3 )3 + K 2 OS0 3 + 3PbOS0 3 + (H 2 0) 33 . This last method being more expensive is not so much used now as formerly. We learn from the above equations the proportion in which the ingredients must be mixed together in order to produce red liquor ; thus, from the first equation we see that 103 parts by weight of alumina require 360 parts by weight of pure acetic acid, or 1,200 parts by weight of the commercial acid containing about 30 per cent., in order to form 463 parts of alumina acetate. By the 2nd equation we find that 474 parts of pure dry acetate of lime require 343 parts of anhydrous sulphate of alumina by weight, PREPARATION OF MORDANTS. 3 1 to produce 409 parts of alumina acetate and 408 parts of sulphate of lime. From the 3rd equation we find that 1,137 parts of crystallised acetate of lead require 949 parts of alum to produce 409 parts of alumina acetate, 174 parts of potash sulphate, 909 parts of lead sulphate and 594 parts of water by weight. The above examples illustrate the great value of chemical equations, as they not only show the way in which the chemicals act upon one another, but also the exact proportions by weight in which we must mix them in order to produce any substance we may require. The advantages of acetate of alumina over most other alumina salts as a mordant are — 1st, its com- paratively low price ; 2nd, its extreme solubility, as owing to this, cloth may easily be charged with a large quantity of the mordant ; 3rd, its unstability, by virtue of which the acetic acid is readily given off, leaving the insoluble alumina upon the cloth in a condition in which it will readily combine with the acid colouring matters. FerPOUS acetate or "black liquor" is a similar compound to "red liquor," and is used in the same way and for the same purpose — i.e., as a mordant for the acid colouring matters ; it is prepared by the following methods, which are very similar to those by which "red liquor " is prepared : — 1st. By dissolving iron or the hydrate of iron or the carbonate of iron in acetic acid, generally the crude pyroligneous acid is used — Iron. Acetic Acid. Ferrous Acetate. Hydrogen. Fe + H 2 OC 4 H 6 3 = FeOC 4 H 6 3 + H 2 . Ferrous Hydrate. Acetic Acid. Ferrous Acetate. Water. FeOH 2 + H 2 OC 4 H 6 3 = FeOC 4 H e 3 + 2H 2 0. Carbonate Carbonic of Iron. Acetic Acid. Ferrous Acetate. Water. Anhydride. FeOC0 2 + H 2 OC 4 H c 3 = FeOC 4 H c 3 + H 2 + C0 2 . 2nd. By mixing lime acetate and ferrous sulphate (copperas) — Lime Acetate. Ferrous Sulphate. Ferrous Acetate. Lime Sulphate. Water. CaOC 4 H 6 3 + FeOS0 3 (H 2 0) 7 = FeOC 4 H 6 3 + CaOS0 3 + 7H 2 0. 3rd. By mixing lead acetate and ferrous sulphate — Lead Acetate. Ferrous Sulphate. Ferrous Acetate. Lead Sulphate. Water. PbOC 4 H 6 3 + FeOS0 3 (H 2 0) 7 = FeOC 4 H O 3 + PbOS0 3 + 7H 2 0. The quantities by weight of each of the substances to be taken can be easily calculated from the above equations. 32 BLEACHIXi; AND CALICO-PRINTING. CHAPTER IV.— STYLES OF CALICO-PRINTING. The two mordants, red liquor and black liquor, are very largely ttsed by calico-printers in what is called THE DYED, OR MADDER STYLE. This is one of the oldest and most important of the various styles of calico-printing. In this style the thickened mordants are first printed on, then dried, aged, duuged, and dyed with alizarine, or other acid colouring matters. The mordants have first to be made into what are technically called " colours " before they can be printed; that is, they have to be made into a kind of paste by means of some thickening matter, as starch, gum, Arc. These colours are not necessarily coloured substances, though they do usually contain some kind of colouring, but this is only for the purpose of sightening, so that the printer may be able to see his work on the cloth ; this sightening is washed out of the cloth after it is printed during the process of dunging (see patterns 1 to 1e). The following are recipes for some of the colours generally used in the " dyed styles " : — Colour No. L— 8" Tw. Red. Water, 8 gallons. Magenta, \ oz. Red liquor, 16° Tw., 8 gallons. Wheat starch, 16 to 32 lbs. Colour oil, i gallon. Boil, and stir till cool, then add Tin crystals, .2 lbs. This colour, when dyed up with alizarine, gives a medium red — hence the term red liquor ; but the same colour if dyed up with quercitron bark would give a yellow ; if dyed up with cceruline paste an olive green would be produced; and, again, if dyed up with alizarine blue paste a kind of indigo blue would be obtained. Therefore, the term 'red liquor" must only be understood in its technical sense, as almost any kind of shade can be dyed upon this mordant ; the shade really depends upon the colouring matter used, the mordant only regulates the depth of the shade. If we want to produce a darker shade we must use a stronger mordant ; if we want a lighter shade a weaker mordant must be used. The following would give a very full red, yellow, olive, »tc. : — DYED OR MADDER STYLE. ?-> No. 2.-12° Tw. Red. Water, 4 gallons. Magenta, 2 oz. Red liquor, 16° Tw., 12 gallons. Wheat starch, 16 to 32 lbs. Colour oil, • h gallon. Boil, cool, and add Tin crystals, •3 lbs. For pinks, light yellows, olives, &c, the following may be used : — No. 3.-1° Tw. Red. Water, 15 gallons. Magenta, ......... 4 oz. Red liquor, 16° Tw., 1 gallon. Wheat starch, 16 to 32 lbs. Colour oil, ......... 4. gallon. Boil, and cool, then add Tin crystals, ........ 4 lb. It will be observed that in these recipes the amount of starch to be used as thickener varies considerably — from 1 to 2 lbs. per gallon of colour; the reason of this is that the consistency of colour re- quired depends upon the pattern, the depth of the engraving, > >i soda, ..... 8 ,, Wheat starch, 20 ,, British gum, ....... 32 ,, Boil, and then add Acetate of iron, 24° Tw., 3 gallons. And when quite cold, add Nitrate of iron, 80° Tw., 1 gallon. After the discharge colours have been printed on the dyed cloth, the pieces are passed in open width through a cistern fitted with rollers, over which the cloth travels up and down through a bath of a clear solution of bleaching liquor at 12° Tw., in which it remains for about one minute, and in coming out of the bath is nipped between rollers which remove the excess of liquor ; it is then passed through water and well washed. Chalk or lime must be added to the chemic bath to neutralise any free acid that might get into the bath, for if this free acid is allowed to accumulate in the bath, free chlorine will be produced, and will so act on the cloth as to destroy the red ground altogether. The reaction which takes place in this process is the production of hypochlorous acid by the action of the tartaric acid on the bleaching powder, and this hypochlorous acid acts at once on the spot where the colour was printed. In order to raise the lead yellows and greens, the cloth is next passed through a weak solution of bichromate of potash, which con- verts the lead salts into the yellow chromate of lead. ' In the discharge style on indigo blue (see patterns 17 and 17a), the cloth is first dyed a plain indigo blue, then soured, washed, dried, and afterwards printed with' the following colours : — No. 17.— Discharge White. Water, 16 gallons. Bichromate of soda, ; . 32 lbs. Caustic soda, . 8 „ Wheat starch, ..... . . 24 „ Olive oil, ...... 4 lb. Boil, &c. This colour must be reduced for light shades of indigo, especially on blotchy patterns. 44 BLEACHING AND CALICO-PRINTING. No. 18.— Discharge Yellow. Water, 2 gallons. Bichromate of soda, ....... 16 lbs. Caustic soda, . . . . . . . . 4 ,, Dissolve, and add Lead yellow paste, . . 4 gallons. 12 ozs. gum tragacanth, . . . . . . 2 ,, And when cold add 6 lbs. blood albumen solution, . . . . . 8 ,, Lead Yellow Paste. (a) In 40 gallons of hot water dissolve 343 lbs. white sugar of lead. (b) In 40 gallons of hot water dissolve 147 lbs. bichromate of soda. Add (b) to (a), wash by decantation, and filter to 15 gallons. Blood Albumen Solution (6 lbs. per gall.). Water at 130° P., 20 gallons. Dry blood albumen, . . . . . . .120 lbs. Add about 1 lb. at a time, stirring well till dissolved, which will take about thirty minutes: No. 19.— Discharge Red. Water, 2 gallons. Bichromate of soda, ....... 16 lbs. Caustic soda, ........ 4 ,, Dissolve, and add 12 ozs. gum tragacanth, ...... 2 gallons. Vermilion, . . . . . . . .120 lbs. 6 lbs. blood albumen solution, ..... S gallons. No. 20.— Discharge Green. Water, 2 gallons. Bichromate of soda, . . . . . . .16 lbs. Caustic soda, . . . . . . . . 4 ., Dissolve, and add 12 ozs. gum tragacanth, .... . . 2 gallons. Guignef s pigment green paste, SO lbs. 6 lbs . blood albumen solution, 8 gallons. No. 21— Discharge Light Blue. Discharge white, 2 gallons. Starch thickening, . . . . . . . 13 ,, Prussian blue pulp, ....... 1 gallon. No. 22.— Discharge Brown. Water, 2 gallons. Bichromate of soda, . . . . . . .16 lbs. Caustic soda, ........ 4 ,, Dissolve, and add 12 ozs. gum tragacanth, ...... 2 gallons. 6 lbs. blood albumen solution, . . . . . S ,, Pigment brown, 64 lbs. INDIGO DISCHARGE COLOURS. 45 No. 23— Discharge Buff. Water 2 gallons. Bichromate of soda 16 lbs. Caustic soda, 4 , , Dissolve, and add 12 ozs. gum tragacanth, 2 gallons. Pigment buff, . • 64 lbs. 6 lbs. blood albumen solution, 8 gallons. By mixing or reducing the above stands, almost any required shade may be produced. The pigments are those usually sold for printing purposes ; they must have been ground to a very fine pulp. Any pigment may be used which does not coagulate the albumen, and will stand the action of the "cutting liquor." After the goods are printed they are passed through the "cutting liquor," which is contained in the box of the padding machine. The box of the padding machine is fitted up with copper rollers, three at the top and three at the bottom. The cloth passes up and down (by means of these rollers) in the cutting liquor, in which it remains for about ten seconds, and then immediately passes through several cisterns containing plenty of cold water in order to remove every trace of acid before the cloth is dried. The cutting liquor is sulphuric acid at 10° Tw., containing 4 ozs. oxalic acid per gallon, and is kept at a temperature of 160° F. The theory of this process is — 1st, the formation of chromic acid by the action of the cutting liquor on the chromate of soda ; 2nd, the action of the chromic acid on the indigo, changing the latter into soluble isatine ; third, the fixation of the coloured pigments by the coagulation of the albumen. Much care and judgment must be exer- cised in this, as indeed in all branches of bleaching, dyeing, and printing, in order to obtain good results. The proper quantity of chromate of soda must be added to the printing colour according to the depth of shade of indigo to be discharged, as also the strength of pattern to be printed ; for if enough chromic acid is not produced in the cutting bath the indigo will not be sufficiently discharged, and the results would be flat and poor shades. On the other hand, if too much chrome be used the cloth will be found to be tendered when it is dried, especially after it has been in use for a short time ; this tendering of the cloth has been a source of great loss to many calico- printers, and many attempts have been made to avoid it ; some add methylated spirits, sugar, glucose, starch, and many other things to the cutting liquor for this purpose, but nothing is so successful as carefully regulating the amount of chrome to the quantity of indigo to be discharged. Another source of trouble in this style is a " tailing " of the pattern (spreading of the pattern beyond its proper limits, especially in one direction) ; this tailing is not due to bad printing, but to too much chrome in the printing colour, or else to the 46 BLEACHING AND CALICO-PRINTING. cutting liquor being too weak or too low in temperature, or, lastly, to the cloth being damp when entering the cutting liquor. A white discharge on indigo can be produced by reversing the above process — that is, by first padding the indigo-dyed cloth on the padding mangle with a solution of bichromate of soda, 1 lb. per gallon ; after drying, the following acid colour is printed on : — No. 24.— 12 oz. - 12 oz. Acid. Water, . . . . . . . . .15 gallons. Wheat starch, 32 lbs. Boil, stir till half cold, then add Oxalic acid, ......... 12 lbs. When quite cold, add Sulphuric acid, 12 lbs. previously mixed with Water, ......... 1 gallon. This colour must be reduced for light shades of indigo. After the cloth is printed and not over-dried, it is well washed in warm water ; coloured discharges cannot be obtained by this method. A third method of discharging indigo is by means of red prussiate and a weak alkali — such as chalk, bicarbonate of soda, carbonate of magnesia, &c. — with or without addition of chlorate of soda ; coloured discharges may be produced by this method. The following are a few examples : — No. 25.— White Discharge. Water, ......... 14 gallons. Red prussiate of potash, ...... 32 lbs. Wheat starch, 20 ,, Colour oil, ........ 4 gallon. Boil, and stir till cold, then add Bicarbonate of soda, ....... 8 lbs. This colour will only discharge medium shades of indigo ; for light shades, the colour may be reduced with starch paste ; but for very dark shades the following may be used : — No. 26.— White Discharge. Water, ......... 14 gallons. Red prussiate of potash, ...... 28 lbs. Chlorate of soda, . . . . . . . 4 , , Wheat starch, 20 „ Colour oil, ......... 4 gallon. Boil, stir till cold, then add Alkaline blue (S ozs. per gallon), i gallon. Chrome mordant, 2 gallons. Mix cold. No. 40.— Extract Violet (Stand). Extract paste, 11 gallons. Alizarine-cyanine, 20 per cent., . . . . . 2 ,, Red mordant, . . . . . • • • 3 ,, Mix cold. No. 41.— Extract Black. Water, 3 gallons. Chlorate of soda, 2 lbs. Logwood extract, 12° T\v. , 8 gallons. Acetic acid, 30 per cent., ...... ^gallon. Colour oil, ......... \ )> Wheat starch 20 lbs. British gum, . . . . • • • • S » Boil, and stir till cold, then add Acetate of chrome, 32° Tw., 2 gallons. No. 42.— Aniline Black (for Steaming-). Yellow prussiate of soda, 12 lbs. Chlorate of soda, . • 6 ,, Water, 12 gallons. Wheat starch, 18 lbs. British gum, . . . . • • • • 8 ,, Colour oil, 2 gallon. Boil, and stir till cold, then add Aniline salts, 18 lbs. Many other " stands " might have been given for this style of work ; but as the author's aim is to reduce everything to the simplest possible condition (as by this means mistakes are often avoided, which is not the case where more complex and more numerous "stands" are worked), the intelligent colourist will find these "stands" quite sufficient for the production of an almost infinite variety of shades. The following are given as a few examples : — No. 43.— Medium Brown. Extract bronze (stand), . 13 gallons. ,, claret (stand), ...... o ,, No. 44. — Tan Shade. 3 Lt. off medium brown. 52 BLEACHING AND CALICO-PRINTING. No. 45.-Buff Shade. 12 Lt. oft" medium brown. No. 46.— Medium Olive. Extract paste, 10 gallons. ,, bronze (stand), 3 ,, ,, slate (stand), 3 ,, No. 47.— Brown Olive. Extract paste 9 gallons. ,, bronze (stand), 4 ,, slate (stand), . 2 ,, ,, claret (stand), 1 gallon. No. 48.— Green Olive. Extract paste, 9 gallons. ,, bronze (stand), 3 ,, ,, slate (stand), 2 ,, ,, blue (stand), 2 ,, No. 49— Yellow Olive. Extract paste, 6 gallons. ,, bronze (stand), ...... S ,, ,, slate (stand), . . . . . . . 2 ,, No. 50 -Old Gold. Extract paste, 4A. gallons. ,, bronze (stand), ...... 11 ,, ,, slate (stand), A gallon. No. 51.— Salmon. Extract paste, S gallons. ,, orange (stand), 4 ,, ,, bronze (stand), . . . . . . 4 ,, No. 52— Terra-Cotta. Extract paste, 8 gallons. ,, red (stand), ....... 4 ,, ,, bronze (stand), ...... 4 ,, No. 53— Chocolate. Extract red (stand), 8 gallons. ,, claret (stand), . . . . . . 6 ,, ,, slate (stand), 2 ,, It will be observed that all the above colours contain acid colouring matters, and are, therefore, fixed with a basic mordant. They stand light and soaping fairly well. The basic colouring matters are often used for the extract style of colours (see patterns Nos. 54 to 60), but these do not stand light nearly so well as the acid colours, many of them fading in a few days if exposed BASIC ANILINE COLOUBS. 53 to direct sunlight; nor do they stand soaping unless combined with such poisonous substances as arsenic or antimony, which is a decided draw- back to the use of the basic colouring matters ; otherwise these basic colouring matters would be very useful, as they produce some of the brightest shades that it is possible to obtain. The following examples will illustrate the composition of the colours containing basic colouring matters. Tannic acid is given as the fixing agent, as the use of arsenic paste ought to be condemned as injurious to the health both of the workmen who have to produce the goods, and of the public who have to handle them : — Methylene blue, . Water, Acetic acid, 30 per cent., Water, Wheat starch, Colour oil, . Boil, and stir till co Tannin paste, . No. 54.-3 ozs. Methylene Blue. 3 lbs. 3 gallons. d, then add dissolve, and add 8 ,, 18 lbs. i gallon. 3 gallons. No. 55.— Tannin Paste. Water, 12 gallons. Tannic acid crystals, ..... 96 lbs. Tartaric acid, . . . . . . 8 ,, British gum, . . . . . . 48 ; , Boil and stir till dissolved. No. 56.-3 ozs. Methyl Green. Methyl green, 3 lbs. Water, 3 gallons. Acetic acid, 30 per cent., . . . . 2 ,, Water, 8 ,, Wheat starch, . . . . . . 18 lbs. Colour oil, ....... ?t gallon. Boil, and stir till cold, then add Tannin paste, . . . . . . 1 ,, Sumach extract, 4S° Tw., .... 2 gallons. dissolve, and add No. 57 Auramine yellow, Water, Acetic acid, Water, Wheat starch, Colour oil, . -2 ozs. Auramine Yellow. 2 lbs. 3 gallons. 2 ,, dissolve, and add ,, 18 lbs. i gallon. Boil, and stir till cold, then add Tannin paste, 2 gallons. 54 BLEACHING AND CALICO-PPJNTIXC No. 58.-2 ozs Bismarck Brown. then add Bismarck brown, Water, Acetic acid. Water, Wheat starch. Colour oil, . Boil, stir till cold Gall extract, 4S Tw., . No. 59.-4 oz. Safranine, . Water, Acetic acid, Water, Wheat starch, Colour oil, . Boil, stir till cold Tannin paste, No. 60—2 OZS Methyl violet, Water, Acetic acid, 30 per cent., Water, Wheat starch, Colour oil, . Boil, and stir till cold, then add Tannin paste, Sumach extract, 4S° Tw., 2 lbs. 3 gallons. 2 ,, dissolve, and add 9 „ 18 lbs. \ gallon. 2 gallons. Safranine Pink. Hb. 4 gallons. 1 gallon, dissolve, and add 10 gallons. 18 lbs. \ gallon. then add 1 Methyl Violet. 2 lbs. 2 gallons. dissolve, and add 10 „ IS lbs. \ gallon. 1 „ 1 ,, After printing, drying, and steaming, it is usual to pass goods containing basic anilines in their colourings through a solution of an antimony salt containing 1 to 2 per cent, of the double tartrate or the double oxalate of antimony and potash, or of the fluoride of antimony. The addition of 1 per cent, of ground chalk will prevent the antimony bath from becoming too acid by neutralising the free acid liberated from the antimony salt, as the base of the latter combines with the colour lake to form a more complex compound of the tannate of antimony and colour base. It is no doubt owing to the greater complexity of these double tannates of a metal and colour base that they resist the action of light and washing better than is the case if the antimony bath is not given. Most likely the same explanation holds good to a great extent with respect to the action of oleine oil upon the colour lake formed in the case of the combi- nation of the acid colouring matters w 7 ith a mineral base ; in these latter it is a double compound of a mineral base with a colour acid and a fatty acid. It may perhaps be as w T ell to observe here that the base oxide of chromium forms a more permanent combination with the colour acids than is the case with alumina, especially with regard to the action of soaping upon these colour lakes ; this is most likely owintr to the fact that alumina is soluble in caustic soda, whilst the PIGMENT COLOURS. 55 oxide of chromium is not. Hence, when soaping goods printed in the extract style we must be careful to select a soap containing very little free alkali. It is in this soaping process after the goods have been printed and steamed that so many failures are made in the extract style. Of course it will be evident that in combinations which must be soaped there must be no very loose colours, or they would be al- most entirely removed in the soaping pi-ocess. But even those colours which are considered moderately fast will not stand a rash and severe treatment with an alkaline soap. As one of the chief objects of soaping in this style of work is to remove the thickening used in the printing- colour, some printers prefer to steep the goods before soaping in a bath of malt liquor, kept at a temperature of about 140° F., which has the power of converting starch into sugar, and thus rendering it more soluble in water, and, therefore, the more easily removed from the cloth without taking the colours with it ; after this treatment a very slight soaping, especially in the open soaper, is sufficient to brighten up the colours to the desired extent. Some colourists print the goods in a much darker colour than is necessary and afterwards soap down the colour to the shade required ; but this is a bad practice, as some colours come down very much more than others in soaping, and where there are a number of colours in a combination, in getting one or two of the colours down to the required shade others may be brought too low and so spoil the effect. Pigments or Pigment Colours.