h, 101W BARNES-'' APPLICATION OF TITANIUM TANNO OXALATE TO TEXTILES." 141

electrolyte in solution is applied, or further, even if the purcst, form of water is applied, there is some definite change of molecular aggregation set up, and this effect can be brought to visible demonstration by means of reagents which produce colour effects.

We express our thanks to Mr. W. 1). Dick and to Dr. S. Judd Lewis for their contributions noted in the text; also to our friend M i . S. 8. Napper (of C'ourtanlds, Ltd.) for analytical results also recorded.

The C'hairman (Dr. A. RBe) said there were many Societies in t,he country which he was sure would have considered i t a great privilege to have such a paper read before them, and they were very grateful to Mr. Cross for placing before t,he Societ,y of Dyers and Colourist,s t,he results of his investigat,ions.

Prof. E. Knecht aslied what nietzhod had been used for quantitative estimatioii of phloro- glucinol 1 He had personally carried out a number of determinations on mecha.nica1 wood pulp, and had used the paranit)raniline method. He had treated a known weight of wood pulp with a standard solution of p-nitraniline in hydrochloric acid, and had estimated the excess of p-nitraniline in the filtrate by ineans of t.it.anous chloride. As the combinston of the Ligno-cellulose with the paranitraniline was slowly decomposed by water, it was necessary, in order to obtain concordant' result's, to work empirically, using a, definite amount) of water for washing. His result's bore out Mr. Cross's contention that the a,niouiit of reagent actually taken up was very small. Another question he desired to ask was " What time docs Mr. Cross suggest for the drying of paper impregnated with hydrochloric acid and phloroglucin '1 '! Was i t air-dried, or was i t dried in an oven '4 Another point in connection with the interesting obscrvation of the formatJion of nmltol froni cellulose by heating to 140" C:. wa,s thc yield, or t,he approximate yield, of the 1~iiiltol.

Mr. Cross, in reply to Prof. Knecht, said foi estiniating the trihydric phenols they used a volumetric process, based on their reaction with formaldehyde or furfuraldehyde. With regard t,o the yield of inaltol, it was prospcctivelg considerable, but they had not yet cletcriiiiiied the actua.1 quant,ities formed. They were following up t,he point in tjhis direction, and hoped to largely increase the quant,ity by gett,ing the right conditions.

Mr. J. R. Dellison asked whether nisltol woiild be formed by high pressure steam.

Mr. Cross : I certainly think so. Chlitjionb would have t'o be devised t,o prcvcw t interioi condensations.

- Mr. Deriison pointed out that under the

influence of steam cotton became tender, but it retained its form as fibre. Did that mean that it had been entirely converted into maltol ?

Mr. Cross said he did not think so. The general case was that of migration of hydrogen and hydroxyl. Referring to the C'hairman's observations, he had come to their Society because he knew there was an earnest band of workers centred in it, who only wanted re- minding, a t this time of crisis, of the vast national interests coiinoted by " cellulose," and the potentiality of scientific progress centreing in " ligno-celluose."

MANCHESTER SECTION.

Meeting held March 17t,h, 1916, Mr. W. H. PENNMGTON in the cha.ir.

Application of Titanlum Tanno Oxalate to Textiles.

By JOSEPH BARNES, F.1.C'.

The most striking feature of titanium from a tiiictorial point of view is the formation of the brownish-orange compound when its salts are mixed with tannic acid. This compound, when deposited on the fibrc of textiles, varies from a light yellow to a deep yellowish-orange, axid is very resistant to light and to washing. As a means for fixing tannic acid on the fibre, titanium is quite as efficient as antimony, and for certain shades the yellow colour of the titanium tannate is an advantage when the yarn or cloth is sub- sequently dyed with a basic dye. The method of applying a solution of taiinate of titanium in oxalic acid (tanno-oxalate) is so simple, quick, and effectual that, i t is surprising i t has attracted so little at'telition. The shades of yellow and gold are pleasing, and in the case of mercerisecl cotton are especially so, seeing that the lustre of the material is not impaired by the process. During the shortage of dyes, titanium has un- doubtedly a distinct usc in enabling one to produce certain shades of green, red, and brown from basic dyes which are still procurable.

The samples shown are inercerised em- broidery cotton.

The titanium tannate colour may be modified by mixing certain Alizarin or allied colours with the tannin " prepare," passing through a titanium bath-eit'her the oxalate or the sodium- titanium sulphatc-and developing the shade by boiling in water or steaming, part of the

ABSTRd CTS-MORDANTS, B

titanic oxide in this case acting as a mordant for the Alizarin.

