Chapter 15

There is little doubt, however, that the question of the future industry in the various forms of cellulose, thread, film, structureless powder or solid aggregate, obtainable by artificial means, mainly turns upon cost of production. Irrespective of cost, there would, no doubt, be a market for all these products, based upon such of their properties or effects as are indispensable and not otherwise obtainable. As an illustration, we may cite the extraordinary selling prices of 40-50 fr. per kilo, for the 'artificial silks' (collodion process) which ruled some three years ago; and we may note that for a special application of viscose the dissolved cellulose is paid for at the rate of 10 per lb. These facts are certainly worthy of mention, and should be borne in mind as an index of some special features of modern manufacturing industry. But with a material like cellulose rendered available in a new shape the question which always arises more prominently than that of limited uses at high prices is that of consumption on the extensive scale which marks the older and well-known products. That question is rapidly solving itself in this country as regards the 'artificial silks.' There is at present a limited market at 9s.-10s. per lb., a price which on the one side excludes extensive consumption, and on the other practically bars manufacture in this country by any of the collodion systems. It will appear from a very elementary calculation of what we may call the theoretical costs that the above selling price would not have a remunerative margin. The theoretical costs are made up of

Raw materials[14] {Cotton. Nitrating acid. Ether-alcohol (solvent). {Denitrating chemicals.

{(a) Nitrating and preparing collodion. Denitrating { and bleaching. Labour {(b) Textile operations. Spinning. Winding and twisting. {Rewinding.

Power {Making, filtering, and distributing collodion. {Driving textile machinery.

Added to which are the costs of expert management and supervision and general establishment expenses. It is evident that raw materials make up a large fraction of the total cost; also that a very large item is the waste work of converting the cellulose into nitrate, only to remove the nitric groups so soon as the cellulose is obtained as thread.

It is clear that the aqueous solutions of cellulose have a double advantage in this respect--not only do they readily yield an approximately pure cellulose as a direct product of regeneration or decomposition, but the first cost of the solution is very much less. With these newer products, therefore, the spinning problem enters on a new phase of struggle. It is certain that at selling prices at or about 5s. to 7s., very large markets will be open to the product or products. The two processes which are or may be able to fulfil this demand are those based (1) on cuprammonium solutions of cellulose, (2) on the sulphocarbonate or viscose. As regards _first cost_ of the solution the latter has a large advantage. One ton of wood pulp (at 12l.) can certainly be obtained in solution in a condition ready for spinning at a total cost (materials) of less than 30l. The cuprammonium process, so far as 'outside' information goes, requires for production of the solution (1) cotton as raw material, (2) ammonia (calc. as concentrated aqueous) equal to 1-1/2 times its weight, and (3) metallic copper 25 p.ct. of its weight; and the costs are approximately 100l. per ton. It is obvious that the materials are recoverable from the precipitating-bath, but at a certain added cost. We have no statements as to the proportion recoverable nor the costs incurred, and we are therefore unable to measure the total net cost of the regenerated cellulose by this process. It is certainly much less than by the collodion processes. As to the textile quality of the thread, the product has not yet been on a sufficiently wide selling basis for that to have been determined. There are a great many factors which enter here. Not merely the external characters of lustre, softness, and translucency, but the all-important quality of uniformity of thread. The collodion-spinning is a process still very defective in this respect, and the defect is no doubt referable to the difficulty of securing absolute physical invariability of the collodion. It is to be regretted, in the interests of scientific development, that none of the technologists who have published investigations of these processes have entered into the discussion of the fundamental factors of the spinning processes; we are, therefore, unable at this stage to discuss these elements of a full comparison in greater detail. We cannot, for this reason, say how far the cuprammonium process diverges in point of control from the standard of the collodion processes. Of the 'viscose' product we have a more intimate knowledge, and it certainly reaches a higher general standard than the older and now well-known artificial silks. The process is also sufficiently developed to enable the total costs of production to be estimated at a figure less than one-half that of the 'collodion' processes. This would assure to this system an _entrée_ in this country, and a basis of expansion limited only by the ordinary laws of supply and demand.