— Another class of colours that may be used for the steam or extract style are the so-called pigments or pigment colours (see patterns Nos. 61 to 65). These are generally coloured minerals very finely ground, and fixed upon the cloth by means of a solution of albumen. For dark and flat shades blood albumen is generally used, but for light and bright colours egg albumen (owing to its greater transparency) is the best. The albumen acts both as the thickening agent and also as the mordant, and as it coagulates at a temperature of about 70° C. the water used for dissolving it should not be above 50° C. Below are a few recipes for the pigment colours. No. 61—3 lbs. Blue (Stand). Ultramarine blue, ....... 4S lbs. Water, 5 gallons. Mix, and add 8 ozs. gum tragacanth, 2 gallons. 6 lbs. blood albumen solution, . . . . . 7 , , Mix cold. No. 62.-4 lbs. Green (Stand). Pigment green pulp, ....... 64 lbs. Water, 3 gallons. Mix, and add 5 ozs. gum tragacanth, - 2 gallons. 6 lbs. blood albumen solution, ..... 7 ,, Mix cold. 56 BLEACHING AND CALICO-PRINTING. No. 63.-2 lbs. Aniline Grey (Stand). Aniline grey, ........ 32 lbs. "Water, 4 gallons. Mix, and add 5 ozs. gum tragacanth, ...... 3 gallons. 6 lbs. blood albumen solution, ..... 7 ,, Mix cold. No. 64.-4 lbs. Lead Yellow (Stand). Lead Yellow, 64 lbs. Water, 2 gallons. Mix, and add 5 ozs. gum tragacanth, .2 gallons. 6 lbs. blood albumen solution, . . . . . 9 ,, Mix cold. No. 65.-6 lbs. Vermilion Red (Stand). Vermilion, 96 lbs. Water, 3 gallons. Mix, and add 5 ozs. gum tragacanth, ...... 2 gallons. 6 lbs. blood albumen solution, . . . . . 9 ,, Mix cold. From the above " stands" a great variety of shades may be produced by reducing and mixing ; although expensive, these colours are very much used, as they are very fast, especially to light. The pigment colours are fixed by steaming, and only require a slight soaping after, to remove any odour of albumen; but the following colours, which may also be used in the steam style, require to be passed through a solution of bichrome in order to develop or raise the colours, and are, therefore, spoken of as Chromed or Raised Colours (see patterns Xos. 66 to 71)— No. 66.-2 lbs. Catechu Brown (Stand). Catechu liquor, ........ 9 gallons. Red liquor, 16° Tw 4 ,, Gum Senegal, 40 lbs. Boil till dissolved, then add Alum, 4 lbs. Chlorate of potash, . . . . . . . 4 ., Stir till cold, then add Oxalic acid, 1 lb. In hot water, £ gallon. Catechu Liquor. Water, 6 gallons. Acetic acid, 30 per cent. ....... 1 gallon. Catechu, ......... 32 lbs. Boil three hours, then make up to 9 gallons. No. 67.^ lbs. Lead Yellow (Stand). White sugar of lead, ....... C4 lbs. Water, . . . . . . . . .10 gallons Wheat starch, 24 lbs. Boil, and stir till cold. CHROMED OR RAISED COLOURS. 57 No. 68.-6° Tw. Iron Buff (Stand) Acetate of iron, 24° Tw., ...... 4 gallons. Water, 12 „ Wheat starch, 24 ,, Boil, &c. No. 69.-2 lbs. Prussiate Blue (Stand). . Water, ......... 9 gallons. Sal-ammoniac, ........ 3 lbs. Wheat starch, 24 ,, Colour oil, ......... 1 quart. Boil, and add Yellow prussiate of soda, iu hue powder, ... 24 lbs. Red prussiate of potash, ,, ,, . . . S ,, Prussiate of tin pulp, ....... 6 gallons. And when cold, add Oxalic acid, ........ 1 lb. In water, ......... ^ gallon. Sulphuric acid, ........ 2 lbs. Mixed with cold water, A gallon. Prussiate of Tin Pulp. (a) Tin crystals, 22 lbs. Dissolved in water, ....... 40 gallons. (b) Yellow prussiate of potash, . . . . . '20 lbs. Dissolved in water, ....... 40 gallons. Add (b) to (a), stirring well all the time, let the precipitate settle, wash pre- cipitate, and filter down to 16 gallons. No. 70.— Prussiate Green (Stand). 2 lbs. prussiate blue (stand), ..... 12 gallons. Extract paste, . 2 ,, Persian berry extract, 4S° Tw., ..... 1 gallon. Acetate of chrome, 32° Tw., ..... 1 ,, No. 71.— Prussiate Olive (Stand). 2 lbs. prussiate blue (stand), ..... 6 gallons. Chrome black, . . . . . . . . 2 ,, Extract paste, . . . . . . . . 4 ,, Persian berry extract, 48° Tw. , . . . . . 2 , , Acetate of chrome, 32° Tw., ..... 2 ,, Chrome Black. Same as steam aniline black, p. 51. By reducing and mixing these stands a great variety of shades may he produced, but after steaming they will all require a passage through a solution of bichrome of about 2 ozs. per gallon of water (in order to raise the colours), and then a good wash in water to remove the chrome. In addition to the above there are many colours in use which do not come under any particular group, and to give recipes for all of them would very much increase the size of this volume without adding to its usefulness, but the following are a few of the more important of recent introduction : — ^ 8 BLEACHIXt; AXD CALICO-PRINTING. NO. 72.— IndigO Blue (for direct printing). (a) S oz. gum tragacauth, 4 gallons. Glucose, 6 quarts. Mix and strain. (&) Well ground indigo, 10 lbs. 8 lbs. caustic stand, 24 gallons. 8 lbs. Caustic Stand. 8 lbs. dry caustic soda to 1 gallon water. Mix and strain through a fine sieve. When cold, add (b) to (a) just before printing. For darker shades decrease the quantity of thickening, and for lighter shades use more. This colour must he printed from a doctor box with not too much pressure on the printing roller. The drying tins must be lapped to prevent over-drying, the cloth must be left quite damp, and must he steamed immediately after printing, otherwise the caustic soda in the colour will be converted into carbonate, and so prevent the proper reduction and fixing of the indigo. The steaming box is a specially constructed one placed im- mediately behind the drying tins of the printing machine, thus enabling the steaming to be proceeded with at once, without having to remove the printed cloth, which would not bear handling in the damp state in which it leaves the drying tins. If everything is right, thirty seconds in the steamer is sufficient to fix the indigo. After steaming the goods are hung up on rails and exposed to the air for twenty-four hours before washing off. No. 73.— Artificial Indigo. This is not much used on account of its high price. Water 4 gallons. Starch, 6 lbs. Colour oil, 1 quart. Boil, and add Powdered borax, ........ 6 lbs. And when cold, add Propiolic acid, 20 per cent, paste. . . . 32 ,, Xanthate of soda, . . . . . . . 4 ,, 1 oz. methylene blue iu i gallon water. Print, dry, hang for twenty-four hours in warm room, then pass through soda solution, soap, and wash. The only advantage of this colour over huligo is that it may be printed along with other colours. No 74.— Indophenol Blue. Indophenol powder, ....... 6 lbs. Solution of stannous chloride (8 lbs. per gallon), . 2 gallons. Acetate of lime, 2i~ Tw., . . . . . . 2 ,, Acetic acid, ......... 2 ,, British gum 24 lbs. Heat to 120' F. and let stand all night. Print, dry, steam for one hour, then pass through solution of bichromate of soda (1 oz. per gallon). PRINTING COLOURS. No. 75.— Indigen Blue. Citric acid, .... Alcohol, .... Indigen blue paste, Starch thickening, Tannic acid (10 lbs. per gallon) Print, dry, steam for one hour, and fix with tartar 59 4 lbs. A gallon. 12 lbs. 8 gallons. 1 gallon, emetic as usual, before soaping. No. 76.— Indulin Blue. Indulin blue paste, ....... 12 lbs. Ethyl tartrate, ........ 1 gallon. Starch thickening, ....... 8 gallons. Tannic acid (10 lbs. per gallon), ..... 1 gallon. Print, and steam for one and a-half hours without pressure ; after steaming pass through a chalk bath, then malt and soap. No. 77.— Galloeyanine Violet (L. Durand, Huguenin & Co.)— Dye- Way. Mordant. 80 parts bichromate of potash, dissolved in 100 ,, water. 60 ,, liquid ammonia. 80 ,, hyposulphite of soda, dissolved in 200 , , tragacanth thickening. 50 ,, acetate of magnesia, dissolved in 200 ,, tragacanth thickening. Sieve the three solutions and mix them together, print, steam for two hours, wash, and for 100 yards dye in 4i ozs. galloeyanine insoluble powder. Start cold, and raise to 160° P. in one hour, and keep this temperature for thirty minutes more. Give very light soaping, and finish with light cbloring to clear the whites. No 78.— Fast Myrtle (L. Durand, Huguenin & Co. )— Dye-Way. Mordant. The cloth is mangle-padded with the following mixture : — 20 parts gum Senegal (6 lbs. per gallon). 50 ,, water. 10 ,, acetic acid, 10° Tw. ,30 ,, pyrolignite of iron, 24° Tw. 2 , , sal-ammoniac. Dry in a hot flue, then print on. Lime juice discharge. Lime juice, 24° Tw, British gum, S gallons. 40 lbs. Steam for five minutes in a Mather & Piatt's apparatus, and dung in the usual way; then for every 100 yards of cloth dye with 4 lbs. fast myrtle paste, and proceed as in last recipe. 60 BLEACHING AND CALICO-PRINTING. No. 79.- Fast Myrtle. Print on. 200 parts fast myrtle paste. 250 ,, acetic acid, 10° Tw. 32 ,, nitrate of iron, 100° Tw. 32 ,, acetate of magnesia, 50° Tw. 25 ,, chlorate of potash. 630 ,, tragacanth thickening. 32 ,, acetate of chrome, 32° Tw. Print, steam for cue hour, soap at 120° F. No. 80— Chrome Violet. Thickening, ........ 8 gallons. Chrome violet (Bayer & Co.'s), ..... 16 lbs. Acetate of chrome, 32° Tw., . ..... ^ gallou. No. 81.— Chrome Blue. Thickening, ......... 8 gallons. Chrome blue (Bayer & Co.'s), ..... 16 lbs. Acetate of chrome, 32° Tw.,. ..... J gallon. No. 82.— Chrome Green. 150 parts chrome green (Bayer & Co.'s) to be dissolved in 220 ,, of warm water. 550 ,, thickening. 80 ,, acetate of chrome, 32° Tw. No. 83— Chrome Yellow. 150 parts chrome yellow (Bayer & Co.'s). 770 ,, thickening. SO , , acetate of chrome, 32° Tw. The last four colours are very bright (for colours fixed with chrome); they should be printed on oiled cloth, and steamed for one hour at ."1 or 4 lbs. pressure. No. 84— Brilliant Yellow. Extract paste, S gallons. Brilliant yellow (Alph. Huillard & Co.), . . . 8 lbs. Acetate of chrome, 32° Tw., . ..... 1 gallon. Print, steam, and soap. No. 85.— Brilliant Alizarine Blue G. Extract paste, ........ S gallons. Brilliant alizarine blue G (Bayer & Co.'s), . . . S lbs. paste. Acetate of chrome, 32° Tw., . ..... (gallon. Print on oiled cloth, steam for one hour, pass through chalk bath, soap, wash, and dry. The Insoluble DiazO-ColOUrS. — When aniline hydrochloride is treated with a solution of sodium nitrite and hydrochloric acid, the following reaction takes place : — C 6 H 6 N:NC1 + NaCl + 2H 2 0. Diazo-benzene Sodium Water. Chloride. Chloride. C C H S NH 2 HC1 + NaNOg + HCl = Aniline Sodium Hydro- Hydrochloride. Nitrite. chlcnc alkI. INSOLUBLE DIAZO-COLOURS. 6l If this diazo-compound of aniline be added to an alkaline solution of beta- naphthol, an insoluble scarlet coloured compound is formed, thus — C G H 5 N:NCI + C ]0 H r OH + NaHO Diazo-benzene Beta-naphthol. Sodium Chloride. Hydrate. C H 5 N:NC 10 H C OH Scarlet Compound. + NaCl + H 2 0. Sodium Water. Chloride. Now, as previously explained, an insoluble compound can only be fixed upon cloth by means of albumen, or some similar substance, and this is sometimes done; but generally another method altogether is adopted — viz., the colour is developed directly upon the cloth. and, being insoluble, remains fixed there. A large number of patents have been taken out during the last fifteen years by Messrs. Read Holliday &: Sons ; Meister, Lucius & Bruning ; the Actien Gesellschaft fur Anilin-Fabrikation, and other colour inakei-s, for the production of these insoluble diazo-colouring matters directly upon the cotton fibre. Several methods have been proposed, but the following is the best for producing the diazo-colours upon cotton piece goods : — (1) The goods are "bottomed" by padding through an alkaline solution of beta-naphthol, or alpha-naphthol, on the padding machine (Fig. 12), and dried at a low temperature (about 100° F. to 150° F.). (2) Immediately after being padded, the goods are printed with a thickened solution of the diazotised amine. The following are some of the colours produced by diazo-compounds upon alpha- and beta- naphthols : — On Alpha-Naphthol Ground. Beta-Naphthol Ground. Diazo-Compound. Reddish-brown. Orange. Aniline. Yellow- ,, Yellow-orange. Meta-nitraniline. ,, ,, Scarlet-red. Para-nitraniline. Puce. Dark Amidoazo-benzol. It Dark brown. Bordeaux. Turkey red. Puce. Alpha-naphthylamine. Beta-naphthylamine. Benzidine. ,, violet. Violet. Diauisidine. Red. Blue. Orange-red. J Dianisidine, with chloride \ of copper. Xylidine. In practice many precautions have to be taken to get good results. In the first place, the goods should not be bottomed with the alkaline naphthol solutions long before they are wanted for printing, nor should they be dried at too high a temperature, or exposed to the direct sun- light, for the grounds easily deteriorate, owing to most of the diazo-com- pounds being very unstable, and decomposing easily on standing any length of time, especially if allowed to become warm ; on this account it is necessary to use ice-cold water when making up the colours in summer time. The following are a few of the best direct prints by this method : — 62 BLEACHING AND CALICO-PRINTING. No. 86.— Para-nitraniline Red (Meiater, Lucius & Briining). Prepare a naphthol grounding by padding the cloth with li lbs. beta-naphthol in \ gallon soda lye, 36° Tw., add 10 gallons water and i gallon oleine oil. Dry at a low temperature, and print on the following as soon as convenient. Printing Colour. 1 gallon water. & „ gum tragacanth (1 lb. per gallon). 1 quart acetic acid. 3 lbs. wheat starch. Boil well, cool, and, when quite cold, add 2 ,, crystallised acetate of soda. Add ,1 oz. para-nitraniline (powder) dissolved in 1 quart hydrochloric acid, 36° Tw. , by boiling, then add 1 ,, of water, cool, and add 1 lb. of broken ice, then add oz. nitrite of soda dissolved in •i gallon water.* After printing, dry, wash, and soap, and wash again. No. 87.— Amidoazo-benzol Dark Red (Meister, Lucius & Briining). Ground with beta-naphthol (as above) and print with Printing Colour as follows : — 1 gallon water. h ,, gum tragacanth (1 lb. per gallon). 3 lbs. wheat starch. 1 quart acetic acid. Boil well, cool, ami add 1 lb. crystallised acetate of soda, and, when quite cold, add 1J lbs. amidoazo-benzol N, dissolved in -i gallon water. 1 pint hydrochloric acid, 36° Tw.; cool, and add 12 ozs. nitrite of soda dissolved in l gallon water. Print, dry, soap, ami wash. No. 88.— Alpha-naphthylamine Bordeaux. Ground Avith beta-naphthol as above, and print with the following : — 1 gallon water, i „ gum tragacanth. j ,, acetic acid. 3 lbs. wheat starch ; boil well, cool, and add 14 lbs. acetate of soda, and when quite cold add 'S ozs. alpha-naphthylamine melted with gallon hot water. 3 gills hydrochloric acid, 36° Tw. Stir well, and add 2 lbs. of crushed ice ; keep stirring, and add 4 ozs. nitrite of soda dissolved in 1 lb. water. ,1 lb. ice. Print, dry, soap, and wash. * N.B.— The bracket indicates that the substances enclosed must be mixed together first before they are added to the remainder. INSOLUBLE DIAZO-COLOURS. 63 No. 89.— Dianisidine Blue. Ground with beta-naphthol, and print with the following : — 1 gallon water. £ ,, gum tragacanth. ^ ,, acetic acid. 3 lbs. wheat starch ; boil well, cool, and add 1 lb. acetate of soda, and when quite cold add (4 ozs. dianisidine. 7 ozs. hydrochloric acid, 36° Tw. 3 quarts water. -\ 1£ lbs. crushed ice ; then run in slowly 1 1 lb. nitrite of soda dissolved in I -| gallon water ; and lastly, add VI gill of chloride of copper, 70° Tw. Print, dry, soap, and wash. No. 90.— Azo-Turkey Red (K. Oehler). 3 lbs. 2f ozs. /3-naphthol dissolved in 3 lbs. 81 ozs. of caustic soda solution, 64° Tw. 3^ gallons water. 2 ,, gum mucilage. The goods are first printed in this colour, and, after cooling, immediately passed through the following Preparation of Diazo Solution. 3 lbs. 2i ozs. of finely-ground /3-naphthylamine. 2 lbs. 7 ozs. of hydrochloric acid, 32 per cent. 44 lbs. water. Boil a quarter of an hour, and stir till quite cold, then add 4 lbs. 13| ozs. hydrochloric acid, 32 per cent. 20 lbs. of ice or cold water, to reduce the temperature to 34° F., then add 1 lb. 11 ozs. of nitrite of sodium, 96 per cent., dissolved in 11 lbs. water, run into the cold mixture slowly through a long funnel reaching to the bottom of the mixing vessel, keeping the mixture well stirred all the time, and the temperature below 40° F., with ice if necessary. Next add a solution of 5 lbs. of pure acetate of sodium, and make the mixture up to 220 lbs. with cold water. This diazo solution will keep good only a very short time (two or three hours), aud must be kept cold. After printing in the naphthol colour and padding in the diazo solution, the goods are to be washed in water, then soaped, and finally washed and dried. Resists or reserves are obtained in this style by printing on the material, previously prepared with the alkaline solution of naphthol, a body which will react on the diazo-cornpound, and thus prevent the formation of coloured compounds. The substance most effective for this purpose is stannous chloride (tin crystals). The change which takes place in the constitution of these compounds, and which prevents the formation of colour with the naphthol, is represented by the following equation : — C 6 H 5 N : NCI + 2SnCl 2 + 3HC1 = NH 2 - NH - C C H 5 + 2SnCl 4 . Diazo-benzene Stannous Hydrochloric Phenylhydrazinc. Stannic Chloride. Chloride. Acid. Chloride. 64 BLEACHING AND CALICO-PRINTING. No. 91.— White Reserve. The material is prepared as above with the beta-naphthol solution, and dried ; then print on the following : — 1 gallon gum solution (1 in 1). 10 lbs. tin crystals. 5 lbs. oxide of tin paste. Dry at a low temperature, and then pass into a developing bath made as follows : — 54 lbs. para-nitrauiline N (Meister, Lucius & Briining). 4 gallon water. Place ice in this mixture, and pour in slowly, with constant stirring, I gallon hydrochloric acid, filter if required, and add cold water to make up to 8 gallons ; then add a solution of 74 lbs. sodium acetate in 2 gallons of water. Work the goods in this bath for a short time. Wash, soap for ten minutes at 60° C, then rinse, and dry. No. 92.— Blue Reserve under Para-nitraniline Red. Prepare the goods as above with the beta-naphthol, then print on the following : — 1 lb. 6 ozs. dianisidine salt (Meister, Lucius & Briining). 1 lb. hydrochloric acid, 36° Tw. 24 gallons water and ice to reduce to 0° C, then add 12 ozs. sodium nitrite in h gallon water, and 3 lbs. chloride of copper, 70° Tw. Make up to 5 gallons with cold water, and add to the following thickening : — 24 gallons water. ^ gallon acetic acid, 9° Tw. 2 gallons gum tragacanth (1 lb. per gallon). 10 lbf. wheat starch ; boil well, and cool ; just before printing add 4 lbs. ammonium persidphate. Bed Developing Bath. 1 lb. 6 ozs. para-nitraniline extra, dissolved in 24 gallons water. 1 gallon gum tragacanth (8 ozs. per gallon). 5 gallons ice water. 2 lbs. oxalate of ammonia in 1 }, gallons water, and 3 lbs. acetate of soda crystals. The red developer shoidd be padded on with a padding mangle, of which only the lower roller, which dips into the developer, is evenly lapped with cloth. When leaving the wringing rollers the goods pass a system of syringes, and a vat with running water. After a good wash they are soaped broadwise with f oz. soap. § oz. oxalate of ammonia to each gallon of water. No. 93.— Yellow Reserve. Print the following on goods prepared with naphthol ; dry well ; then pass through the developing solution, and wash well : — NEW PRINTING COLOURS. 65 1 gallon of water. 3 pints acetic acid, 12° Tw. 4 lbs. wheat starch ; boil well, and add 1 lb. auramine cone. (Meister, Lucius & Briining) in i gallon acetic acid, 1 pint glycerine ; and when cold add J 3 lbs. tartaric acid, ( 3i lbs. acetic-tannic acid solution (1 in 1) ; and t 6 lbs. tin crystals, < 2 lbs. oxide of tin paste in ' ^ gallon gum solution (1 in 1 ) . No. 94.— Green Reserve. Print the following on goods prepared with naphthol ; dry, and pass through developing solution ; wash well : — !1 gallon water. 