Cot.ton already coloured with tannin-titanium may be dyed up with Aliza,rin Orange, Alizarin Brown, Alizarin, &c., and if the dyeing is carried on for a sufficient length of tinie pra,ctically the whole of the tannic acid becomes replaced by the Alizarin dye. An addition of acetate of lime to the dyebath inay in some cases be advisable. It is thus an easy matter to obtain a great variety of fast art shades by this process, which may be sumniarised as follows :-Pass through a, bath of tanno-oxalate of titaniiun, wring up or squee.ze, pass t.hrough a hot, bath of common salt, wash and dye up with the Alizarin.

It would seein that the tannate of titaiiiuni might serve a,s a ground for khaki shades on cotton as well as upon wool. Attention inay be drawn to the fact that, quite a good scarlet. may be produced on wool morclanted with tit'anic oxide by dyeing with Alizarin Orange. Certain precaut,ions have to be taken in order to get a bright shade. The materia,ls must be as free as possible from iron, and care inust be taken to avoid the change of the titanic oxide into the iveta conclition. A sufficiency of oxalic or tartaric acid inust be used in the niordanting bath, and prolonged boiling must be avoided. Tartaric acid seeins to have a better effect in preventing the change to the meta state than oxalic.

The process of dyeing 'the saniples may be briefly described as follows :-

No. I.-Turn for a few minutes in the tanno- oxa,late bat'h a t 1" Tw., wring up, and pass into a 5 per cent. salt bath a t 110" F.; wash and turn in a warm soap bath, wring up and dry.

No. 2.-As No. 1, only using the tanno-oxalate at 3" Tw.

No. 3.-As No. 1, but with the addition of a little Methylene Blue to the soap bath. The yarn was then wrung up and again worked in the tanno-oxalate bath strengthened, wrung up, then into the salt bath, washed a i d finished in the soap bath.

No. 4.-Tanno-oxalate a t 3" Tw.; s d t bath ; wash and dye up with Alizarin Orange, keeping a t the boil for about half an hour ; wash aiid soap.

No. 5.-Tanno-oxalate a t 2" Tw.; salt bath, &c., and dye up with cmrulein.

NO. 6.-As No. 5, but, dye up with .Alizarin, adding a littale acetate of lime to the dyebath, which was kept a t the boil for one hour.

No. 7.-As No. 6, using Alizarin Brown for the dyeing. All t,he samples were soaped.

No. 8 is a sample of wool dyed up to t8he boil in a single bath of tanno-oxalate with an addition of 4 per cent. oxalic acicl reckaned on weight of wool.

DISCUSSION.

Mr. 12. G. Jones asked whether the results the lecturer had shown on yarn could be proclucecl on piece goods with uniform results.

- . 142 -

[DS, ALKALIS, - N D SA4LTS. [May, 1916. -- -

Mr. G. E. Holden inquired whether the lec- turer had tried the effect of adding other colour- [rig matters to the titanium-tanno-oxalate bath.

Mr. W. Thonisoii said he understood Mr. Barnes to say that the orange titanium-tannate 311 cloth was insoluble in water after treatment with a solution of salt. What was the r6le of thc salt in effecting this precipitation and fixa- tion of the colour 1

The Lecturcr, in reply to Mr. Jones, said there was no reason why the same results could iiot be obtained on rnercerisecl piece goods. With regard to Mr. Holden's question, Cutch could be substituted for tannic acid, and the mordant colours could be applied in the first bath. It was not possible to use the basic zolours, LES these at once precipitated the tannic mid. Alizarin Orange could be fixed by applying it with taiinic acid, and then passing through titanium oxalate. He was not satisfied as to the nature of the reaction taking place when the titanium tannate was precipitated by salt. The fact that it was possible to obtain soluble lakes of alumina and iron with certain dyewoods was lmown to John Mercer, who also knew that these lakes were precipitated by saline solutions.

Mr. J. R. Haniiay suggested that the effect was perhaps due to the colloidal solution of titanium tannate being precipitated as a colloid.

'Elbetracte front Ett~Ifeb airb $orefen 3owrnaIe anb patetite.

(The Titles of Patents are in some cases abridged.)

11.-MORDANTS, ACIDS, ALKALIS, AND SALTS.

Electrolytic Production of Perborates. K. ARNDT.

Electrolysis of a solution containing 45 grms. borax and 120 grnis. sodiuin carbonate per litre, using 6 volts, gives a satisfactory yield of sodium perborate (NaBO3.4H,O). The anode is coin- posed of a pIatinum wire network, ancl the cathode made up of zig-zag tin tubes through which water is passed for cooling, the bath being kept a t 17"-18" C. When the electrolysis has given a solution of sufficiently high active oxygen content, the electrodes are renioved and the perborate crpstallises out, is washed with iced water and dried. By adding chromate and Turkey-red oil, only 3 per cent. of the hydrogen is used for the reduction of the per-salt. A high concentration of the per-salt, e.g., 27 grins. per litre, is attained by covering the cathode with vaseline.-Zeit. angcw. C?~em., 1915, 28, p. 621.

17. W. A.