This prospect is opened up precisely at the moment when, for various reasons connected both with the difficulties of manufacture and the narrowing of the margin of profit, the proprietors of the two systems of collodion-spinning have decided to abandon all idea of manufacturing by these systems in this country.[15] We leave the discussion of the industrial problem at this point.

In regard to other developments based upon the exceptional character and properties of the sulphocarbonate, their further discussion will exemplify no general principles; and as regards technical detail they have been dealt with in the papers previously noticed.

As a purely general question, if there is to be any industry in these 'artificial' forms of cellulose, commensurate with the magnitude that usually belongs to the cellulose industries, it must come by way of a plastic or soluble form prepared at low cost, and conserving the essential molecular properties of the cellulose aggregate. These are the particular features of the sulphocarbonate. The obvious difficulties in the way of its industrial applications are those caused by the presence of alkali and sulphur compounds. These are dealt with by appropriate chemical means; but the fact that there is a special chemistry of the product has rendered its industrial progress slow. The work of the last five years in this, as in other applications of cellulose in its many derived forms, has resulted in a considerable addition to the domain of practical chemistry.

Further developments will make an increasing demand upon our grasp of the fundamental constitutional problems, to which it is the main purpose of the present volume to contribute.

FOOTNOTES:

[11] This is the most complete notice that has appeared and the bibliography is exhaustive. The publication comes into our hands too late to be noticed in detail.

[12] _Text-book on Paper-making_, Cross and Bevan (Spon, London: second edition, 1900). _Chemistry of Paper-making_, Griffin and Little (New York, 1894: Howard Lockwood & Co.). _Handbuch d. Papierfabrikation_, C. Hofmann (Berlin). _Paper Trade Review_, London (weekly). _Papier-Zeitung_, Berlin.

[13] William Mather, M.P., of the firm of Mather & Platt, Limited, Manchester.

[14] The actual costs varying considerably in the various countries, we cannot make any specific statement. But from estimates we have made, the costs of obtaining cotton in filtered solution as collodion multiply its value by 12-14, the denitrations adding further costs and raising this multiple to 18-20. In the same estimates we arrived at the conclusion that the item for raw materials made up 60 p.ct. of the total cost of the yarn.

[15] The recent failure of a French company founded for the exploitation of the cuprammonium process may be taken as showing that it presents very considerable technical difficulties. It is a matter of common knowledge that this company _estimated_ the costs of production to be such as to enable the product to be sold at 12 fr. per kilo., whereas the costs actually obtaining were a large multiple of this figure.