3 pints acetic acid. 4 lbs. wheat starch. Boil well, and add r 14 ozs. brilliant green crystals, in ) 3 pints acetic acid, ) 2 lbs. tartaric acid, \ 1 pint glycerine, and when cold, add ( 3 lbs. acetic-tannic acid solution (1 in 1), ( 3 , , acetate of tin, 36° Tw. Preparation 0/ Acetate of Tin Solution o/36° Tw. Solution (a) 12 lbs. tin crystals, dissolved in 1 gallon acetic acid. 14 ,, water. Solution (b) 12 lbs. white sugar of lead, in 1 gallon acetic acid. 1| ,, water. Add (a) to (b) hot, during constant stirring, cool, allow to settle, and filter off from the chloride of lead. No. 95.— Gallazine Blue. Extract paste, S gallons. Gallazine A (Durand, Huguenin & Co.), . . . 16 lbs. Acetate of chrome, 32° Tw. , £ gallon. Print, steam for one hour, and soap lightly. No. 96.— Azo-Green. Extract paste, 8 gallons. Azo-green paste (Bayer & Co.), 16 lbs. Acetate of chrome, 32° Tw. , i gallon. No. 97.— Diamond Yellow. Extract paste, 8 gallons. Diamond yellow paste (Bayer & Co.), .... 10 lbs. Acetate of chrome, 32° Tw., . . . . • . ^gallon. Acetate of lime, 24° Tw., i ,, 5 66 BLEACHING AND CALICO-PRINTING. No. 98.— Diamond Orange. Extract paste 8 gallons. Diamond orange (Bayer & Co.), ..... 12 lbs. Acetate of chrome, 32° Tw., i gallon. The above three colours are to be printed on oiled cloth, steamed for one hour at 2 or 3 lbs. pressure, passed through a chalk bath at 168° F., then malted and soaped. No. 99— Brilliant Chrome Red. Extract paste, 8 gallons. Brilliant chrome red (Bayer & Co.), .... 16 lbs. Acetate of chrome, 32 D Tw., ..... i gallon. No. 100.— Chrome Rubine. Extract paste, 8 gallons. Chrome rubine (Bayer & Co.), ..... 10 lbs. Acetate of chrome, 32° Tw. , ..... ^ gallon. The above two colours are to be printed on oiled cloth, steamed for one hour ■with pressure, then passed through a chalk bath, malted, and soaped. No. 101.— Alizarine Cyanine Black. Extract paste, 8 gallons. Alizarine cyanine black (Bayer & Co.), . .16 lbs. Acetate of chrome, 32° Tw., ..... h gallon. Acetate of lime, 24° Tw., £ ,, No. 102— Blue Grey. Extract paste, S gallons. Alizarine cyanine black G (Bayer & Co.), . . . 4 lbs. Acetate of chrome, 32° Tw., ..... 1 quart. Acetate of lime, 24° Tw. 1 pint. Print on oiled cloth, steam for one hour at 7 lbs., chalk, malt, and soap at 90° F. No. 103— Dark Grey. Extract paste, 8 gallons. Sterosine grey (Read Holliday & Sons), . . . ^ gallon. Acetate of chrome, 32° Tw., . . . . . \ ,, No. 104— Light Grey. Extract paste, 8 gallons. Sterosine grey, . 1 pint. Acetate of chrome, 32° Tw. , . . . . . 1 , , Print on oiled cloth, and steam at 2 or 3 lbs. pressure. The following are new colours for discharging indigo blue dyed cloth :— No. 105.— Yellow Discharge. 40 parts chrysophenine (Bayer & Co.). 240 ,, 8 ozs. gum tragacanth. 70 , , wheat starch. 2S0 ,, water. Boil, and when cool, add 230 ,, red prussiate of potash. 140 ,, carbonate of magnesia. NEW PRINTING COLOURS. 6 7 No. 106.— Orange Discharge. 40 parts Congo orange G. 240 ,, gum tragacanth (S ozs.). 70 ,, wheat starch. 280 ,, water. Boil, and when cool, add 230 , , red prussiate of potash. 140 , , carbonate of magnesia. No. 107.— Red Discharge. 40 parts brilliant geranine B. 240 ,, gum tragacanth (8 ozs. ). 70 ,, wheat starch. 370 ,, water. Boil, and when cool, add 180 ,, red prussiate of potash. 100 ,, carbonate of magnesia. No. 108.— White Discharge. 240 parts gum tragacanth (8 ozs. ). 70 ,, wheat starch. 410 ,, water. Boil, and when cool, add ISO ,, red prussiate of potash. 100 ,, carbonate of magnesia. Print the above four colours with brush furnisher ; steam for fifteen minutes Avithout pressure; wash, and dry. The carbonate of magnesia paste is prepared by- precipitation of 250 parts of sulphate of magnesia with 100 parts of Solvay soda dissolved in a good quantity of water, pouring off several times, filtering, and allowing to drain. No. 109— Yellow. Extract paste, 8 gallons. Diamond flavine G (Bayer & Co.), . . . . 1 gallon. Acetate of chrome, 32° Tw., 1 quart. Acetate of alumina, 16° Tw., . . . . . 1 ,, Acetate of lime, 24° Tw., 1 ,. No. 110— Cutch Shade. Extract paste, ..... Alizarine SX, 20 per cent. (Bayer & Co.), Diamond flavine G, ,, Acetate of chrome, 32° Tw., Acetate of alumina, 16° Tw. , Acetate of lime, 24° Tw., 8 gallons. i gallon. 1 quart. 1 ,, 1 „ 1 „ No. lll.-Claret Shade. 928 parts extract paste. 28 ,, alizarine Bordeaux (Bayer & Co.). 24 ,, tartrate of alumina, 18° Tw. 16 ,, sulphocyanide of lime, 23° Tw. 4 ,, oxalate of tin, 25° Tw. No. 112.— Plum Shade. 920 parts extract paste. 40 „ alizarine Bordeaux B P (Bayer & Co.). 40 ,, acetate of chrome, 32° Tw. 68 BLEACHING AND CALICO-PRINTING. No. 113— Slate Shade.! 893 parts extract paste. 3 ,, alizarine Bordeaux B P. S4 ,, ,, cyanine black G. 14 ,, acetate of chrome, 32° Tw. G ,, ,, lime, 24° Tw. No. 114.— Tobaeeo-Brown Shade. 842 parts extract paste. 13 ,, alizarine Bordeaux B B. 17 ,, ,, oraDge II. 67 ,, ,, yellow GG (Bayer & Co.). 61 ,, acetate of chrome, 32° Tw. No. 115— Olive Shade. 819 parts extract paste. 13 ,, alizarine cyanine 3 R (Bayer & Co.). 100 ,, ,, yellow G G. 68 ,, acetate of chrome, 32° Tw. No. 116— Extract Black. 816 parts extract paste. 54 ,, alizarine Bordeaux B P. 50 ,, yellow GG. 80 ,, acetate of chrome, 32° Tw. These last eight colours are to be printed on oiled cloth, steamed for one hour at 7 lbs. pressure, malted, and soaped. STARCH THICKENEES. 69 CHAPTER V.— THICKENERS. Thickening- Materials Employed in the Printing" of Calico.— Under the name of thickeners are understood such preparations as are- added along with the colouring matters in order to give them the necessary amount of consistency to allow them to be printed on the required parts in order to produce the patterns without being liable to run or pass beyond their proper limit. The part played by the thickening is simply a mechanical one and has nothing to do with the fixing of the colours ; there is, however, one exception to this in the case of albuminous substances, which act as fixers of the colours as well as thickeners. The thickening substances are generally some varieties of the gums or amylaceous matter so plentifully found in the vegetable kingdom, such as starch and its derivative dextrin, and the different kinds of gum, such as gum arabic, Senegal, tragacanth, &c. They belong to the class of carbohydrates having the same empirical for- mula as cellulose. Amylum or Starch, C 6 H 10 O 5 , is found very largely spread in nature, being the principal constituent of some seeds, as for instance in the case of cereals ; it is also found in the roots, stems, and fruits of many plants. Starch is found in the form of minute granules which, although possessing the same chemical composition, still show a great variety in their characteristics, according to the plants from which they are derived, especially on account of their sizes and shapes when viewed under the microscope, Figs. 17 to 22; the different starches Fig. 17. — Tapioca starch. Fig. IS.— Wheat starch. can readily be distinguished from each other in this way. Starch is a white substance insoluble in cold water, but possessing the peculiarity, when treated with boiling water, of swelling and form- ing a kind of gelatinous mass, the so-called starch paste, a property 7o BLEACHING AND CALICO-PRINTING. for which it is utilised in. practice, since by this process of boiling, the starch granules largely increase in size, and absorb at the same time a large quantity of water, and if the amount of water and starch have been taken in the right proportion, all the water is taken up and a jelly-like mass is formed, from which the water cannot be separated by mechanical means, not even by straining it through cloth. To this valuable property of starch granules is due *l* & a> ? % 7$ 3 CO Fig. 19. — Rice starch. Fig. 20. — Potato starch. the employment of starch in calico-printing, since by being capable of absorbing solutions of mordants and colours, and keeping pigment* in suspension, it enables printers to obtain mixtures capable of being properly printed on cotton. A very characteristic reaction of starch is that, when boiled with water, it gives a blue colour when treated with a solution of iodine in iodide of potassium. Fi2\ "21. — Maize starch. Fig. 22. — Sago starch. Wheat Starch is by far the best thickening for calico-printing, and is the thickening material most employed for the preparation of colours to be printed on the roller printing machine. Good wheat starch should not contain more than 15 per cent, of moisture nor more than a h per cent, of mineral matter, and should be perfectly free from grit. The admixture of wheat starch with potato or other cheaper starches is best detected under the microscope. Maize Starch is sometimes used as a thickening for indigo-printing by the glucose process, as it stands the strong caustic soda very well. GUM THICKENERS. 7 1 Dextrin (known as British gum, guru substitute, &c.) is prepared from starch by a process which alters the properties of the starch without changing the chemical composition. There are several methods for changing starch into dextrin, such as exposing it to a dry- heat of about 200° C. The method most generally adopted is that proposed by Payen, which consists of treating 400 parts of starch with 1 part of nitric acid and enough water to make into a stiff paste, which is dried and then exposed to a temperature of 200° C. The product thus obtained is lighter coloured than that produced by the first method ; hence we have light and dark British gums. Dextrin is soluble in water, but the various samples differ very much in their thickening power, some requiring as much as 8 or 10 lbs. to the gallon of water, while other samples will thicken with 2 or 3 lbs. Those samples of dextrin which thicken with 2 or 3 lbs. per gallon contain much unconverted starch ; while those which require a very large amount, say 12 or 14 lbs. per gallon have been acted upon too much and changed into glucose. For printing purposes dextrin is best when it will thicken with about 6 lbs. per gallon. Colours thickened with dextrin penetrate less deeply into the fibre than those printed with starch thickening ; hence after washing the •dextrin colours are found to be lighter in shade. Natural Gums (Arabic, Senegal, Indian gums, &c.).- — They are not so largely used now as formerly. As found in commerce they differ very considerably both in price and quality. The best Arabic and Senegal gums are readily soluble in water, producing a clear solution, leaving but a small amount of insoluble residue, consisting of dirt, wood, &c. The Indian and other inferior gums are only partially soluble in water ; even after long boiling only a semi-solution is obtained, which, on cooling, becomes "ropey" like a cold solution of soap. 2 lbs. of Indian gum at, say, 4d. per lb. will give a thicker solution than 5 lbs. of Arabic gum at lOd. per lb. ; still the latter is preferable for some kinds of work. Gum tragacanth, commonly called "gum dragon," is a very useful, though somewhat expensive, thick- ening agent. It is the most powerful thickener used by the calico- printer, for if well boiled it gives a good thickening with ^ lb. per gallon. Albuminoid Thickeners. — The best, and in many print works the only, thickener of this class now in use is : — Mood Albumen. — This substance is the dried serum of the blood of animals. The quality of this preparation has been much improved lately • in fact, so much so that but few printers will go to the expense of egg albumen, except for very special colours'. Blood albumen as usually found in commerce is a dry thin scaley substance of a brownish colour. Lately a much improved brand of blood albumen has been placed on the market ; it is in the liquid state and almost colourless ; it is very cheap, and will keep for a long time as it contains an _ ■- 7. a -■' — - PREPARATION OF COLOURS. antiseptic which, without injuring the albumen, preserves it from decomposition. Albumen should not be heated above 50' C. before printing, as it coagulates a: The following table shows the amount of each of the thickeners in general use required to make 1 gallon of thickening for the average class of work, also the approximate cost per gallon of each of these thickenings : — '•'•'li:.-. •- .: i '-t - - - : >-- Maize starch, 1 3J. Light dextrin, 6 ,, Is. 3d. Gem Senegal, 5 ., 3s. 9d. Gam tragacanth, Is. !■'.:■: 1 ;/.' ::.;- . . . . . . . "• Preparation of Thickeners.— For the 'purpose of dissolving thickeners, and also for the preparation of the printing colours, special vessels called "colour pans Pig 23) are employed; these "colour pans " are double-cased copper vessels heated bj steam, which is ad- mitted between the pan and its outer casing. There are arrange- ments for admitting cold water between the pan and its outer casing, in order that the colour when sufficiently boiled may be quickly cooled. Water is also supplied to the pan itself by means of a swing-arm tap, and the entire pan is made to revolve on pivots, so as to be the more easily emptied and cleaned. During the whole of the time that the ingredients of a colour are being boiled, they should be constantly stirred, and this operation is in many cases continued until the mixture is cold. For this purpose the pans are provided with mechanical stirrers. These pxns vary in size from 4 to 36 gallons. To make a thickening of wheat or maize starch, the starch is first mixed with the cold water and about 1 quart of olive oil to every 10 gallons. It is then raised to the boil and kept boiling for half an hour, stirring all the time in order to produce a smooth paste, rin and gum Senegal are simply agitated with hot water until dissolved. Albumen is dissolved by agitation in water heated to not above " Lrum tragacanth should be steeped in warm water for twenty-four hours ; then boiled for six hours in the colour pan. Straining". — A very important operation in colour mixing is straining, the object of which is not only to remove any lumps or grit from the colour, but also to effect a more thorough mixing, and give more homogeneity and softness to the mass. Many attempts have been made to devise apparatus for straining by mechanical means, and where large quantities of the same colour are made these mechanical contrivances are fair!" sue >sfuL But in works where a if colours are required, the old laborious method of forcing the colours by hand through straining cloths is still employed. If the colours have to be strained by hand they should be first sent 74 BLEACHING AND CALICO-PRINTING. through a coarse cloth, and then through one or more finer cloths. "Very fine grit cannot be removed from thick colour by straining, as the pressure necessary to send the colour through the cloth will also force the grit through ; it is, therefore, necessary to be very careful when making up a colour to see that no substance containing fine grit is used. The grit can easily be removed from liquids by allowing the liquid to run slowly through a fine cloth. LOGWOOD PREPARATIONS. 75 CHAPTER VI.— NATURAL ORGANIC COLOURING MATTERS. LOgWOOd (Campeachy WOOd). —This is the heart-wood of a tree, a native of South America and the West Indies, and known botanic- ally as Hcematoxylon campechianum. This dyewood is generally found in commerce in the form of logs, hence its name, but is supplied to customers either rasped or chipped, or in fine powder, or as extract, The colouring matter contained in the wood is found as a glucoside. The ground wood is moistened with water, and undergoes a species of fermentation, in order to decompose the glucoside, when Itamatoxylin is formed, and this, by oxidation, is converted into lunnatein, the colouring principle of logwood — CjgHhOo + = C lfi H 12 0„ + H 2 0. Hematoxylin. Hsematein. Haematein is a polygenetic colouring matter, as it forms differently coloured lakes with different metallic oxides. With alumina it gives purple. With oxide of copper it gives indigo blue. With ferrous oxide it gives bluish-black. With ferric oxide it gives brownish-black. With chromic oxide it gives black. Logwood and its commercial extract, which is a syrupy liquid of 48° Tw., are largely used for dyeing, and in the latter form is much used for printing, principally for the production of blacks, dark blues, drabs, greys, browns, and olives. A peculiar reaction of the colouring matter of logwood is that it turns red when treated with dilute acid. This reaction is very often utilised as a test for dyed goods which are sup- posed to be dyed or topped with logwood, by placing a small bit in water acidulated with sulphuric or hydrochloric acid ; if the piece contains logwood, it will be shown at once by the red colouration it imparts to the dilute acid. The testing of the commercial value of logwood (as of all other natural organic colouring matters) is best effected by practical trials of dyeing and printing. RED WOODS. These are divided into two classes : — 1st. Those, the colouring matter of which is easily soluble in water, such as peachwood, Brazil wood, sapan, Lima wood, etc. 76 BLEACHING AND CALICO-PRINTING. 2nd. Those possessing the colouring matter not readily soluble in water, such as barwood, camwood, &c. The red woods have sunk considerably in importance since the introduction of coal-tar colours. Red woods with soluble colouring matter belong to the genus CcBsalpinia, and seem to contain the same colouring principle. The Brazil, Lima, and peachwood are produced in South and Central America, while sapan is brought into commerce from India, Japan, and China. The coloui'ing matter is found in the wood in the form of glucoside, which, when decomposed, produces a sugar, and a product called brasUin, Co.,H 00 O r . The red dyewoods are not largely used as self colours, but principally in combination with other dyestuffs for the production of compound shades, both in dyeing and in calico-printing (especially in the steam styles), when they are generally connected with mordants, and a certain amount of chlorate; with alumina mordants bluish-reds are produced; with iron and alumina, browns; with chrome, brown tip to chocolate shades. The commercial extracts generally show 40° to 50 3 Tw. They are principally employed for the preparation of red lakes, for paper staining, painting, Arc. Of the other class of red woods, barwood and camwood are now used in diminishing quantity in cotton dyeing, but never in direct printing. Barwood was at one time used, and is yet to a small extent, for the production of colours on cotton cloth, which imitate, pretty well, the old Turkey-reds. Barwood comes from the tree Baphia nitida, growing in Sierra Leone. Red sanders or santal wood is yielded by the small tree Pterocarpus santalinus, a native of India, and contains the colour- ing matter Sanlalin. YELLOW DYESTUFFS. Quercitron Bark. — This is the bark of a species of oak, Quercus tinctoria, growing abundantly in some parts of the United States, particularly Pennsylvania. This colouring matter is also found in the form of a glucoside called Quercitrin, which can be split up into a kind of sugar, and (Juercetin, Co 7 IL s 12 , which is the colouring principle. Quercitron or bark extract, as found in commerce, is a thick syrupy liquid much used by calico-printers for the production of browns, olives, and many other shades ; it is especially useful, in combination with logwood, "ra CO >b cb CO CO CO CO CO CO CO o CO CI oo 00 ifS • CI CI o C) CI ib -* -* TH •* TjH TiH CI m o CI t-- U5 as CI w Highest. T 1 CO !>• p 1>. i~~. p p r^ CO CI CI CI CI ib -* Tt* ■* -t ■* t!H CI -* o CO O o (M lO o ^H Mean. © p "T 1 p p ■^ p p P © ■* CO f-H r* CO CO t-~ 00 H lO -* tR -* ■<* "# CO CO >o as o >•'§ Lowest. CO p p as T* 1 "-•S OS co 1— 1 Cl cb o rji ^* •* TlH CI 00 CO >o co Highest. © p CO p 1— 1 ■ p CO p cb CO o CO CO ■* o o t>- CO Mean. cp p p p p p P p CI t~~ ib as tH CO (N CO Tfl CO «5 K> ■* >o «o (M O ,H CI as o »o «3 _l o CO o -H CI © CI ,_, Mean. !>. p p p p p p p CO CO cs t- CO as cb ib cb CO CO lO «o lO lO oo CO CI CI as rH lO Lowest. CO p p i^H p p ■H K H CO 00 1-- CO 00 cb in CO m w »o >o Sh CO CI m CO >o T(H 00 Highest. t-» : p p ■? p P p CO OS r— as as CO ib CO io lO K> lO 00 W CO "* nH t-- CO os as Mean. ■T" 1 ITS t^ CO p p p p p CO CO 00 o 00 ob 4j< CI r-H t- t- CO CO CO CO >o 1>- in a> CI lO ^1 Lowest. p p p p GO p p -5 t~ r- CO CO CO CO (M CM CI CO o >o o Highest. cp p p p p p p CO co 00 00 as -* t- t- CO CO CO CO • a s • 3 m g - "»" S" as « "o 3 1= O >H s o • — ■ M i> )H ^ as 2. — - M O . S3 o3 ■ Sh" * rO >>t3 ^ ~ o a as "ei CD r*. . S.1 OS * r» ^2 a • — s3 I. o3 oS EH 3 C 03 o3 .7; 1* 13 "3 cj _o .2-8-2 o-=3 g fl & g O "73 '43 o o s " 6 2° | s Pm S3 ° O S3 a> --3 »fto Ph o _£ PH 0) 2 3 ft^S ^3 a i— i o3 +=• S3 as o " •—J ci CO -# >d CO P^ •r M i>i t< r-l <, <1 2 ° (6 m < a ^ to S- 13 Q W 55 ft 80 BLEACHING AND CALICO-PRINTING. Example. — One gramme of indigo is reduced by a mixture of sodium hypo- sulphite and lime water. The liquid measured 935 c.c. 500 c.c. are oxidised, and treated as above described. Weight of precipitate = - 243 : •243 x 935 x 100 .... ...... .... . .•. — = 4o 44 per cent, indigotin and indigo-red. 500 x 1 * ° ° The filter is placed in the extraction apparatus, and the red dissolved by means of alcohol. The alcohol solution is evaporated to dryness, dried at 100 D , and weighed. Weight of extract = "015. From this amount 1 milligramme is subtracted, in order to allow for the slight solubility of indigotin in alcohol. 0135 x 100 x 935 ' — — = Z"52 per cent, indigo-red. SOU F Indigotin (by difference) = 42 "92 per cent. A very quick and practical method of testing the value of indigo is as follows : — Weigh off 1 gramme of the finely powdered sample, and put into a litre flask, avoiding any loss. Add 25 c.c of a normal solution of sodic hydrate (40 grammes per litre) and 10 c.c. of a saturated solution of hyposulphite of soda, then fill to the stopper with boiling water. If the flask be laid on its side and rolled over occasionally, it will be found that all the indigo will be dissolved in less than fifteen minutes. The contents of the flask is then emptied into a stone jar of about the capacity of a litre ; the solution of indigo is allowed to settle in the jar for half an hour in order to cool and become clear. Xow, take a strip of calico 8 inches by 2 inches, and holding the calico by one end, let about 5 inches of the other end dip into the jar of indigo and leave it there one minute ; now withdraw the calico and hang up to dry without allowing it to crease or touch anything. Of course with this small strip of calico we shall not remove all the indigo from the solution, but it will be dyed to a shade the depth of which will depend upon the quality of the indigo under examination. If 1 gramme of pure indigotin be taken and treated as described above, it will be found to dye the strip of cloth a rather darker shade than can be got from any sample of commercial indigo. But if we take respectively T ^, T 6 ^, ^ and -f v gramme of indigotin and treat in the same way, we shall produce standard shades, against which we can compare the samples we want to test. In this way, using 6 flasks, jars, Arc, a man can test 20 to 30 samples in one day. The hyposulphite for the above must be freshly prepared, by shaking up in a stoppered bottle 1 pint of bisulphite of soda with 2 oz. of zinc powder for five minutes, then allowing it to settle and using the clear solution. Indigotin is insoluble in all ordinary solvents, and, therefore, cannot be used as a dye until it has undergone some chemical change. The best substance known for bringing about this change is nascent hydrogen, which, by combining with the indigotin, converts it into what is called indigo-white. ClcHjoXoC^ + Ho = C16H12X2O2. Indigotin. Indigo-white. INDIGO-WHITE AND ISATIN. 51 When the cotton is immersed in a solution of indigo-white, and then exposed to the air, the oxygen of the air combines with hydrogen, and removing it from the indigo-white, reconverts that substance into indigotin, which thus becomes fixed on the cotton. There are various ways of producing nascent hydrogen — ■ 1st. By fermentation of organic matter. This was the old method of producing indigo-white, or reducing the indigo, as it was called. 2nd. By some metallic hydrate, as ferrous hydrate, which, by decom- posing water, liberates nascent hydrogen, thus — 2FeH 2 2 + 20H 2 = Fe 2 H 6 6 + H 2 . The ferrous hydrate is formed when copperas and lime are mixed with water, as in the copperas vat. 3rd. By the action of metallic zinc on caustic soda or lime and water, thus — Zn + 2NaHO + 2H 2 = ZnNa 2 H 4 4 + H 2 . 4th. By the action of hyposulphite of soda on water, thus — Na 2 OSO + H 2 = Na 2 OS0 2 + H 2 . The above are the usual methods for reducing indigo, or, as it is called, " setting the blue vat." There are many ways of producing nascent hydrogen from acids ; but these are not available, as the " blue vat " must be a slightly alkaline liquid in order to keep the indigo-white in solution. Indigo is destroyed by nascent oxygen by being converted into isatin, thus — Ci 6 Hi N 2 O 2 + 2 = C 16 H,oN 2 04. Indigotin. Isatin. This reaction is taken advantage of in the production of a pattern in discharge by printing upon indigo-dyed cloth (see p. 45). It is easy to distinguish indigo from all other colouring matters by the following tests : — ■ 1st. Dilute sulphuric acid has no action. 2nd. Caustic soda solution has no action. 3rd. Strong nitric or chromic acids destroy the indigo, which cannot be recovered. 4th. Treated with a solution of hyposulphite of soda (out of contact with air), the blue is discharged ; but if the solution be shaken up with air, it becomes blue again. 5th. Heated in a small porcelain dish, violet vapours are given off. MADDER. This is the root of Rubia tinctorium and Rubia peregrina, plants which grow in Europe. The best madder is grown in the Levant, and is known by the name of alizari. But madder, like most other vegetable dyestuffs, has been driven out of the market by the cheaper and handier coal-tar colour, alizarine, so that madder has become a very unimportant substance to the calico-printer and dyer. 6 82 BLEACHING AND CALICO-PRINTING. CHAPTER VII.— TANNIN MATTERS. Under this head are included a great variety of vegetable products, the active principle of which is tannin or tannic acid. They include sumach, gall-nuts, myrobolans, divi-divi, barks, kino, hemlock, valonia, catechu, and many others. The most valuable of these are Gall-nutS, an excrescence formed by the puncture of the gall-fly upon the twigs of certain species of oaks. Several varieties of gall- nuts are found in commerce, among which the principal are Aleppo or Turkish galls, China galls, French galls, &c. They vary consider- ably in price and quality, according to the proportion of tannic acid contained in them. The Aleppo galls are the best, containing some- times as much as 77 per cent, of tannic acid, then come the China galls, which are nearly as good as the Aleppo. The French galls are much inferior, containing only 20 to 30 per cent, of tannic acid. Gall- nuts were formerly much used as a mordant in dyeing, and are used for the preparation of gall extract ; but the principal use of ^all-nuts is for the preparation of pure tannic acid. Tannic acid, C 14 H 10 O 9 , is produced on a large scale, and is much used for dyeing, and especially for calico-printing, when delicate shades- are required. It is sold either as a powder or as needle-shaped crystals. Tannic acid forms insoluble lakes with the basic coal-tar colouring matters, and insoluble tannates with many metallic oxides ; but it is in the form of the double tannate of the colour base and a metallic oxide that the fastest and best colours are produced ; hence the neces- sity for treating with a bath of tin or antimony salts cloth which has been dyed or printed with tannin and a basic colouring matter. Sumach is the dried and ground leaves and young twigs of different plants of the family of Terebinthacece, genus Rhus; the most important is the Sicily sumach {Rhus coriaria), but there are many other varieties grown in Europe and America. The best sumach contains 20 per cent, of tannic acid, and is much liked by fancy-shade dyers on account of its containing only a small amount of colouring matter. MyPObolanS contain more tannic acid than sumach, and are pre- ferred for dyeing a full jet black. The commercial article is the dried and crushed pulp of the fruit of Terminalia chebula, which grows in India. Valonia, Divi, Hemlock, Oak bark, «fec, although they contain a comparatively large quantity of tannin, are not largely used for" TANNIC ACID. 8* dyeing and printing, but are extensively used in the manufacture of leather. The chemical methods for determining the proportion of tannic acid in these wares are somewhat difficult to carry out, but the method which is generally employed is to dye a fent of calico which has been printed all over, or in stripes, with a standard iron mordant, and com- pare the depth of shade against that obtained by a similar trial with pure tannic acid. Decoctions of tannin matters, if kept for a long time, undergo a fermentation and split up into gallic acid and glucose, which do not act as mordants for the basic colours, and are, therefore, useless. 84 BLEACHING AND CALICO-PRINTING. CHAPTER VIII.— OILS— SOAPS— SOLVENTS. OILS. — Colour Oil. — Paste colours for printing are much better if made with the addition of a small quantity of oil (from 1 in 32 to 1 in 16); the colours thus made are better to print with, and keep much better than when made without oil ; they are also much better to .strain, especially after they have been kept a few days, and they froth less in working. The best oil for this purpose is olive oil, though many other cheaper oils are used ; but olive oil imparts the least objectionable odour to the printed goods, some oils being very bad in that respect, especially after the goods have been kept in stock for some time. Olive oil consists of two fatty bodies, trioleine, CH.'Ot; .H 0),., and tripalmtiin, aH-(OC 10 H 31 O) 3 . A variety of olive oil, the Gallipoli, or emulsive oil, was formerly much used in the production of Turkey-reds. The Gallipoli oil is olive oil which has been extracted from unripe olives ; it has been allowed to become rancid, and contains free oleic acid. It readily forms permanent emulsions with weak alkalies. The finest kinds of olive oil have a pale yellow colour with a tinge of green, are almost free from odour, and possess a mild and agreeable taste. Inferior qualities have a greenish- yellow or brownish-yellow colour, an unpleasant odour, and an acid taste. Owing to its superior commercial value, olive oil is very liable to adulteration — cottonseed, nut, poppy, rape, and other oils being used for the purpose. Castor Oil is the fixed oil pressed from the seeds of the plant Ricinua communis; as found in commerce it is a colourless oil of high density and viscosity, having a faint odour and disagreeable taste. It consists of a mixture of solid fat — tripalmitin — with the glyceride of ricinoleic acid, C : ,H./OC' b H :: 0. J )... At one time it was only used in medicine, but it is now very largely used in the preparation of "oleine" or alizarine oil, an oil mordant largely used in alizarine dyeing and printing. PREPARATION OF OLEINE OR ALIZARINE OIL.— Many dye and print works prepare their own oleine oil ; the details of the method of preparation vary with each works, and are generallv kept jealously secret, but the process is a very simple one, consisting in the main as follows : — To 100 parts of castor oil of good quality, add slowly 30 parts of sulphuric acid of 1 -5 specific gravity, and leave the mixture over-night. It is best to make the mixture in a leaden vessel, pouring in the acid in a thin stream, and keeping the mixture stirred with a mechanical agitator; the temperature of the mixture should not rise OLEINE OR ALIZARINE OIL. 85 above 35° C. After standing over-night, the excess of sulphuric acid in the product is then removed by agitating (in a large wooden barrel) with a solution of common salt ; after settling, the salt water is drawn off from the bottom of the cask, and the oily product which remains is mixed again with salt water, and after settling, the salt water is drawn off as before. After washing, the oleine is nearly neutralised with caustic soda, and finally completely neutralised with a solution of ammonia. The oleines of commerce are sold according to the amount of fatty acid they contain, which may vary from 25 to 15 per cent., the usual proportion being about 50 per cent. The product consists chiefly of sodium-sulpho-ricinoleate, C ls H 33 (NaS0 3 )0 3 . A good method of estimating the amount of sulpho-ricinoleic acid present in a sample of oleine oil, though perhaps not strictly accurate, consists in treating 50 c.c. of the sample with about 60 c.c. of water and 20 c.c. of sulphuric acid, 1-5 specific gravity. The operation is most conveniently conducted in a flask, the body of which holds 200 c.c, and the neck — which should be long, narrow, and graduated — an additional 50 c.c. 60 grammes of salt are then added, the contents of the flask well shaken up ; and, lastly, the flask filled up to the top mark on the neck with water. After standing about one hour, the volume of fatty acid which rises into the neck of the flask can be read off. Another method is to heat 10 grammes of the sample in a porce- lain dish on the water bath with sufficient dilute sulphuric acid to decompose it, adding 75 c.c. of a saturated solution of common salt and 25 grammes of wax. The sulpho-ricinoleic acid is insoluble in the brine, and therefore rises to the surface and combines with the melted wax. After cooling, the cake of wax is removed, dried as completely as possible on filter paper, carefully heated to remove the last trace of water, and weighed ; the excess over 25 grammes gives the weight of fatty acid in 10 grammes of the sample. SOAPS. — By the term soap is usually understood the various com- mercial products obtained by the action of alkalies on fatty oils. The soaps of commerce may be divided into two classes — hard and soft. Hard soaps are made with solid animal and vegetable fats, free oleic acid, and rosin, by treatment with caustic soda. They are the soda salts of the fatty and resin acids, the excess of alkali and glycerine having been separated. Soft soaps are made with fish oil or vegetable drying oils, by treatment with caustic potash, the excess of alkali and the glycerine being left in ; hence soft soaps are generally more caustic than hard soaps. There are various methods by which soap is manu- factured — the cold process; the boiling method, followed by salting out, &c. The so-called "cold process" consists in mixing the fat, previously melted at as low a temperature as possible, with just suffi- cient strong soda ley (at about the same temperature) to effect complete saponification. The process has the advantage of being simple, and is often employed for the preparation of the cheaper kinds of soap. But 86 BLEACHING AND CALICO-PRINTING. the saponification is apt to he very incomplete, the product often con- taining both free alkali and unsaponified oil, besides which only the purest materials are available, as the whole of the glycerine and ex- traneous matters are retained in the final product. " Marine soap," so called from its valuable property of forming a lather with sea water, is made by boiling palm-nut or coco-nut oil with caustic soda ley of 1-163 specific gravity. The alkali is added gradually until the presence of a faint excess is indicated by the taste. A good soap for the calico-printer and dyer must possess two im- portant properties : it must be as neutral as possible, and thoroughly saponified ; this second quality is of great importance, since two soaps may contain exactly the same amount of alkali, and yet one will not act as well as the other if it has not been well boiled or saponified, since in this case it will not consist entirely of the combination of the fatty acid with the alkali, but will contain also both undecomposed fat and soda. A good and sufficiently long boiling of the soap in manu- facturing, and a good mixing when salting out, will give a good product, since any free alkali will be dissolved in the salt liquor along with the glycerine, and a second washing of the separated soap with hot salt water will, if well stirred, remove any excess of alkali still left in the product. ASSAY AND ANALYSIS OF SOAPS.— A comparative assay of different soaps can be effected in a very simple manner by ascer- taining what measure of a standard solution of the sample must be added to a given quantity of a standard hard water in order to obtain a persistent lather on shaking (see p. 127). One gramme of each sample to be tested should be dissolved in 100 c.c. of proof spirit. The test is made exactly as in determining the hardness of water, the soap solution being added to the standard hard water in small quantities at a time till a lather is obtained on shaking, which remains for at least five minutes ; the smaller the quantity of soap solution required to produce a permanent lather, the better the sample of soap. The complete analysis of soap is a somewhat difficult and tedious operation, but a determination of the leading constituents will be sufficient for most purposes. Soaps for use in printing and dyeing should be tested for the proportions of water, total alkali, free caustic alkali, combined fatty acids, and unsaponified fats ; and alkali in combination as soap. Determination of Water. — The determination of water in soap is important. If the soap is a solid one a fairly representative sample should be reduced to fine shavings by scraping with a knife, 10 grammes is then exposed in a watch-glass for some time to a tem- perature of about 50° C, the heat being gradually raised to 100° C, and continued at that temperature as long as a loss of weight is observed. The soap should not be allowed to melt. The proportion of water in soap varies enormously ; in some of the best kinds of curd ANALYSIS OF SOAP. 8 J soap it does not exceed 16 or 20 per cent., while in inferior soaps it sometimes reaches as high as 40 or 50 per cent. To determine the amount of unsaponiiied fat, place the 10 grammes of dried soap in a plaited filter paper, and exhaust it with redistilled petroleum ether in a Soxhlet's fat extractor. The solution will contain the unsaponiiied fat, the amount of which may be ascertained by evaporating off the ether, drying the residue at 100° C, and weighing. To Determine the amount of Fatty Acids combined as Soap. — Dissolve 10 grammes of the soap in hot water (using a beaker to contain the solution), add a known measure of standard sulphuric acid to the hot solution, using a moderate excess of the standard acid over that required to neutralise the alkali of the soap. While the solution is hot add 20 grammes of white beeswax, then allow it to become quite cold. The fatty acids become amalgamated with the wax, and on cooling, a firm coherent cake is formed, which may be at once rinsed, dried, and weighed ; this weight less 20 grammes gives the total amount of fatty acids, and the amount of unsaponiiied fat previously deter- mined deducted from this, gives the amount of fatty acids combined as soap ; this latter in good soaps should be not less than 60 per cent., whilst the uncombined fatty acids should amount to very little, •5 per cent., or nothing at all. To Determine the Total Alkali. — Add a small quantity of methyl orange to the acid solution, from which the cake of separated fat and wax has been removed, and titrate with standard alkali. The difference between the free acid thus found and that previously added gives the equivalent of acid required to neutralise the total alkali of the soap, which should not amount to more than 9 per cent. To Determine the Free Caustic Alkali. — Exhaust 10 grammes of the sample with 150 c.c. of absolute alcohol, by shaking in a stoppered bottle. jY.B. — A good sample of soap will almost entirely dissolve, leaving only a very small amount of insoluble residue (about 1 per cent.). When the soap has dissolved, filter the solution, and add a few drops of a neutral alcoholic solution of phenolphthalein ; if a pink colour is produced, titrate cautiously with a decinormal acid (1 c.c. = - 004 caustic soda), the volume of which required corresponds to the free caustic alkali of the soap, and should not much exceed 1 part per thousand. If no pink colouration is produced on adding the phenol- phthalein, the liquid should be titrated with decinormal caustic soda: the volume of this required gives the amount of free fatty acids, which again should be very little in a well-made soap. To Determine the amount of Alkali existing in combination toith Fatty Acids as Soap. — To the alcoholic solution, which has been rendered neutral to phenolphthalein, add a few drops of methyl-oi-ange solution and titrate with standard aeid. This gives the alkali combined as soap, and should be about 7 per cent. The number of c.c. of acid 88 BLEACHING AND CALICO-PRINTING. required multiplied by -04 = alkali (soda) in soap. A good soap should, therefore, consist of about from 20 to 30 per cent, water, 60 ,, 70 ,, fatty and resin acids, 6 ,, 8 ,, soda as soap, 01 ,, free caustic soda, Not more than 1 ,, matters insoluble in alcohol, And little or no unsaponiried fatty matters. SOLVENTS. Acetic acid, HC o H 3 2 , is the most useful oi'ganic acid used in dyeing and printing, owing to its property of being a solvent of aniline dyes, as well as of metallic oxides and colour lakes ; whilst at the same time it has no injurious action on the cotton fibre. Acetic acid should be nearly colourless, should give no turbidity when a solution of nitrate of barium or of nitrate of silver is added, and should leave no residue when evaporated to dryness. The strength of acetic acid (such as is suitable for dyeing and colour-making purposes) can easily be deter- mined by titration with standard alkali, using phenolphthalein as the indicator. The commercial acetic acid generally has a strength of about 30 per cent. There is a very pure acid (containing upwards of 97 per cent.) called glacial acetic acid, but this is seldom employed in dyeing and printing, as it is too expensive for that purpose. There is also a crude acid called pyroligneous acid, but it contains too much colouring matter to allow of its being used for most purposes in dyeing and printing, though it is from this crude acid that most of the acetic acid of commerce is made. Glycerine, C :; H.(OH),, a bye-product in the manufacture of stearine candles, and also in the manufacture of soap, is used largely by some colour-makers who think it improves the printing qualities of the colours. It is also used as a solvent of "white arsenic" in the pre- paration of an arsenious mordant used for the fixing of basic aniline colours ; but this way of fixing colours is very objectionable owing to the poisonous nature of the arsenic, and ought not to be tolerated. Glycerine is very liable to impurities and adulterants, especially that which is produced from soapmaker's waste. Distilled glycerine leaves only a very small amount of ash, - 2 per cent., whilst crude glycerine may leave 10 per cent., or even more. Pure glycerine does not blacken when gradually mixed with its own volume of cold strong sulphuric acid ; sugar and other impurities cause a marked darkening or even charring ; pure dilute glycerine does not reduce Fehling's copper solution when heated with the reagent to 100° 0. for a few minutes; but glucose, if present, will reduce the copper compound even before the boiling point is reached. Acetin. — This solvent is used in printing colours containing some basic colouring matters, as indulins, tfcc, which are not soluble in water SOLVENTS. 89 or acetic acid. It is prepared by heating a mixture of 2 parts of glacial acetic acid and 1 part of glycerine for forty-eight hours at the boil, in an apparatus fitted with an inverted condenser. Ethyl Tartrate. — This solvent of coal-tar colouring matters is an article of commerce, and is prepared by heating a mixture of finely- powdered tartaric acid and pure alcohol in the same kind of apparatus that acetin is made in ; the mixture is boiled until the alcohol has combined with the tartaric acid. 90 BLEACHING AND CALICO-PRINTING. CHAPTER IX.— ORGANIC ACIDS— SALTS. ORGANIC ACIDS. CitPiC Acid, C 6 H 5 4 (OH) 3 + H 2 0, is very largely used in calico- printinc as a discharge or resist on alumina and iron mordants, in the madder styles. It occurs in a free state in the juice of many fruits, especially those of the genus Citrus, the lemon, lime, &c, from which it is extracted. The so-called " acid " used by printers for the above purpose is merely the concentrated juice of the lime and lemon fruit. This "acid" or lime juice contains many organic substances, but the citric acid is the only one of any use. Lime juice is usually bought and sold according to its specific gravity in Twaddel degrees ; but this method of valuation is open to many frauds, for many substances may be added to increase the density or even the acidity of the juice, which are of no value to the printer. The following is a better method of finding the value of a sample of lime juice :— To 10 c.c. of the juice add 5 c.c. of rectified spirit free from acid, then add a small quantity of a solution of caustic potash, and stir the cold liquid in a test tube with a glass rod, rubbing the side of the tube with the glass rod for a few minutes; if any precipitate forms, tartaric acid is present and must be removed by filtration. If no precipitate forms (or if formed, after it has been removed), the contents of the test tube mus f be poured into a porcelain basin, rinsing the tube and rod with water, allowing all to pass into the basin without loss. The contents of the basin is now heated until it begins to boil ; if the odour of pine apple is given off, acetic acid is present, and the evaporation should be continued until all the acetic ether has been evolved. The contents of the basin is next exactly neutralised with dilute pure caustic soda, using phenolphthalein as the indicator; now evaporate to dryness on a bath of glycerine, remove from the bath and carefully ignite at a low red heat to convert the citrates into carbonates. Treat the residue with water to dissolve the carbonates, add a quantity of peroxide of hydrogen (sufficient to convert any sulphides into sulphates), and boil. A known quantity of standard sulphuric acid (sufficient to more than neutralise the alkali) is then added, the liquid boiled and filtered, and the excess of sulphuric acid determined in the filtrate by standard alkali. The amount of sulphuric acid neutralised by the ash is equivalent to the total citric acid in the sample. Alkaline citrates will be included in the above estimate of citric acid, but this is only TIN SALTS. 91 just, since alkaline citrates are equally as effective for resisting mordants as is citric acid in the free state. Bisulphate of soda — the most common adulterant — will be ignored if the precaution is taken of adding hydrogen peroxide after ignition. Tartaric Acid, C 4 H 4 4 (OH) 2 , is used in the preparation of some steam colours, and very largely in the discharge colours in the Turkey- red process. It is obtained from tartar, or argol, a deposit formed on the bottom and sides of the vessels in which wine is manufactured. It is a well-crystallised acid, generally of great purity. It is easily estimated by the usual method of titration with normal caustic soda, using phenolphthalein as indicator. Oxalic Acid, C 2 2 (OH) 2 ,2H 2 0. — This acid is used, together with sulphuric acid, in the indigo-blue discharge style ; it is also used some- times in steam colours, but it is very risky to do so as it reacts on cotton in steaming like a mineral acid, having a very destructive action. Oxalic acid is found in commerce in a very pure state, it can be easily estimated by titration with caustic soda in the usual way. SALTS. Stannous Chloride, SnCl 2 + 2H..O, generally known as "tin crystals " or " tin salt," is largely used both in cotton dyeing and printing. It is prepared by dissolving metallic tin previously feathered, in hydrochloric acid, the solution being afterwards concentrated to the crystallising point. It should contain from 50 to 52 per cent, of metallic tin. It is supplied by chemical manufacturers in a state of almost chemical purity. The dry tin salt should be clean, and should give a slippery feeling to the fingers, not wet nor yet too dry. When 2 ozs. are mixed with a gill of water it should dissolve to a clear solution, but when the same quantity is added to a gallon of water, the liquor ought to be milky looking ; this test shows, in the first case, that the salt is acid enough, and, in the second, that it is not too acid. Stannous chloride is often sold in the liquid state under the names of muriate — standing about 60° Tw. — and double muriate of tin, .standing about 120° Tw. ; but the number of degrees Twaddel is no sure indication of the strength of the solution, since common salt or other chlorides, if added, would increase the density, and, consequently, either in the case of stannous chloride or tin solutions, it is best to estimate the amount of tin by volumetric analysis as follows: — Weigh off ^ gramme of the tin salt or 2 grammes of tin solution and dissolve in about 50 cc. of water ; add 2 grammes of pure hydrochloric acid and h gramme of pure zinc foil, and boil till all the zinc is dissolved (this is to reduce any stannic salt to the stannous state) ; add Rochelle salt and bicarbonate of soda in excess (if enough of Rochelle salt is present the solution 92 BLEACHING AND CALICO-PRINTING. will remain clear) ; starch liquor is then added and the solution is titrated with -— iodine till a blue colouration appears. 1 c.c. of the iodine solution = -0059 gramme metallic tin. Stannic Chloride, SnCl 4 , is obtained by oxidation of the stannous salt by different methods ; the purest salt is obtained when chlorine gas is passed into a solution of stannous chloride. But the cheapest method of oxidation is by means of chlorate of soda and hydrochloric acid, thus — 3SnCl 2 + 2aq. + NaC10 3 + 6HC1 = 3SnCl 4 + NaCl + 5 aq. The proportions to be taken are, therefore — 675 parts of tin crystals. 648 ,, hydrochloric acid (33 per cent. ). 106o ,, chlorate of soda. The tin crystals and hydrochloric acid are first mixed together in a stoneware vessel, with about their own weight of boiling water, and then the chlorate of soda in small portions at a time ; an excess of chlorate is shown by the evolution of chlorine gas. By this method of preparation the stannic chloride is mixed with a small amount of common salt, but for most purposes this will be no detriment to it. Stannic Oxide, Sn0 2 , is produced when carbonate of soda is added to a solution of stannic chloride. SnCl 4 + 2Na 2 OC0 2 = Sn0 2 + 4NaCl + 2C0 2 . The precipitated stannic oxide must be well washed by decantation to free it from common salt. This oxide is never used in dyeing and printing, but it is largely used for making stannic salts, which are much used for that purpose. Stannate Of Soda, Na.,OSnO.>, is simply stannic oxide dissolved in a solution of caustic soda, thus — Sn0 2 + 2NaHO = Na 2 OSn0 2 + H 2 0. This salt has been very largely used as a preparation in the "steam styles," but is not nearly so much used now, since good steam colours can be produced upon the much less expensive oleine-oil preparation. To prepare with stannate of soda, the goods are first taken through a solution of the stannate, 10° to 20° Tw., and afterwards through sulphuric acid at about 2° to 4° Tw., then well washed. The sulphuric acid combines with the soda and precipitates the stannic oxide on the fibre, thus — Na 2 OSn0 2 + H 2 OS0 3 = Na 2 0S0 3 + Sn0 2 + H 2 0. Stannic Oxalate, Sn0 2 (C 2 3 ) 2 , and Stannic Citrate, (SnOoy/CioH^Ojj).,. — These are used in some steam colours; they are both prepared by dissolving stannic oxide in the acids; the oxide is not completely soluble, but the milky liquid is what is used. ANTIMONY AND LEAD SALTS. 93 Stannous Acetate, SnO(C 4 H 6 3 ).— This salt is now largely used for producing discharge effects upon cloth dyed with benzopurpurine and other direct colours (stannous chloride when used for this purpose tenders the cloth). Stannous acetate is produced when a solution of stannous chloi'ide is mixed with a solution of acetate of lead, thus — SnCl 2 + PbO(C 4 H c 3 ) = SnO(C 4 H c 3 ) + TbClo. Potassium Antimony Tartrate, KSbOC 4 H 4 6 , commonly called tartar-emetic. This commercial product has been largely used for giving greater fastness to the tannates of the basic coal-tar colours. In its pure form, tartar-emetic is a clear crystallised salt containing 35-5 per cent, of metallic antimony ; it is prepared by boiling in water a mixture of antimonious oxide and cream of tartar, and crystallising the salt. As the virtue of the tartar-emetic is due to the antimony alone, the expensive tartaric acid is now generally replaced by the much cheaper oxalic acid to form the Potassium Antimony Oxalate, K 3 Sb0 3 (C 2 3 ) 3 + 6 aq., which con- tains about 20 per cent, of antimony. Although the oxalate contains a much smaller proportion of antimony than the tartrate, yet, as the selling price is in a still lower proportion, the oxalate is the cheaper salt of the two. Antimony is best determined by iodine in an alkaline solution. 1 gramme of the antimony compound is dissolved in 20 c.c. of water, 20 c.c. of a saturated solution of Rochelle salt is added, also 20 c.c. of a saturated solution of bicarbonate of soda, together with a few drops of starch liquor. A decinormal solution of iodine is then run in from a burette till a blue colouration occurs. Each cubic centimetre of decinormal iodine required = - 0061 gramme of metallic antimony. LEAD SALTS. Acetate Of Lead, PbO(C 4 H G 3 ) + 3 aq., is a salt which has been very largely used both by dyers and printers. In commerce two qualities are distinguished, generally known as white and brown sugar of lead. Lead Nitrate, PbO(NoO-), is a white crystalline salt, which is sometimes used in place of acetate of lead. These lead salts are gener- ally used for the production of chrome yellows, which are simply chromates of lead (pigment-yellow), thus — PbO(N 2 5 ) + Na 2 OCr0 3 = PbOCr0 3 + Na 2 0(N 2 5 ). The amount of lead in acetates and nitrate of lead may be estimated as follows : — Weigh off 2 grammes of the lead salt and dissolve in hot water, adding a drop or two of nitric acid if necessary, precipitate the lead as carbonate by adding excess of carbonate of soda, wash the pre- cipitate well, and dissolve in a measured quantity of normal nitric acid; titrate for excess of nitric acid. Each cubic centimetre of normal 94 BLEACHING AND CALICO-PRINTING. nitric acid required to dissolve the carbonate of lead = -1035 gramme of metallic lead. Bichromate Of Soda, Na^Ci^O^. — This salt has now come to be of verv great importance since it has replaced the more expensive potassium salt. It is largely used by calico-printers as a source of chromic acid in the indigo-blue discharge style, also for the production of acetate of chrome now so largely used in the extract style. It is also lai'gely used by dyers and printers in the production of chrome- lead yellows, chrome -iron buffs, catechu browns, and other raised colours in the chromed or raised style. Bichromate of soda is very deliquescent, readily attracting moisture from the atmosphere, and when exposed for a long time in damp places, it has been found to attract so much water as to form a solution, and leak out of the vessel containing it, but this can be easily avoided by keeping it in a dry room. When of good quality, it will be found an advantageous sub- stitute for bichromate of potash ; its greater solubility is in its favour. Bichrome should be thus tested for the amount of chromic acid : — Weigh off 5 grammes of the sample, dissolve in water and make up to 1 litre. Take off 20 c.c. of the solution, and mix with it 5 c.c. of hydrochloric acid and 10 c.c. of a 10 per cent, solution of potassium iodide. The mixture is allowed to stand about half an hour, and then the liberated iodine determined with decinormal hyposulphite and starch liquoi\ Each cubic centimetre of decinormal hyposulphite required = -00438 gramme of Na 2 Cr o 7 . Phosphate Of Soda, Na.OHPCX + 12 aq. — This is a very useful fixing agent for alumina and iron mordants, being far preferable to the poisonous arsenite of soda too often used. To estimate the amount of pure phosphate of soda in a given sample, the following solutions must be prepared : — 1st. Decinormal Solution of Phosphate of Soda. — Dissolve 11 "93 grammes of pure dry phosphate of soda in water, and make up to 1 litre. 2nd. Acid Solution of Sodic Acetate. — Dissolve 100 grammes of sodic acetate in water, add 100 c.c. of strong acetic acid, and dilute to 1 litre. 3rd. Decinormal Solution of Uranium Nitrate. — Dissolve 18 grammes of uranium nitrate in water, and make up to 1 litre. Some finely- powdered yellow prussiate of potash will also be required. As the uranium nitrate cannot be depended on, the solution must be titrated to determine its strength, as follows : — Measure out 100 c.c. of the decinormal sodium phosphate into a beaker, add 5 c.c. of the acid solution of sodic acetate, heat in a water bath to about 80° C, then run into it the uranium solution from a burette, stirring with a thin glass rod ; after about 90 c.c. have been run in, bring a drop of the mixture, on the point of the rod, upon the surface of a white plate, then, with a bit of platinum wire moistened with the breath, bring a LIME AND ALUMINA SALTS. 95 small particle of the powdered yellow prussiate into the middle of the drop on the white plate, and wait a moment to see if any brown stain, however faint, appears. Should this not occur, add cautiously more of the solution until the colouration is produced in fresh drops tested from time to time. Repeat the experiment with a fresh portion to be certain of the exact point, then read off the burette the number of cubic centimetres required. Suppose 96 c.c. of the uranium solution have been required to produce the colour with 100 c.c. of the phosphate solution, then every 96 c.c. of the uranium solution must be diluted to 100 c.c, or 960 made up to 1,000 c.c. The uranium solution will then be strictly decinormal. Any sample of sodium phosphate can now be tested by treating in exactly the same way as the pure sodium phosphate has been — i.e., weigh off 11-93 grammes, and make up to 1 litre, take off 100 c.c, add 5 c.c. of acid sodium acetate, heat to 80° C, and titrate with the corrected decinormal nitrate of uranium, testing carefully towards the end for the appearance of the brown stain. Each cubic centimetre of uranium solution required = 1 per cent, of pure sodium phosphate in the sample. Carbonate Of Lime (Chalk), CaO0O 2 .— This is a very useful dunging material ; it prevents the dunging beck becoming acid by combining with any acid liberated from the cloth. The chalk for dunging purposes should be a finely-ground white powder, almost entirely soluble in pure nitric acid, from which solution it should give no brown precipitate on the addition of ammonium chloride and ammonia. Acetate Of Lime, CaO(C 4 H 6 3 ).— This salt, which is much used in the preparation of extract colours for calico-printing, is best prepared on the works by neutralising acetic acid with chalk or lime; if properly prepared it will stand at 24° Tw. ; it should give no precipitate on the addition of ammonium chloride and ammonia. Alumina Salts have already been treated of under the heading " Mordants," but there is one thing more to be said about them — that is, they should always be tested for traces of iron. This is best done by padding a small bit of white cloth in a solution of yellow prussiate of potash, and then, without drying, dipping it into the red liquor or other solution of alumina salt to be tested; if a blue stain is produced on the cloth, then the alumina solution contains iron, and is not fit for use. The amount of alumina should also be estimated gravimetrically by adding ammonia in excess ; boil well, filter off the precipitate, wash, dry, and carefully ignite and weigh as A1 2 3 , which, in good red liquors at 16° Tw., should be about 4 per cent,, and very little or no precipitate should be given on adding a solution of barium, chloride. 96 BLEACHING AND CALICO-PRINTING. CHAPTER X.— MINERAL COLOURS OR PIGMENTS. These are insoluble substances and, therefore, cannot be used as dyes, but they are fixed upon cotton cloth by means of albumen in the so- called pigment style of printing. White Pigments. — The best of these is oxide of zinc (zinc white) which is used for producing a light pattern on coloured grounds ; also for mixing with other pigments to give body to the printing colour. Sulphate of Barium, BaS0 4 , sometimes called permanent white, is occasionally used for the same purpose as zinc white, but it is very heavy and does not make up a good printing colour, nor has it the same covering power that oxide of zinc has. China Clay (Silicate of Alumina) is largely used for weighting and finishing calico. It is not much used for calico-printing by machine, as the fine particles of grit which it generally contains is very injurious to the copper rollers. YellOW Pigments. — Lead Yelloiv (Chromate of Lead), PbOCrO., is produced by the precipitation of a soluble lead salt by means of bichromate of soda, thus — Na 2 02Cr0 3 + 2Pb0N 2 5 + H 2 = 2PbOCr0 3 t- Na 2 ON 2 5 + 2HN0 3 . This pigment is largely used as an albumen colour; it is a bright and fast yellow, but blackens if exposed to sulphuretted hydrogen. Lead Orange (Basic Chromate of Lead), Pb._,CrO.-, is formed when the yellow chromate of lead is boiled with lime water. The basic chromate of lead is too red of itself for a good orange, hut by mixing with the yellow chromate the right shade is got. These lead chromates are found in commerce in the form of a thick paste ready for use, and in order to test their value it is best to determine their colouring power by a practical printing trial. Cadmium Yellow (Sulphide of Cadmium), CdS. — This is a good yellow pigment, but too expensive for ordinary printing. The advantage this yellow has over lead yellow is that it is not blackened by sulphuretted hydrogen. Barium Yelloiv (Chromate of Barium), BaOCrO... — This pigment yellow has not got the colouring power of the lead yellow ; therefore it is not much used, although very cheap and free from the objection of going black. There are several other yellow pigments, but they are not nearly so good as lead yellow, and are, therefore, not much used. PIGMENTS. 97^ Iron Buff is a pigment largely used by some printers, especially as a pad colour. It is imported into this country in the form of a thick paste which should be smooth and free from hard lumps and grit, and of a clear buff shade. Red Pigments.— Vermilion (Sulphide of Mercury).— This is a very heavy, bright red powder; it is very expensive, and is often adulterated, the chief adulterant being vermilionette. Vermilionette is a mixture of red lead, eosiue, and some white pig- ment. Bed Lake is another substitute for vermilion ; but none of these substitutes are equal to the genuine vermilion for printing indigo-blue discharge colours, the purpose for which vermilion is chiefly used. Green Pigments. — Guignet or Chrome Green is the hydrate of chromium, CroH^. This important pigment is prepared on a large scale by heating a mixture of bichromate of potash and boracic acid. The pigment is found in commerce as a paste ready for use. Although not a very bright green, it is largely used, because it is not nearly so poisonous as the other mineral greens ; it is also a very fast colour, and stands strong acid, which is necessary when used in the indigo discharge style. Scheele's Green (Arsenite of Copper) is a very bright pigment, but too poisonous to be used for calico-printing. Blue Pigments. — Ultramarine. — This very important pigment was originally prepared by grinding to a fine powder the precious stone Lapis laztili, but is now prepared artificially by a chemical pro- cess. Ultramarine comes into the market as a dry powder of a bright blue colour. The pigment not only varies in shade from a greenish to a rather violet blue, but is also very liable to adulteration with kaolin, sulphate of barium, etc., which reduce the strength of the colour. The difference in the strength and shade of samples of ultramarine can be seen by placing small quantities near together upon a sheet of white paper; but the most reliable test is to print the samples as albumen colours. The great advantage of ultramarine blue over all other bright blues is its fastness against air and light. Ultramarine blue is de- stroyed by acids. Prussian or Berlin Blue, Fe 7 Cy ls ,. is prepared by precipitating a solution of a ferric salt with a solution of ferro-cyanide of potash, according to the following equation — 2Fe 2 Cl 6 + 3K 4 FeC fi N 6 = Fe 7 Ci 8 N 18 + 12KC1. The commercial product is a dark blue paste. It is not much used in cotton printing. Many other pigment colours were formerly in use, but they have been superseded by alizarine and other acid coal-tar colours, fixed with acetate of chrome and developed by the steaming process. 9 8 BLEACHING AND CALICO-PRINTING. CHAPTER XL— COAL-TAR COLOURS. The very remarkable substance coal tar is the source of a large and most important class of colouring matters. Coal tar consists of a large number of different substances ; the separation of these substances in the pure state forms a special branch of industry. THE DISTILLATION OF COAL TAR. The separation of the different constituents of coal tar is effected by means of fractional distillation, a process which depends upon the fact that, on heating a mixture of different liquids, the one which has the lowest boiling point will pass over first into the distillate, the others following in order according to their boiling points. The boiling points of the different constituents of coal tar vary considerably ; it is, there- fore, possible, by separating the fractions of the first distillation, to obtain certain constituents in the first fraction only, while others are contained in the second or third. The process of distillation is carried out in large iron retorts. The first distillate, containing all the pro- ducts which pass over at a temperature not exceeding 180°, is techni- cally known as light oil. The second fraction consists of heavy oil, so called because it sinks in water. The third fraction of the distillate is the so-called green grease or anthracene oil. Not one of the preceding three distillates consists of a pure and simple body, but each yields a typical substance. From the light oil we get benzene and its homo- logues ; from the heavy oil, naphthalene ; and from the green grease, anthracene. The coal-tar colours may be divided into three classes, viz. : — 1st. Benzene colours, comprising the so-called aniline dyes. • 2nd. Naphthalene colours or azo dyestufis. 3rd. Anthracene derivatives or acid colours, as alizarine, etc. Benzene is a colourless liquid. Its specific gravity at 15° C. is 0885. It boils at 80°, and is insoluble in water, dilute acids, and alkalies. Benzene may be regarded as the simplest representative of a large class of compounds which are known as " aromatic compounds," to which nearly all the artificial organic colouring matters belong. It consists of 6 atoms of carbon and 6 atoms of hydrogen ; the carbon atoms are bound together in such a manner as to form what is known as the benzene ring, thus : — COAL-TAR PRODUCTS. H 99 H— C I H— C • l C— H II C— H Cfi Hn Symbolic ormula of benzene. H Graphic formula of benzene. The benzene ring is very stable, and is only split up by very energetic chemical action. Toluene, C C H 5 CH,, is one of the homologues of benzene, and is obtained from the light oil by fractional distillation. If one of the hydrogen atoms of benzene is replaced by methyl (CH 3 ), methylbenzene, or toluene, is formed. Experience has shown that whichever hydrogen atom in the benzene ring is replaced, one and the same toluene is in- variably obtained. Toluene is lighter than benzene. Its specific gravity is 0-872 at 15°. It does not solidify on cooling, and its boilino- point is 111° C. Xylenes, C c; H 4 (CH 3 )o. — If two atoms of hydrogen in the benzene ring are replaced by methyl, three isomeric xylenes are formed which each possess the formula C 6 H 4 (CH 3 ) 2 . They are distinguished from each other by their constitutional formula? in the following manner: CCH 3 c.CH 3 c.CH, C.CHg HC HC, HC CH CH S HC HC CH CH CH CH c.CH, ( l >2-) (1,3.) (1,4.) For convenience sake the carbon atoms of the benzene ring are numbered from 1 to 6, beginning usually at the top and proceeding to the right hand. By this means it is possible to express a constitutional formula without making a diagram. The position (1, 2) is known as the ortho, (1, 3) as the meta, and (1, 4) as the para position. The three xylenes referred to above are thus known as ortho-, meta-, and para-xylene respectively. As another instance, the three isomeric dinitrobenzenes would be shown thus : — C.N0 2 C.N0 2 c.N0 2 HC HC CH Ortho. C.NOa CH HC, HC CH 'CH C.N0 2 Para. IOO BLEACHING AXD CALICO-PRIXTIXG. The xylene obtained from coal-tar consists of a mixture of the three xjlenes, which can exist according to theory; but of these, metaxylene is present in by far the largest proportion. The boiling points of the three xylenes lie so near each other (about 140°) that a separation by fractional distillation is not possible. Xylene is lighter than benzene or toluene. Its specific gravity is 0-866 at 15° C. Naphthalene. — Naphthalene consists of white leaflets, which pos- sess a peculiar smell and sublime slowly at the ordinary temperature. It melts at 79 - 2 = and boils at 216°. The constitutional formula of naphthalene can be regarded as a double benzene ring, and is ex- pressed as follows : — CH HC CH It will be seen in looking at this formula that in the formation of mono-substitution products two isomers are obtained, according as the hydrogen atoms marked /3 or those marked a are replaced in the following scheme : — Thus by replacing one hydrogen atom by OH, two isomeric naphthols are obtained which are known as alpha-naphthol and beta-naphthol, but both possess the rational formula C lfl H r OH. Anthracene, C u H 1lV — Anthracene forms leaflets with a violet fluorescence. They melt at 213° and boil at 360°. Anthracene contains two separate benzene rings, which are joined together by the group CH.,. The constitution is shown in the following graphic formula: — CH PREPARATION OF ANILINE. ioi Aniline, C H 5 NH,, and Toluidine, C V H 7 NH 2 .— These amines are obtained from benzene and toluene, by nitration and reduction of the resulting nitro bodies. The nitration is effected, with certain precautions, especially with regard to temperature, with a mixture of nitric and sulphuric acids. If the mixture becomes too strongly heated, dinitro products are pro- duced in place of the mononitro derivatives desired. Nitrobenzene, C c; H 5 N0 2 , is formed according to the equation : — C C H C + HN0 3 = C 6 H 5 N0 2 + H 2 0. Benzene. Nitrobenzene. It is a yellow liquid, solidifying at + 3°, boiling at 213°, and is heavier than water (specific gravity T2). It possesses a smell resem- bling that of oil of bitter almonds, and is sometimes used in pei-fumery under the name of "artificial oil of bitter almonds," or " mirbane oil.' 7 The first name often leads to confusion with the benzaldehyde prepared from toluene, which is distinguished from the natural product by the name " artificial oil of bitter almonds." In accordance with the benzene theory, there is only one mononitro- benzene, while there are three mononitrotoluenes, C (; tl 4 , NO.,, CH 3 , which are distinguished as ortho (O), meta (M), and para (P) nitro- toluenes. By nitration of toluene, a mixture of ortho- and para-nitrotoluene is formed, with only a very small quantity of the meta compound. A separation of these two nitrotoluenes is never carried out on a large scale. Ortho-nitrotoluene is a liquid which boils at 223°. It solidifies at -20°. Specific gravity, 1*17. Para-nitrotoluene forms crystals which melt at 54°, and boil at 238°. The reduction of nitrobenzene and toluene is effected by iron and hydrochloric acid. C G H 5 N0 2 + 3Fe + 6HC1 = C G H 5 . NH 2 + 3FeCl 2 + 2H 2 0. Nitrobenzene. Aniline. The ferrous chloride yields with the aniline, ferrous hydrate and aniline hydrochloride. The ferrous hydrate reduces more nitroben- zene, whilst the aniline hydrochloride acts on the metallic iron again, producing ferrous chloride and free aniline. The reduction is carried out with the aid of a gentle heat. When it is over, slaked lime is added to decompose any aniline hydro- chloride, and the product is then distilled with steam. The oily layer of the distillate is separated from the aqueous one, and purified by dis- tillation. Aniline, C^H^NH.,, is a colourless oil which boils at 183°. On exposure to the air it becomes brown. Its specific gravity is 1-03. One part of aniline dissolves in 31 parts of water; it is easily soluble in alcohol, ether, ifec. It is a good solvent for many substances 102 BLEACHING AND CALICO-PRINTING. which are sparingly soluble in other liquids — e.g., indigo. One method of purifying aniline blue is based upon its solubility in aniline oil. Aniline is a very strong base, forming with acids well crystallised salts. Ortho-toluidine is a liquid boiling at 198°, which does not solidify at — 20°. Its specific gravity is nearly the same as that of water. Para-toluidine forms leaflets which melt at 45°, and boil at 198°. For the qualitative detection of toluidine in aniline, a small sample is shaken with water, and chloride of lime or sodium hypochlorite is added to the aqueous solution. The purple-violet solution is shaken with ether. In presence of toluidine the ethereal layer will assume a permanent brown colour, while the aqueous solution is blue. This reaction furnishes, at the same time, an example of the property of aniline of yielding colouring matters by oxidation. The nature of the colouring matters formed depends upon the duration of the oxida- tion, the temperature, the proportions employed, and the quantity of toluidine in the aniline. The aniline oils of commerce are a mixture of aniline and ortho- and para-toluidine. They sometimes also contain xylidine, C 6 H 3 (OH 3 ) 2 NH 2 . The following varieties ai*e distinguished : — Pure aniline, or aniline for blue, with very little toluidine. Aniline for safranine contains 35 per cent, of aniline ; the rest consists of toluidine and a little xylidine. Aniline for red (red oil) contains 20 per cent, of aniline, 40 per cent, of para- and 40 per cent, of ortho-toluidine. Toluidine is a mixture of ortho- and para-toluidine with very little aniline. Naphthylamine, C 10 H 7 NH 2 . — Alpha-naphthylamine forms fine needles, which melt at 50°, and possess a disagreeable smell ; it is almost insoluble in water. It yields colouring matters by oxidation. In order to prepare it, naphthalene is heated with nitric and sulphuric acids, and the resulting alpha-nitronaphthalene, C 10 H r ]S"O.„ is reduced with iron and hydrochloric acid. It serves for the preparation of magdala-red, the naphthylamine fancy colours on cotton, and some azo dyes. Beta-naphthylamine forms white leaflets, which melt at 112°. It dissolves in hot water. It is prepared by heating fused beta-naphthol with gaseous ammonia. Some azo dyes are derived from it. Aniline Salts.— Hydrochlorate of Aniline, C ( ,H 5 NH 2 HC1.— This salt is formed when aniline oil is neutralised with hydrochloric acid. It is largely manufactured and brought into commerce in the form of crystals. It is largely employed for cotton dyeing and calico-printing for the production of aniline black, a colour of great fastness. The aniline group of colours is built upon what is called the methane type — that is to say, their constitution is expressed by formula} similar to that of marsh a;as or methane — COLOUR BASES. IO3 (H L )H (H Thus, para-rosaniline, one of the colour bases of magenta, has the formula — I C C H 4 NH 2 p, ) C6H4NH2 ^ ) C C H 4 NH 2 (OH Magenta, and many of the basic aniline colours, are derivatives of two compound methanes, viz. : — (C G H 5 ° ) C 6 H 5 (h Triphenylmetliane. and C C G H 4 CH3 C 6 H 5 1 C G H 5 H Tolylcliphenylmethane. We have seen how benzene, by treatment with nitric acid, is converted into nitrobenzene, and also how nitrobenzene by reduction is changed into amidobenzene (aniline); in a similar way, triphenyl- methane and tolyldiphenylmethane are converted first into the nitro and then into the amido compounds — i C 6 H 5 r> ) C G H 5 L ) C G H 5 Triphenylmethane. I C6H4CH3 q ) C G H 5 ) Cf,H 5 (H Tolyldiphenylmetham + 3HN0 3 ( C G H 4 N0 2 _ r ) C 6 H 4 N0 2 - C ) C 6 H 4 N0 2 (H Tiinitrotriphenylmethane. C 6 H 3<^CHs + 3HN0 3 C-i C 6 H 4 N0 2 + C 6 H 4 N0 2 B. Trinitrotolyldiplienylmethane. 3H 2 C G H 4 N0 2 C G H 4 N0 2 C 6 H 4 N0 2 H C 6 H 3 TT J (CH 8 ) 2 Uotls t— N=N-C1. This combines in the nascent state with the naphthol to form xylidine red. The whole reaction is expressed by the following equations : — C H 3 | ^f 2 + C 10 H 7 OH + NaNO, + NH 4 C1 Xylidine. Beta-naphthol. _ r H I (CH 3 ) 2 - L fi tt 3 j _Nr=N.C 10 H c OH + NaCl + 2H 2 + NH 3 . Scarlet. The Anthracene Colouring- Matters.— Although the number of colouring matters obtained from anthracene is very limited, they all resemble each other so closely in their chemical properties, and at the same time differ so widely from the other coal-tar colours, that they form a natural group of the latter. In the free state they are almost insoluble in water, but are easily soluble in ammonia and caustic alkalies. With the alkaline earths and most metallic oxides they yield richly-coloured insoluble lakes. This behaviour towards bases indicates the acid nature of these colouring matters, and a more thorough examination will show that they contain free hydroxyl groups, and, therefore, belong to the phenols, hence they are some- times spoken of as phenolic colouring matters. The anthracene colouring matters can only be used with the help of mordants. The shades produced with them are much faster to soap, chloride of lime, dilute acids, and in most cases also to light, than those obtained with the other coal-tar colours, while, at the same time, they are faster than most of the natural colouring matters. Manufacture Of Alizarine. — The method usually adopted for the transformation of anthracene into alizarine is effected in three distinct operations. Anthracene is first oxidised to anthraquinone — c (; h 4 ^ 1 >c c h 4 + o 3 = c (i ir 4 <^>r^>c (; H 4 + h 2 o. Anthracene. Anthraquinone. The anthraquinone is next treated with sulphuric acid. Anthra- quinone forms three sulphuric acid compounds — viz., monosulphonic acid and alpha- and beta-disulphonic acids ; and, according as one or the other is produced, a different result is obtained, since the mono- sulphonic acid compound yields pure alizarine, while the alpha-disul- phonic acid produces flavopurpurine, and the beta-disulphonic acid yield anthrapurpurine. Anthraquinone-monosulphonic acid — C c H 4 <^gg^C ti H 3 S0 3 H PREPARATION OF ALIZARINE. IO9 is formed when authraquinone is heated to 160° C. with fuming sul- phuric acid. If the quantity of sulphuric acid is increased without raising the temperature, the chief product of the reaction is the beta- disulphonic acid. But if the temperature be kept for some time at 180° to 185° C, the chief product will be the alpha-disulphonic acid — ■ SQ 8 H - C (i H 3 \cS^> C " H 3S0 3 H. Alpha- and beta-antliraquinone disulphonic acids. The next process in the manufacture of alizarine is heating in strong boilers at a temperature of 190° C. for twenty-four hours, a mixture of 3 to 4 parts of solid caustic soda with 1 part of anthra- quinone monosulphonate of soda and a small quantity of chlorate of potash. The reactions take place according to the following equa- tions : — C C H 4 <^gg ^> CVH3SO3II + NaHO = C C H 4 <^QO^> C c H 3 S0 3 Na + H,0. 3C G H 4 <^ CO / C 6 H 3 SO s Na + ONaHO + KC10 3 = 3C C H 4 <^C0 / G eH 2 (ONa) 2 + 3Na,S0 3 + 6H...0 + KC1. The alizarate of soda is then neutralised with hydrochloric acid, when alizarine is set free, thus — C 6 H 4 <^g \ C 6 H 2 (ONa) 2 + 2HCI = C G H 4 / gO \ c 6 H 3 (OH) a + 2NaCl. Alizarine. Commercial alizarine is always sold in the form of a paste, containing 20 per cent, of the colouring matter in a very fine state of division. It usually goes by the name of blue shade of alizarine, as it gives with alumina mordant a bluish shade of red ; with smaller quantities of alumina mordant very good pinks are obtained. With iron mordant good fast violets are produced. If beta-anthraquinone disulphonate of soda be melted with caustic soda and chlorate of potash, then anthrapurpurine OHC G H 3 <^ £0 \ Co e 2 (OH) 2 is produced. If alpha-anthraquinone disulphonate of soda be melted with caustic soda and chlorate of potash, then we get flavopurpurine, which has the same formula as anthrapurpurine. A mixture of flavo- and anthrapurpurine goes by the name of "yellow shade of alizarine," because it gives yellower shades of red than those produced by means of pure alizarine. Yellow shades of alizarine must not be used for violets, as they do not yield good shades. The principal combinations of alizarine with metallic oxides are the following : — I o BLEACHING AND CALICO -PRINTING. Reds and pinks, with alumina. Purple or violet and lilacs, with oxide of iron. Chocolates, with mixtures of alumina and oxide of iron. Clarets, with oxide of chromium. I 'ranges, with oxide of tin. The valuation of the alizarines is usually effected by estimating the percentage of dry substance and the ash, and by carrying out com- parative dye trials. In estimating the percentage of dry substance, it should be borne in mind that the temperature should not be allowed to rise much above 100°, since alizarine begins to sublime at 110°. The residue should appear yellow and not dark brown. Alizarine pastes sometimes contain glycerine, Turkey-red oil, etc., which have been added in order to thicken the paste. These can be separated from the colour- ing matters by diluting with water and filtering. The filtrate may contain, besides, small quantities of salts, which have not been properly removed in the manufacture. It should have neither a- brown nor a reddish tinge, but should be perfectly colourless. The ash should not weigh more than 1 per cent, of the dry alizarine, and should be free from iron. Alizarine Orange, C 6 H 4 = CO = C 6 H(OH.,).,lSrO.,, is prepared from alizarine by treating that substance with nitrous fumes; its chemical name is, therefore, nitro-alizarine. Alizarine orange is used chiefly in calico-printing as a steam colour, and is fixed, like alizarine, by means of a basic mordant. With alumina (as sulphocyanide) a good bright orange is produced if the cloth be well oiled. With acetate of chrome as the mordant alizarine orange gives a good brown shade j these colours are remarkably fast to light, and stand soaping well. Coloui*s made with alizarine orange do not keep so well as those made with alizarine, as the nitro-alizarine is a much stronger acid, and has a great tendency to combine with the metallic bases to form lakes, even in the cold. Alizarine orange is found in commerce as a paste, containing 20 per cent, of the dry colouring matter ; it is valued in the same way as alizarine. Alizarine Blue is a derivative of nitro-alizarine, from which it is obtained by treatment with glycerine and sulphuric acid — CH,OH C C H4 x £o C, ; H(OH) : ,NO, + CHOH Nitro-alizarine. CILOH Glycerine. = CeH 4 S^5 cS = SS + 2H *° + Oo. Dioxyanthraquinone qninoline or Alizarine blue. Alizarine blue is used as a steam colour in calico-printing, with acetate of chrome and lime as a mordant; the colour is not very bright, and CCERULEINE— GALLOCYANINE. I I I is only moderately fast to light. For cotton dyeing it is neither as "ood nor as cheap as indigo. Alizarine blue combines with sodium bisulphite to form alizarine blue S, a dry powder which is soluble in water. This is the form in which it is now generally used. Cceruleine or anthracene green — probable constitutional formula — CO — C c HOHO, C G H 4 / \ CO — C G HOHO, is not obtained from anthracene, but by the dehydration of gallein — C 2 OH 10 O 7 — OH 2 = C 20 H 8 O 6 . However, since cceruleine has the constitution and properties of an anthracene derivative, it may well be classed with anthracene colours. Cceruleine, if fixed with a chrome mordant, is remarkably fast to light and soaping, but the shade it gives is rather an olive than a green ; it is also a rather expensive colour. Cceruleine is found in commerce both in the form of a paste and also as a dry powder ; the latter is the sulphite compound, and is known as cceruleine S. Gallocyanine (Durand & Huguenin).— Chloride of dimethylphenyl- ammoniumdioxyphenoxazin carbonic acid, C^(CH 3 ) 2 C G H 3 < C :>C G H<[ H C) H. obtained by acting with nitrate of nitrosodimethylaniline upon gallic acid or tannin (1881— H. Koechlin) is a greenish-grey paste, which when dried gives a bronze-coloured powder. It is insoluble in water, soluble in alcohol to a blue-violet solution, in strong sulphuric acid to a pale bright blue solution ; on diluting with water gives a bluish- red solution ; soluble in hydrochloric acid to a crimson-red solution, in caustic soda to a red-violet solution. Dyes chrome-mordanted wool blue-violet shades, fairly fast to acids, light, and washing. Applied in calico-printing with a chrome mordant. Known also as solid violet. Anthragallol — Anthracene Brown — Alizarine Brown. — Trihydroxy- anthraquinone, C G H 4 ; g° C G TIOH( 1 )OH(o)OB( 3 ), is formed by heating a mixture of gallic acid, benzoic acid, and sul- phuric acid together. It is isomeric with anthrapurpurin, crystallises in yellow needles, and sublimes at 290° C. ; it is slightly soluble in water, readily in alcohol, and in alkalies to a green solution. Alizarine browns come into the market as brown pastes. They give, with chrome mordants, rich nut browns ; with alumina mordants, redder shades of brown ; and with iron mordants, deep full browns. The most suitable brands to use are anthracene brown (Badische), anthracene brown W or G (Farbenfabriken), or alizarine brown paste (Farbwerke). 112 BLEACHING AND CALICO-PRINTING. Alizarine Yellow GG (Meister, Lucius, and Briining). — J/-nitroben- zene azo-salicvlic acid, C c H 4 X0 2 X. XC (; II 3 ()HCOOH, is obtained by combining m- diazonitrobenzene with salicylic acid (1889). The pure product crystallises from alcohol in pale yellow needles, m.p. 230° C. It is very slightly soluble in cold, easily in hot, water. The commercial product is in the form of a yellow paste, con- taining about 20 per cent, of colouring matter. Cotton, mordanted with alumina or chrome, may be dyed. For printing, the printing colour is made with starch and tragacanth thickening, acetate of chrome, acetic acid, and colouring matter, printed and steamed. Alizarine Yellow R (Meister, Lucius, and Briining). — P-nitrobenzene azo-salicvlic acid, C 6 H 4 N0 8 N SQH^OHCOOH, is made by combining ^-nitrodiazobenzene with salicylic acid (1890). Its properties and uses are similar to those of alizarine yellow GG, but it gives brownish-yellows on chrome-mordanted fibres. (ritUnjlavine (Badische) is prepared by oxidising gallic acid in alka- line, aqueous, or alcoholic solution with air (English patent, 6,413, 1886). It is a greenish-yellow paste, insoluble in water, very slightly soluble in alcohol ; the solution has a pale yellow colour and weak green fluorescence. It is soluble in strong sulphuric acid to a scarlet solution ; on diluting with water a greyish precipitate is obtained. Hydrochloric acid added to the paste, diluted with water, causes little change ; caustic soda turns it red. Dyes wool and silk mordanted with chrome yellows, and is fast to light and soap. When applied in calico-printing with a chrome mordant, it gives greenish-yellow shades, which are fast to light and soaping. Ali-.ariric Black S (Badische) is a sodium bisulphite compound of nnphthazarine — C 10 H 4 (OH) 2 <^2^ + NaHSO s . Naphthazarine or dioxynaphthaquinone is formed by treating dinitro- naphthalene with zinc and strong sulphuric acid, and this, when acted on by sodium bisulphite, yields alizarine black S. Alizarine black comes into the market in the form of either a powder or paste, and gives, with chrome or iron mordants, deep bright jet blacks of great beauty, which are exceptionally fast to light, soap, and acids. The best brand to use is alizarine black SRW paste, manufactured by the Badische Anilin and Soda Fabrik. The Farbenfabriken vormals F. Bayer & Co., Elberfeld, send into the market some very useful colouring matters, which are of the alizarine group, and are similar in point of application and fastness to air, light, and washing. They are easier to fix than the alizarines, and for dark Bordeaux and indigo shades are, if anything, superior. The blues obtained from the alizarine cyanine are exceptionally fine, and ALIZARINE COLOURS. II3 on wool they are certainly improved by milling. They are applicable also for calico-printing, and give fine results. Alizarine Bordeaux is sent into commerce in four distinct shades — a blue shade of Bordeaux or claret, as alizarine Bordeaux B ; a red shade, as alizarine Bordeaux R; and two yellow shades, as alizarine Bordeaux G and G G. These products are obtained from ordinary alizarine by heating it with fuming sulphuric acid, when the sulphur trioxide acts as an oxidising agent and forms tetraoxyanthraquinone, from which the alizarine Bordeaux is obtained. By using various brands of alizarine the various shades above named are obtained. These are identical with the chinalizarine obtained by Liebermann some time ago. It is a brownish -red paste, insoluble in water, but soluble in strong sulphuric acid to a purple solution ; on dilution it forms a red-brown ; caustic soda produces a violet solution. Alizarine Cyanine. — This colour is sent into the market in various shades (marked B and G) of blue, superior to alizarine blue in respect of application and strength, being also faster, especially in light shades. It is produced by still further oxidising alizarine Bordeaux with man- ganese dioxide and fuming sulphuric acid, when alizarine cyanine or pentaoxyanthraquinone is produced. By working at higher tempera- tures more fully oxidised bodies are obtained and are used as dyes. Thus alizarine cyanine RRR double is a brownish -red paste, which gives with chrome mordants fine purple shades ; with alumina mor- dants, maroons ; and with iron mordants, very rich full purples. Alizarine cyanine R is a brown paste, giving with chrome mordants bright blues ; with alumina mordants, magenta-coloured shades ; and with iron mordants, greyish -blues. Alizarine cyanine GG is a brown paste, giving with chrome mordants, corn flower blues; with alumina mordants, lilac shades; and with iron mordants, stone greys. Alizarine cyanine G extra is also a brownish coloured paste which gives with chrome mordants, blues ; with alumina mordants, reddish-purples ; and with iron mordants, steel greys. 114 BLEACHING AND CALICO-PRINTING. CHAPTER XII.— DYEING. IndigO Dyeing" — The Blue Vat. — Indigo, unlike the bulk of dye- wares, is, as such, insoluble in liquids which the dyer can employ. If treated with sulphuric acid, indeed, it is rendered soluble in water, and can be used for dyeing blues on animal fibres and tissues. But it has undergone a change which very seriously interferes with its most valued property — its fastness. In order to fix unaltered indigo-blue upon the fibre, we take advantage of the circumstance that this indigo -blue or indigotin, in the presence of certain agents, is reduced to a white compound (known as indigo-white), which is soluble. Fibres or tissues are then steeped in the solution, taken out and exposed to the air, when the white indigo adhering to their surfaces becomes re-oxidised and remains permanently attached to them as indigo-blue. There are various agents by which indigo can be reduced to the white soluble condition. That generally selected for cotton dyeing is copperas, the sulphate of protoxide of iron (ferrous sulphate) in presence of lime. The copperas, in contact with lime yields hydrated protoxide of iron (ferrous oxide), which greedily absorbs oxygen from any substance with which it comes in contact, and in this way reduces the indigo. The indigo to be used in setting a vat is generally first broken up into small fragments, wetted with hot water, and then ground to a paste in a peculiarly constructed mill. The chief features of this mill are a strong iron cylinder, capable of being made to revolve rapidly on an axle, and smaller, solid, very heavy iron rollers placed within. Sometimes, instead of the rollers, there are three heavy iron globes like cannon balls. The moistened indigo being introduced, the cylinder is made to rotate by steam-power, and the indigo is ground to a fine uniform pulp by the action of the rollers or of the balls- It should be reduced to a perfectly creamy paste, quite free from fragments. If such remain, they generally escape thorough reduction and solution in the vat, and are consequently wasted. The lime should be of the best quality, recently burnt, fresh slaked, and sifted. The dyer in setting his vat should know how much actual dry indigo is contained in a gallon of his fine pulp. The vats are generally made of flag-stones or slate, well jointed and clamped together, and secured by cement. As the copperas vat used for vegetable fibres is worked in the cold, no heating arrangement is needed. The size of the vats INDIGO DYEING. 15 differ. In large establishments they are often 9 feet long and deep, by 3i feet wide, and are conveniently arranged in sets of ten. In small dye works wooden tubs are often used. The proportions of the materials may vary within certain limits. A common proportion is — ground indigo, 80 lbs. ; copperas, 120 lbs. ; lime, 160 lbs. The vat is filled with water, the lime added and well stirred up, so as to form a uniform milk of lime. The indigo is next stirred in, and the solution of the copperas is gradually added, still stirring. When the mixture is thoroughly made, the whole is left for some hours, but with occasional stirring. As soon as it turns a yellow with an olive cast it is ready for use. The dyeing process is very simple. The yarns or pieces are first wetted out uniformly with water and then taken through the weakest or the most nearly exhausted vat which is on hand, proceeding thence to a stronger and stronger vat till the shade is reached. With piece- goods especially it is of importance that they should enter the vat evenly and uniformly, so that all parts may take up an equal pro- portion of the liquid. The next step is exposure to the air for as long a time as the dyeing process itself has lasted — i.e., from five to fifteen minutes. Next, the goods are taken through weak vitriol sours, passed into cold water, and dried. The New Indigo Vat (Schutzenberger and De Lalande's Patent) is set as follows : — A solution of bisulphite of soda at 49° to 59° Tw. is placed in a covered vessel containing zinc clippings, borings, &c., heaped up loosely so as to fill the tank without occupying more than a quarter of its total contents. After these ingredients have remained in contact for an hour the liquid is drawn into a cistern containing milk of lime, which decomposes the zinc salt. The clear liquid is strained off, soda or lime sufficient to dissolve the reduced indigo is added, and the indigo, finely ground as usual, is sth-red in. During all this process access of air is avoided as much as possible. In this manner 1 lb. indigo may be dissolved in 1 to lh gallons of liquid. The vat is then filled with cold water if for cotton, and with hot water if for wool, and a suitable amount of the indigo solution is added. An excess of the hydrosulphite is always present, whence the blue scum (flurry) formed on the surface by the action of the air on the reduced indigo solution in the ordinary process is almost entirely avoided. The dye thus i-esists the action of the atmosphere better than the ordinary copperas vat, and is free from the inconvenience of holding in suspension more or less peroxide of iron, lime, carbonate of lime, &c. By adding to the dye-bath from time to time a little con- centrated indigo solution, the strength can be maintained at any required point, and thus any given shade may be got with the smallest number of dips, the tints being brighter than those produced by the old process. I 1 6 BLEACHING AND CALICO-PRINTING. No. 1.— Dark Indigo, and No. 2.— Light Indigo or Sky. A better and cheaper vat than that of Schiitzenberger and De Lalande is prepared as follows : — Into an iron pan of about 200 gallons capacity put 40 lbs. of well-ground indigo. 80 lbs. of slaked lime, 10 lbs. of caustic soda, and add hot water until the whole measures 70 gallons aud is at a temperature of 1-10° F. ; lastly, add 20 lbs. of zinc powder. Rake the mixture well up about every three hours, when the indigo will be found to have dissolved in from twelve to twenty-four hours, according to the temperature of the room and the degree of fineness to which the indigo has been ground. Xext into a 12-gallon tub draw 10 gallons of bisulphite of soda of good quality, about 70° Tw. To this add 10 lbs. of zinc powder, stirring well all the time the zinc is being added to the bisulphite, and for five minutes after. This mixture is to be then poured immediately into the pan containing the 70 gallons of reduced indigo. After a final raking up the whole is allowed to settle for one hour, when it will be ready for use. Of course the above is a very strong solution of indigo — containing 8 ozs. of indigo per gallon — and is, therefore, much too strong for the purpose of dyeiug as it is, but all that is required is to add the strong solution to water until the proper strength is obtained. 1 oz. or U oz. of indigo per gallon is a good strength for dark shades of blue ; but for light blues (sky), from | to ^ oz. per gallon will be quite sufficient. Indigo is now frequently combined with indophenol, which has similar dyeing properties, this combined vat being somewhat cheaper than pure indigo ; but it will not stand the acid treatment. No. 3.— Dark, and No. 4.— Light Iron Buffs and Creams. 1st. Pass the goods through stannate of soda at \° Tw. for light creams to 8° Tw. for strong buffs. 2nd. Pass them through ferric sulphate at from -J-° Tw. to 8° Tw., according to shade required, and wash off immediately. Dyeing with these colours is best done on the padding mangle (shown in the accom- panying plate). No. 5.— Dark, and No. 6— Light Prussian Blues. These colours are produced by dyeing up the above iron buffs in a solution of yellow prussiate of potash, ^ lb. per gallon, adding 2 ozs. sulphuric acid per gallon ; wash before drying. No. 7.— Lead Yellows. These colours are produced by first padding with acetate of lead, from about 4 ozs. to 1 lb. per gallon (which operation can best be done on a padding mangle). The yellow is then raised by a solution of INSERT FOLDOUT HERE CATECHU AND OTHER BROWN DYES. 117 bichromate of soda, 4 ozs. per gallon. Sometimes the lead is fixed with lime water before raising in the chrome ; but this is better omitted in the case of printed goods. No- 8. -Catechu Browns. Dyeing with these colours is best done in the jigger (see p. 40). 6 pieces = 72 lbs. 16 lbs. catechu. 3 lbs. sulphate of copper. 10 gallons of water. Roil well before entering goods. Give 6 ends, then recharge the jigger with 10 gallons of boiling water, and 24 lbs. bichromate of soda. Give 4 ends, wash, and dry. By reducing the amount of catechu, paler shades of brown, even buffs and creams, may be produced. By adding sumach a great variety of shades may be produced by dyeing with anilines, 9 = 153 , ,, 2 „ 33 ,, 10 — 170 , >j 2 „ 50 ,, 20 = 340 , ,, 5 „ 40 ,, 30 = 510 , >j 1 ounce dram 30 minims 40 — 680 , >> 1 „ 3 drams 20 ,, 50 = 850 , >> 1 „ 6 „ io „ 60 = 1020 , j» 2 ounces 1 o 70 = 1190 , >j 2 „ 3 ,, 50 80 = 1360 , ,, 2 „ 6 „ 40 „ 90 = 1530 , i > 3 „ 1 „ 30 100 = 1700 , 53 3 „ 4 ,, 20 1000 = 1 litre = : 36 fluid ounces nearly, or 1*, pints. The Conversion of French ( Metric) into Eng lish Weight. Although a gramme is equal to 15 "4346 grains, the decimal is one which cannot conveniently be used ; hence in the following table it is assumed to be 153 grains, which is a near approach to practical accuracy : — 1 gramme = 15f grains 2 grammes = 30i „ 3 = 46| ,, 4 = 61f „ 5 — 77 „ 6 = 92f ,, 7 — 107* ,, 8 — 123i „ 9 = 138| ,, 10 „ = 154 11 = 169| ». 12 = 1844 ,, 13 = 200i ,, 14 „ = - 10 T )) 15 = 231 16 ,, = 246| „ 17 = 261* „ 18 „ = 2771 „ 19 = 292£ „ 20 = 308 30 = 462 40 = 616 50 = 770 ,, 60 — 924 „ 70 = 1078 1 dram If grain. 1 „ 17 grains 1 » 32f ,, 1 ,, 47* „ 2 drams 3i, ,, 2 „ 18f „ 2 ,, 34 2 „ 494 „ 3 „ 4^ 3 „ 20* ,, 3 „ 35* ,, 3 ,, 51 4 „ 6* „ 4 „ 2H » 4 „ 37* „ 4 ,, 52f „ 5 „ s 7 „ 42 10 „ 16 12 „ 50 15 „ 24 17 „ 5S ,, J 34 BLEACHING AND CALICO-PRINTING. 80 grammes = 1232 grains, . . . or 20 drams 32 grains. 90 „ = 13S6 ,,...,, 23 ,, 6 100 ,, = 1540 „ ... „ 25 ,, 40 1000 ,, =1 kilogramme = 32 ounces drams 40 grains (apoth. wt.) 1000 ,, = 1 ,, = 35j ounces (avoir, wt.) Thermometry Tables, Showing the relation of the three thermometric scales most in use throughout the world. Celsius. Reaumur. Fahrenheit. Celsius. Reaumur. Fahrenheit. 100 80-0 212-0 49 39-2 120-2 99 79 o 210-2 48 38-4 1184 98 78 4 208-4 47 37-6 116*6 97 77 6 206 6 46 36-S 114-8 96 76 S 204-8 45 36-0 1130 95 76 203 44 35-2 111-2 94 75 2 201-2 43 34 4 1094 93 74 4 199-4 42 336 107 6 92 73 6 197-6 41 32 -S 105-8 91 72 S 195-8 40 32 104-0 90 72 1940 39 31-2 102 2 89 71 2 192-2 38 30-4 100-4 88 70 4 190-4 37 29-6 9S-6 87 69 6 188-6 36 2S-8 96-8 86 68 S 186-8 35 28-0 950 85 68 185-0 34 27-2 93 2 S4 67 2 183-2 33 26 4 9L4 S3 66 4 181-4 32 25-6 89-6 82 65 6 1796 31 24-S 87-8 81 64 S 177-8 30 24 86-0 SO 64 1760 29 23-2 84-2 70 63 2 174-2 28 22-4 S2 4 78 62 4 172-4 27 21-6 80-6 77 61 6 170-6 26 20-8 78-S 76 60 S 168-8 25 20 77-0 75 60 167-0 24 19-2 75-2 74 59 2 165-2 23 1S-4 73-4 73 58 4 163 4 22 176 716 72 57 6 161-6 21 16-S 69-8 71 56 S 159-8 20 16-0 6S-0 70 56 15S-0 19 15-2 66-2 69 55 2 156 2 IS 14-4 64-4 68 54 4 154-4 17 13-6 62-6 67 53 6 152-6 16 12-S 60S 66 52 8 150-8 15 12-0 59-0 65 52 149-0 14 11-2 57-2 64 51 o 147-2 13 104 55-4 63 50 4 1454 12 9-6 536 62 49 6 143 6 11 8-8 51-S 61 48 8 141S 10 8 50 60 4S 1400 9 7-2 48-2 59 47 9 138-2 S 6-4 46 4 58 46 4 136-4 7 5-6 446 57 45 6 134-6 6 4-S 42 -8 56 44 8 132-8 5 4 410 55 44 131-0 4 3-2 39 2 54 43 2 129-2 3 2 4 37-4 53 42 4 1274 2 1-6 365 52 41 6 125-6 1 08 33-8 51 40 8 123 S 00 32 50 400 122-0 HYDROMETER SCALES. I 35 To convert Centigrade (Celsius) into Fahrenheit, if the temperature be above the freezing point of water (and lower temperatures do not occur in dyeing and print- ing processes), multiply by 9, divide the product by 5, and add 32 to the quotient. To convert degrees of Fahrenheit above the freezing point into Centigrade, sub- tract 32, multiply the remainder by 5, and divide the product by 9. To convert Reaumur into Fahrenheit, multiply by 9, divide by 4, and add 32 to the quotient. To convert Fahrenheit into Reaumur, subtract 32, multiply the remainder by 4, and divide the product by 9. Comparative Hydrometer Scale. Specific gravity, Beaume and Twaddel. Specific Degrees Degrees Specific Degrees Degrees Gravity. Beaume. Twaddel. Gravity. Beaum^. Twaddel. 1 000 1-221 26 44-2 1007 1 1-4 1-231 27 46-2 1-014 2 2-8 1 242 28 48-4 1-022 3 4-4 1 252 29 50-4 1-029 4 5-S 1-261 30 52-2 1 036 5 7-2 1-275 31 55-0 1 -044 6 8-8 1-286 32 57-2 1-052 7 10-4 1-29S 33 59-6 1-000 S 120 1 "309 34 61-8 1-067 9 13-4 1-321 35 64-2 1-075 10 15-0 1 334 36 66-8 1-0S3 11 16-6 1-346 37 69 2 1-091 12 18-2 1-359 38 71-8 1-100 13 20-0 1-372 39 74-4 1-108 14 21-6 1 -384 40 76-8 1-116 15 232 1-398 41 796 1-125 16 25-0 1-412 42 82-4 1-134 17 26 8 1-426 43 S5-2 1-143 18 2S-6 1-440 44 ss-o 1-152 19 30-4 1-454 45 90 -S 1-161 20 32-2 1-470 46 94 1-171 21 34-2 1-4S5 47 97-0 1-180 22 36-0 1-501 48 100-2 1-190 23 38-0 1-516 49 103-2 1-199 24 39 1-532 50 106-4 1-210 25 42 To convert Twaddel into specific gravity, multiply by 5, considering the pro- duct as decimals, and add to it l'OOO. Thus, if a sample of soda solution marks 59° Tw., we have — 59 5 •295 1-000 1 -295 = the specific gravity of the solution. On the other hand, if the strength of the solution has been taken by direct specific gravity, we find the degree Twaddel by subtracting 1 000 and dividing the remainder by 5, thus— 1 -295 1-000 295 59° Twaddel. I 7,6 O' BLEACHING AND CALICO-PRINTING. Table showing the Percentages of Real Sulphuric Acid (S0 4 H,) cor- responding to various Specific Gravities of Aqueous Sulphuric Acid. Bineau ; Otto. Temp. 15°. Specific Per Specific Per Specific Per Specific Per gr tvity. cent. gravity. cent. gravity. cunt. gravity. cent. 1 S426 100 1-675 75 1-398 50 1-182 25 1 84-2 99 1 -663 74 1 -3SS6 49 1-174 24 1 8406 9S 1-651 73 1 379 48 1167 23 1 840 97 1 -639 72 1 -370 47 1-159 22 1 8384 96 1-627 71 1-361 46 11516 21 1 8376 95 1-615 70 1-351 45 1-144 20 1 S356 94 1-604 69 1 -342 44 1-136 19 1 S34 93 1-592 68 1-333 43 1-129 18 1 831 92 1-580 67 1 -324 42 1121 17 1 827 91 1-568 66 1-315 41 11136 16 1 822 90 1-557 65 1-306 40 1106 15 1 S16 S9 1-545 64 1 2976 39 1-098 14 1 S09 88 1-534 63 1-2S9 38 1-091 13 1 802 S7 1 -523 62 1-281 37 1 083 12 1 794 86 1-512 61 1 -272 36 1-0756 11 1 786 S5 1-501 60 1-264 33 1-068 10 1 77? S4 1 490 59 1 -256 34 1061 9 1 767 83 1-4S0 58 1-2476 33 1-0536 8 1 756 82 1-469 57 1 -239 32 1-0464 / 1 745 SI 1-45S6 56 1-231 31 1 -039 6 1 734 80 1-448 55 1 -223 30 1 032 5 1 722 79 1-438 54 1 215 29 1-0256 4 1 710 7S I 428 53 1-2066 2S 1-019 3 1 69S 77 1-41S 52 1-198 27 1-013 2 1 '686 76 1-408 51 1-190 26 1 -0064 1 Table giving the Percentage Amount of Hydrochloric Acid contained ix Aqueous Solutions of the Gas of various Specific Gravities. Ure. Temp. 15° Specific HC1 Specific HC1 Specific HCl Specific HCl Gravity. per cent. gravity. per cent. gravity. per cent. gravity. per cent. 1-2000 40-777 1T515 30-582 1-1000 20-3SS 1 -0497 10-194 1-1982 40-369 1 1494 30-174 1 -0980 19-9S0 1-0477 9-786 1-1964 39-961 1 1473 29-767 1-0960 19-572 1-0457 9-379 1 1946 39-554 1 1452 29-359 1-0939 19-165 1 -0437 8-971 1-192S 39-146 1 1431 2S-951 1-0919 18 757 1-0417 8563 1-1910 38-738 ! 1 1410 2S-544 1-0899 IS -349 1 -0397 S-155 1-1893 38-330 i 1 1389 28-136 1-0879 17-941 1-0377 7-747 1-1875 37-923 1 1369 27-728 1-0859 17-534 1 -0357 7 340 1-1857 37 516 1 1349 27 321 1 0838 17-126 1 0337 6-932 1-1846 37-10S 1 132S 26-913 1-0818 1671S 1-03 IS 6-524 1-1822 36-700 1 130S 26-505 1-0798 16-310 1 -0-298 6116 1-1802 36-292 1 1287 26-098 1-0778 15-902 1 -0279 5 709 1-1 7S2 35-884 i 1267 25-690 1-0758 15-494 1 -0259 5-301 1-1762 35-476 1 1247 25-282 1-0738 15-087 1 0239 4-893 1-1741 35-068 1 1226 24-S74 1-0718 14-679 1 -0220 4-4S6 1-1721 34-660 1 1206 24 466 1-0697 14-271 1 -0200 4-07S 1-1701 34-252 1 1185 24-05S 1 0677 13S63 1-0180 3 670 1-16S1 33-845 1 1164 23 650 1 -0657 13-456 10160 3-262 1-1661 33-437 1 1143 23-242 1-0637 13049 10140 2-854 1-1641 33-029 1 1123 22-S34 1-0617 12-641 1-0120 2-447 1-1620 32-621 1 1102 22-426 1 -0597 12 233 1-0100 2039 1-1599 32-213 1 1082 22-019 1 0577 11-825 1 -0080 1-631 1-1578 31-805 1 1 1061 21-611 1 0557 11-418 1-0060 1124 1-1557 31-39S ! 1 1041 21-203 1-0537 11-010 1 -0040 0-816 '1-1536 30-99D 1 -1020 20-796 1-0517 10-602 1-0020 0-408 TABLES OF PERCENTAGES. 137 Table showing Percentage Amount of Soda (Na 2 0) in Aqueous Solutions of various Specific Gravities. Tunnerniarm. Sp. gr. Per cent. | Sp. gr. Per cent. Sp. gr. Per cent. Sp. gr. Per cent. 1-4285 30-220 1-3198 22-363 1-2392 15-110 1-1042 7-253 1-4193 29-616 1-3143 21-894 1 -2280 14-500 1 -0948 6-648 1-4101 29-011 1-3125 21-758 1-217S 13901 1 0855 6-044 1-4011 28-407 1-3053 21-154 1-2058 13-297 1-0764 5-440 1 -3923 27-S02 1-2982 20-550 1-1948 12-692 1-0675 4-835 1-3836 27-200 1-2912 19-945 1-1841 12-08S 1 -0587 4-231 1-3751 26-594 1-2843 19341 1-1734 11-484 1 -0500 3-626 1-3668 25-9S9 1-2775 18-730 1-1630 10-879 10414 3-022 1-3586 25-3S5 1-2708 18-132 1-1528 10-275 1 -0330 2-41S 1-3505 24-780 1 -2642 17-528 1-1428 9-670 1-0246 1-813 1 -3426 24-176 1 -2578 16-923 1-1330 9 066 1-0163 1-209 1 -3349 23-572 1 1-2515 16379 1-1233 8-462 1-0081 0-604 1 -o273 22-967 1-2453 15-714 1-1137 7-S57 1-0040 302 Table showing the Percentage Amount of Ammonia in Aqueous Solutions of the' Gas of various Specific Gravities. Carius. Temp. 14°. Specific NH 3 Specific NH 3 Specific NH 3 Gravity. per cent. Gravity. per cent. Gravity. per cent. 0-S844 36 0-9133 24 0-9520 12 0-8S64 35 0-9162 23 0-9556 11 0-8SS5 34 09191 22 0-9593 10 0-8907 33 0-9221 21 09631 9 0-8929 32 9251 20 0-9670 8 0-S953 31 0-9283 19 0-9709 7 0-8976 30 0-9314 18 0-9749 6 0-9001 29 0-9347 17 0-9790 5 0-9026 28 0-93S0 16 0-9831 4 0-9052 27 0-9414 15 0-9873 3 0-9078 ■ 26 0-9449 14 09915 2 0-9106 25 0-9484 13 9959 1 D. H. HILL LIBRARY North Carolina State College 138 APPENDIX. ADDITIONAL RECIPES. The following are a few examples of the one dip method of dyeing, that is, all the materials, dyestuffs, mordants, &c, heing together in one bath. These are best done on the padding mangle and dried by hot air :— No. 34.— Bordeaux Shade. Cold water, .... 16 gallons Ammonia, 950 specific gravity, Oleine oil, 50 per cent., Alizarine Bordeaux, . . Acetate of chrome, 32° Tw., 1 gallon. 1 » 1 ,, (Bayer & Co.) 4 » No. 35.— Dark Plum Shade. Cold water, , . . . 16 gallons. Ammonia, 950 specific gravity, . 1 gallon. Oleine oil, 50 per cent. , . . 1 ,, Alizarine cyanine, . . . 1 ,, (Bayer & Co.) Acetate of chrome, 32° Tw., . 4 m If the above are for plain shades, they must be steamed for 1 hour ; wash after, but not before, steaming. If the goods are to be printed in a discharge colour, as below, they must be printed before steaming. No. 117.— Yellow Discharge on 1 Dip Dyes. (As above.) (a) 1^ lbs. chrysophenine. 2 gallons water. 2g lbs. wheat starch. Boil and stir till cold. (b) 2 gallons water. 8 lbs. chlorate of soda. 25 ozs. citric acid. 34 ozs. red prussiate of potash. 16 lbs. British gum. Boil and stir till cold. Then add (6) to (a). Print on cloth dyed by the 1 dip method, steam 1 hour, wash aud dry. 139 INDEX. Acetate of alumina, 30, 31. ,, Ferrous, 31. of lead, 93. ,, of lime, 95. Acetic acid, 88. Acetin, 88. Acids, Action of, on cotton fibre, 2. ,, Organic, 90, 91. Albuminoid thickeners, 71. Alizarine, Manufacture of, 10S. Alizarine black, 112. blue, 110. ,, Bordeaux, 113. ,, brown, 111. ,, cyanine, 113. ,, oil, Preparation of, 84, 85. „ orange, 110. ,, yellow, 112. Alkali blue, 105. ,, in soap, Determination of, 87. Alkalies, Action of, on cotton, 2, 3. Alum, 30. Alumina salts, 95. Ammonia, table showing relation of percentage to specific gravity of aqueous solutions, 137. Amylum, 6!', 70. Aniline, 101, 102. blue, 104. ,, greens, 105. red, 104. salts, 102. ,, violet, 105. Annatto, 77. Anthracene, 100. ,, brown, 111. ,, colouring matters, 10S. ,, green, 111. Anthragallol, 111. Anthrapurpurine, 109. Auramine, 106. Azo-blue, 107. Azo-dyestuffs, 106. Barium yellow, 96. Barwood, 76. Benzene, 98. Benzopurpurine, 107- Benzyl violet, 105. Berlin blue, 97. Bichromate of soda, 94. Black liquor, 31. 1 Bleaching, 4-18. ,, Course of operations for, 16. ,, Mather - Thompson process of, 17, 18. ,, new processes, 16-18. ,, Theory of, 13, 14. Bleaching-powder, Testing, 14, 15. Blood albumen, 71, 73. Blue pigments, 97. ,, vat, SI, 114. Bowking, 10. Brasilin, 76. Cadmium yellow, 96. Calico-printing, Styles of, 32-68. Carbonate of lime, 95. Castor oil, S4. Chalk, 95. Chemical elements, 27. China clay, 96. Chlorine, Use of, in bleaching, 13, 14. Chromed colours, 56-58. Chrysamine, 107. Citric acid, 90. Clark's soap test, 126. Coal-tar colours, 9S, 113. Coal tar, Distillation of, 98. Cceruleine, 111. Colour oil, 84. Colouring matters, Affinity of, for cot- ton, 3. ,, Natural organic, 75- 81. Colours, Theory of, 12S-132. Compounds, 2S, 29. Congo red, 106. Cotton blue, 105. ,, fibre, Action of chemicals on, 2, 3. ,, ,, Composition, 2. ,, ,, Impurities of, 4. ,, ,, Mercerised, 3. ,, ,, Physical properties, 1. ,, plant, 1. Crystal violet, 105. Cutting liquor, 45. Cylinder-machine printing, 21-25. Dextrin, 71. Discharge style, 42-48. Divi, 82. Dunging or fixing process, 39. 140 INDEX. Dyed or madder style of printiug, 32-41. Dyeing, 114-124. ,, by the madder style, 39-41. Ethyl tartrate, 89. Extract style, 4S-6S. Fatty acids in soap. Determination of, 87. Flavopurpnrine, 109. Gall nuts, S2. Gallocyanine, 111. Galloflavine. 112, Glycerine, SS. Green pigments, 97. Grey souring, 10. ,, wash, 6. Guignet or chrome green, 97. Gums, 71. PLemateis, 75. Hematoxylin, 75. Hand-block printing, 19, 20. Hemlock, S2. Hydrochlorate of aniline, 102. Hydrochloric acid, table of relation of percentages to specific gravity of acpieous solutions, 136. Hydrometer scale, 135. Ixdicax. 77. Indiglucin. 77. Indigo, 77-S1, 114. ,, dyeing, 114. 115. ,, -rubin. 78. ,. vat, New, 115. ,, white, 7S, 79. Indigotin, 77. 78, 80, 81. Insoluble diazo colours, 60-63. Iron butf, 97. Lafts lazuli, 'J7. Lead orange, 96. ,, yellow, 96. Ley boil. 11. 12. Lime boil, 6-10. „ slaking, 8-10. ,, testing 1 ■ Logwood, 7-">. Madder, 81. ,, bleach, 5. style, 32-41. Magenta, 103, 104. Malachite green, 105. Market bleach, 5. Methyl violet, 105. Methvlene blue, 106. Metric svstem, 132, 133. Mordants, 29-31, 95. Myrobolans, S2. Naphthalene, 100. ,, colours, 106. Naphthylamine, 102. Nicholson's blue, 104. Nitrate of lead, 93. Nitrobenzene, 101. Oak bark, 82. Oils, 84, S5. Old fustic, 77. Oleine oil, Preparation of, S4, 85. Oxalic acid, 91. Perrotine-machixe printing, 21. Persian berries, 77. Phosphate of soda, 94. Pigment colours, 55, 56, 96, 97. Potassium autimony oxalate, 93. ,, ,, tartrate, 93. Preparation of cloth for printing, 25, 26. Printing, 19-26. ,, Cylinder-machine, 21-25. ,, Flat press work, 21. Hand-block, 19, 20. ,, Perrotine-machine, 21. Printing colours, 5S-60. ,, ,, New, 65-68. Prussian blue, 97. Quercitron bark, 76. Raised colours, 56-58. Recipe for acetate of chrome, 50. lime (24° Tw.), 42. tin (36° Tw.), 65. ,, alizarine cyanine black, 66. ,, alpha ■ naphthylamine Bor- deaux, 62. ,, amido-azo-benzol dark red, 62. ,, aniline black, 35, 51. , , ,1 grey (2 lbs. ), 56. ,, artificial indigo, 58. ,, auramine yellow (2 ozs.), 53. ,, azo-green, 65. ,, azo-Turkey-red, 63. ,, Bismarck brown (2 ozs.), 54. ,, black discharge, 43. ,, blood albumen solution, 44. ,, blue (3 lbs.), 55. ,, ,, discharge, 42. ,. grey, 66. ,, ,, reserve, 64. ,, brilliant alizarine blue G, 60. ,, ,, chrome red, 66. ,, ,, yellow, 60. ,, brown discharge, 47. ,, ,, (medium), 51. ,, ,, olive, 52. ,, buff shade, 52. ,, catechu brown (2 lbs.), 56. ,, , > liquor, 56. ,, caustic (S lbs.), 58. ,, chocolate, 52. „ (8/3), 34. „ (8/6),_35. ,, chrome black, 57. INDEX. 141 Recipe for chrome blue, 60. green, 60. ,, ,, mordant, 50. ,, ,, rubine, 66. ,, ,, violet, 60. ,, ,, yellow, 60. ,, citron-oxalate of tin, 49. ,, claret shade, 67. ,, cutch shade, 67. ,, dark grey, 66. ,, diamond orange, 66. ,, ,, yellow, 65. ,, dianisidine blue, 63. ,, discharge brown, 44. buff, 45. ,, ,, ^reen, 44. „ ,, light blue, 44. red, 44. „ ,, white, 43. , 5 ,» yellow, 44. „ dunging liquors, 39. ,, extract black, 51, 68. ,, ,, blue, 51. ,, ,, bronze, 50. ,, ,, claret, 51. ,, ., orange, 49. ,, ,, paste, 49. ,, red, 49. ,, ,, slate, 50. ,, ,, violet, 59. ,, ,, yellow, 50. ,, fast myrtle, 59, 60. ,, gallazine blue, 65. ,, gallocyanine violet, 59. ,, green (4 lbs.), 55. ,, ,, discharge, 47. ,, ,, olive, 52. ,, ,, reserve, 65. ,, gum tragacanth, 49. ,, indigen blue, 59. ,, indigo blue, 58. ,, indophenol blue, 58. ,, indulin blue, 59. ,, iron buff (6° IV.), 57. ,, lead yellow (4 lbs.), 56. ,, paste, 44. ,, light grey, 66. ,, lime juice discharge, 59. ,, methyl green (3 ozs.), 53. ,, ,, violet (2 ozs.), 54. ,, methylene blue (3 ozs.), 53. ,, mordant, 59. ,, old gold, 52. ,, olive (medium), 52. ,, olive shade, 68. ,, orange discharge, 67. ,, para-nitraniline red, 62. ,, plum shade, 67. ,, preparation of diazo solution, 63. ,, printing colour, 62. ,, prussiate blue (2 lbs.), 57. ,, ,, green, 57. „ ,, of tin pulp, 57.- ,, ,, olive, 57. Kecipe for purple (6° Tw. ), 34. ,, ,, fixing liquor, 34. red (l°Tw.), 33. ,, (S°Tw.), 32. ,, (12° Tw.), 33. ,, ,, developing bath, 64. ,, ,, discharge, 67. ,, resist for aniline black, 42. ,, ,, mordants, 41. ,, ,, red, 41. ,, ,, ,, mordant, 49. ,, safranine pink (£ oz.), 54. ,, salmon, 52. ,, slate shade, 68. ,, stannic oxide pulp, 49. ,, starch thickening, 34. ,, sulphide of copper, 35. ,, sulphocyanide of alumina (lS°Tw.), 49. ,, tan shade, 51. ,, tannin paste, 53. ,, terra cotta, 52. ,, thickening for tin salts, 47. 50. ,, tobacco-brown shade, 6S. ,, twelve oz. — 12 oz. acid, 46. ,, vermilion red (6 lbs.), 56. ,, white discharge, 42, 46, 47, 67. ,, white reserve, 64. ,, yellow, 67. ,, ,, discharge, 42, 46, 47, 66. ,, ,, olive, 52 ,, ,, reserve, 64. ,, dyeing with alizarine red, 120. ,, ,, black (fast blue), 120. „ „ blue (dark), 119. ,, ,, (direct), 121. ,, ,, brown (bright shade), 1 17. „ „ (dark), 117. ,, ,, ,, (red shade), 117. ,, ,, ,, (yellow shade), 117. ,, „ buff pad (fast), 123. ,, buff pads, 122. ,, • ,, catechu browns, 117. ,, ,, chrome black, 119. ,, ,, cream pad (fast), 123. ,, >) >» pads, 122. ,, drab (dark), US. ,, ,, (light), US. ,, drabs, 118. ,, ,, greys, 118. ,, indigo (dark), 116. „ (%**), 116. ,, ,, iron buff (dark),. 116. 142 INDEX. Recipe for dyeing iron buff (light), 116. M ,, lead yellows, 116. ,, ,, old gold pad, 123. , , olive green pad (fast bright), 123. ,, ,, pink pad (fast bright), 124. ,, ,, Prussian blue (dark), 116. ,, ,, Prussian blue (light), 116. ,, ,, prussiate green, 119. red (direct), 121. „ ,, slate, 118. ,, ,, sumach bleach, 120. ,, ,. terra cotta pad (fast), 124, „ ,, yellow (direct), 121. i9 >> »> olive pad (fast), 124. Red lake. 97. ,, liquor. 30. ,, pigments, 97. ,, woods, 75, 76. Reserves, 63-65. Resist padded style, 41, 42. Resists, 63-65. Safflower, 77. Saffron, 77. Salts, 91-95. Santalin, 76. Santal wood, 76. Scheele's green, 97. Singeing, 5, 6. Soaps, 85-88. Analysis of, S6-8S. ,, Kinds of, S5, SO. , , Qualities of 86. Soda-resin boil, 11-13. Soda, table showing relation of per- centage to specific gravity of aqueous solutions, 137. Solid violet, 111. Solvents, 8S-89. Spirit soluble blue, 104. Stannate of soda, 92. Stannic chlorides, 92. ,, citrate, 92. ,, oxide, 92. Stannous acetate, 93. Stannous chloride, 91. Starch, 69, 70. ,, Maize, 70. ,, Wheat, 70. Straining, 73, 74. Sulphate of barium, 96 Sulphuric acid, table showing relation of percentage to specific gravity of aqueous solutions, 136. Sumach, S2. Tailing of pattern, 45. Tannic acid, 82. Tannin, Affinity of, for cotton, 3. matters, 82, 83. Tartar emetic, 93. Tartaric acid, 91. Testing bleaching powder, 14, 15. ,, lime, 7. ,, water, 126, 127. Theory of colours, 128-132. Thermometric tables, 134. Thickeners, 69-74. ,, Preparation of, 73. Thickening materials, 69. Tin salt, 91. Toluene, 99. Toluidine, 101, 102. Turmeric, 77. Ultramarine, 97. Valoxia, 82. Vermilion, 97. Vermilionette, 97. Water, 125- 12S. Character, 125, 126. ,, Determination of. in soap, 86, 87. ,, Quantity, 125. ,, Softening hard, 127, 128. ,, supply, 125. ,, Test for hardness of, 126, 127. Water blue, 105. ,, soluble blue, 104. Weights and measures, 132, 133. White pigments, 96. Xylenes, 99. Yellow dyestuffs, 76, 77. ,, pigments, 96. I Zinc white, 96. BELL AND BAIN, LIMITED, l'EINTEES, -11 MITCHELL STREET, GLASGOW. PATTERN SHEET No. 1. Cloth as received at the works. (See p. 6.) First process in bleaching — Singed. (Seep. 6.) Second process in bleaching- boiled. -Lime (See p. 10.) Third process in bleaching- Soured. (Seep. 11.) Fourth process in bleaching- First Ash boil. (See p. 12.) Fifth process in bleaching- Second Ash boil. 1 PATTERN SHEET No. 2. (See p. 12.) Completely bleached cloth. . 64 reduced 4 Lt. (light). (See p. 56. ) No. 64r reduced 4 Lt. (See p. 56.) No. 65 reduced 4 Lt. PATTERN SHEET No. 16. (See p. 56.) No. 66 reduced 1 Lt. (light). (See p. 56.) No. 67 reduced 1 Lt. (See p. 56.) No. 66 reduced 9 Lt. (See p. 56.) No. 67 reduced 9 Lt. (See p. 57. ) No. 68. (See p. 57.) No. 68 reduced 4 Lt. PATTERN SHEET No. 17. mim (Seep. 57.) No. 69 reduced 1 Lt. (light) (See p. 57.) No. 69 reduced 9 Lt. nun (See p. 57.) No. 70 reduced 1 Lt. (See p. 57.) No. 70 reduced 9 Lt. (See p. 66.) No. 99. (See p. 66.) No. 99 reduced 4 Lt. PATTERN SHEET No. 18. -Plain Shades. (Seep. 116. No. 1 Dark Indigo (See p. 116.) No. 2 Light Indigo. (Seep. 116.) No. 3 Dark Iron buff. (Seep. 116.) No. 4 Light Iron buff. (Seep. 116.) No. 5 Dark Prussian blue. (See p. 116.) No. 6 Light Prussian blue. PATTERN SHEET No. 19. -Plain Shades. (See p. 117.) No. 8 Catechu brown. (See pp. 117 and 121.) No. 8 topped with Chrysamine. (See pp. 117 and 121.) No. 8 topped with Benzo orange. (See p. 121.) No. 22 Direct red. (Seep. 121.) No. 24 Direct yellow. WORKS BY GEORGE H. HURST, F.C.S., Member of the Society of Chemical Industry ; Lecturer on the Technology of Painters' Colours, Oils, and Varnishes, the Municipal Technical School, Manchester. PAINTERS' COLOURS, OILS, AND VARNISHES: A Practical Manual. With Numerous Illustrations, Price 12s. 6d. General Contents. — Introductory — The Composition, Manufacture, Assay, and Analysis of Pigments, White, Red, Yellow and Orange, Green, Blue, Brown, and Black— Lakes — Colour and Paint Machinery— Paint Vehicles (Oils, Turpentine, &c. , &c. ) — Driers— VARNISHES. " This useful book will prove most valuable. We feel bound to recommend it to all engaged in the arts concerned." — Chemical News. " A practical manual in every respect . . . exceedingly instructive. The section on Varnishes the most reasonable we have met with." — Chemist and Druggist. " Very valuable information is given." — Plumber and Decorator. " A thoroughly practical book, . . . constituting, we believe, the only English work that satisfactorily treats of the manufacture of oils, colours, and pigments." — Chemical Trades' Journal. " Throughout the work are scattered hints which are invaluable to the intelligent reader. " — Invention. BY THE SAME AUTHOR. GARMENT DYEING AND GLEANING- A Practical Book for Practical Men. With Numerous Illustrations. 4s. 6d. General Contents.— Technology of the Textile Fibres— Garment Cleaning — Dyeing of Textile Fabrics — Bleaching — Finishing of Dyed and Cleaned Fabrics — Scouring and Dyeing of Skin Rugs and Mats — Cleaning and Dyeing of Feathers — Glove Cleaning and Dyeing — Straw Bleaching and Dyeing — Glossary of Drugs and Chemicals — Useful Tables. "An up-to-date hand book has long been wanted, and Mr. Hurst, who has produced several admirable works, has done nothing more complete than this. An important work, the more so that several of the branches of the craft here treated upon are almost entirely without English Manuals for the guidance of workers. The price brings it within the reach of all." — Dyer and Calico-Printer. " Mr. Hurst's work decidedly fills a want . . . ought to be in the hands of every garment dyer and cleaner in the Kingdom." — Textile Mercury. LONDON: CHARLES GRIFFIN & CO., LIMITED, EXETER STREET, STRAND. " The most valuable and ui-eful woks on Dyeing that has yet appeared in the English language . . . likely to bo the Standard Work of Keherenck for years to come." — Textile Mercury. In Two Large 8vo Volumes, 920 pp., with a SUPPLEMENTARY Volume, containing Specimens of Dyed Fabrics. Handsome Cloth, 45s. MANUAL OF DYEING: FOR THE USE OF PRACTICAL DYERS, MANUFACTURERS, STUDENTS, AND ALL INTERESTED IN THE ART OF DYEING. E. KNECHT, Ph.D., F.I.C., Head of the Chemistry and Dyeing Department wf the Technical School, Manchester; Editor of "The Journal of the Society of Dyers anil Colourists ; " CHR. RAWSON, F.I.C., F.C.S., Late Head of the Chemistry and Dyeing Department for the Technical College, Bradford ; Member of Council ot the Society of Dyers and Colourists ; And RICHARD LOEWENTHAL, Ph.D. General Contents. — Chemical Technology of the Textile Fabrics — Water — Washing and Bleaching — Acids, Alkalies, Mordants — Natural Colouring Matters — Artificial Organic Colouring Matters — Mineral Colours — Machinery used in Dyeing — Tinctorial Properties of Colouring Matters — Analysis and Valuation of Materials used in Dyeing, &c, &c. " This most valuable wokk . . will be widely appreciated."— Chemical News. " This authoritative and exhaustive work . . . the most complete we have yet seen on the subject." — Textile Manufacturer. " The most exhaustive and complete wokk on the subject extant." — Textile Recorder. " The distinguished authors have placed in the hands of those daily engaged in the dye- house or laboratory a work of extkeme value and undoubted utility . . . appeals quickly to the technologist, colour chemist, dyer, and more particularly to the rising dyer of the present generation. A book which it is refreshing to meet with."— American Textile Record. LONDON: CHARLES GRIFFIN & CO., LIMITED, EXETER STREET, STRAND. IWRE BOOKCASE N. MANCHESTER, INDIANA 1H BbNBh H i^^H^^HH