INDEX OF AUTHORS

Bardy, C. H., 157

Bokorny, T., 43

Bronnert, E., 54

Bumcke, G., and Wolffenstein, R., 67

Buntrock, 25

Cross, C. F., 139, 152, 155

Cross, C. F., and Bevan, E. J., 92

Cross, C. F., Bevan, E. J., and Briggs, J. F., 118

Cross, C. F., Bevan, E. J., and Heiberg, T., 114

Cross, C. F., Bevan, E. J., and Smith, C., 101, 103, 105, 114, 145

De Haas, R. W. T., and Tollens, B., 151

Faber, O. v., and Tollens, B., 71

Feilitzen, H. v., and Tollens, B., 154

Fenton, H. J. H., 8

Fenton, H. J. H., and Gostling, M., 86

Fraenkel, A., and Friedlaender, P., 26

Gardner, P., 22

Gilson, E., 112

Hancock, W. C., and Dahl, O. W., 135

Hoffmeister, W., 96, 100

Kleiber, A., 97

Kröber, E., 121

Krüger, M., 119

Lange, H., 25

Lewes, V. H., 15

Luck, A., and Cross, C. F., 45

Margosches, B. M., 159

Morrell, R. S., and Crofts, J. M., 114

Mylius, F., 21

Nastukoff, H., 74

Omelianski, V., 76

Ruff, O., 117

Salkowski, E., 113

Schöne, A., and Tollens, B., 124

Seidel, H., 149

Sherman, H. C., 137

Simonsen, E., 146

Storer, F. H., 142

Strehlenert, R. W., 158

Suringar, H., and Tollens, B., 16, 124

Süvern, C., 63

Tollens, B., 148, 151

Tollens, B., and Glaubitz, H., 122

Vignon, L., 43, 70, 72, 94

Will, W., and Lenze, P., 41

Winterstein, E., 109, 144, 153

INDEX OF SUBJECTS

Acetone, action on cellulose nitrates of diluted, 46

Acid-cellulose, 68

Acids, volatile, from cellulose, 145

_Æschynomene aspera_, 135

Alcohol from cellulose and wood, 146

Alcoholic soda, mercerisation results with, 26

Alkali-cellulose, effects of long storage on, 31

Amyloid, vegetable, 153

Arabinose from gluconic acid, 117

'Ash' of plants, 13

_Bacterium xylinum_, 85

Barley plant, chemical processes in the, 103

---- straw, carbohydrates of, 105

Bleaching, 166

Bran, digestion of, 139

Brommethylfurfural, 8, 84, 86

Carbohydrates, action of hydrogen bromide on, 86; action of hydrogen peroxide on, 114; nitrated, as food for mould fungi, 43; nitrates of, 41; quantitative separation of, 96

Carbohydrates of barley straw, 105; of wheat, 137; of yeast, 113

'Caro's reagent,' 118

'Celloxin,' 71

Cellulose, alcohol from, 146; constitution of, 77, 92; fermentation of, 76; industrial uses of, 155; iodine reaction of, 21; methods for the estimation of, 3, 4, 16, 19, 97; nitration of, 43; saccharification of, 73; ultimate hydrolysis of, 11; volatile acids from, 145

---- acetates, monoacetate, formation of, 40; tetracetate, constitution of, 80

---- benzoates, 34; from structureless cellulose, 36; from three varieties of cotton, 35; monobenzoate, properties of, 36; dibenzoate, properties of, 37; acetylation of, 130; nitration of, 38

---- derivatives, commercial aspects of, 171; saccharification of, 73

---- nitrates, 44, 45, 83; structureless, 45, 51; cupric reducing power of, 73; instability of, 50, 53

---- sulphocarbonate, 27; effects of the nature of the cellulose, 28;

---- ---- solutions, analysis of, 32; iodine reaction of, 33; loss of carbon bisulphide, 33; viscosity of, 30

Cell-wall constituents, 97

Cereal celluloses, 101, 105

Chitin, 112

Chlorination, Cross and Bevan's method, 19; statistics of, 134

Chloro-lignone, 126

Collodion. _See_ Silk, artificial

Cotton, lustreing effect of mercerisation, 23; mercerised, structural properties of, 25; pentosane content of, 148

'Crude fibre,' 17

Cuprammonium solvent, 21, 58, 173

Currants, pectin of, 152

Denitration of collodion silk, 56; of jute nitrate, 133; products of, 74

Dioxybutyric acid, 71

Elder pith, 137

Eriodendron, seed hair of, 92

Explosives, 44; sporting powders, 52

Fermentation of cellulose, 76; of furfuroids, 108; of sugar from wood, 148

Fibres, report on miscellaneous, 139

Flax boiling, 168; spinning, 161

Fodder plants, pentosanes of, 122

Fungi, tissue constituents of, 109

Furfural from cellulose, oxycellulose, and hydrocellulose, 70; derivative from lævulose, 8; estimation as hydrazone and phloroglucide, 119, 121; oxidation of, 114, 118 (_refer also_ 'Pentosanes')

Furfuroids, 8, 10, 102, 105; assimilation of, 108

Gabriel's method of cellulose estimation, 18

Gluconic acid, action of hydrogen peroxide on, 117

Glucosamin, 112

Hemicellulose, 96, 97; determination and separation of, 100

Hönig's method of cellulose estimation, 18

'Hydralcellulose,' 68

Hydrocellulose, 73; nitration of, 43

Hydrogen peroxide, oxidations with, 114

Hydroxyfurfural in lignocellulose, 9, 116, 118

Incandescent mantles of artificial silk, 14, 15

Industrial appliances of cellulose, 155

Iodine reaction of cellulose, 21

Isosaccharinic acid, 71

Jute, composition of, 141; quality of, 140; treatment of, 142 (_refer also_ Lignocellulose)

---- acetate, 129

---- benzoate, 127; acetylation of, 130; nitration of, 132

---- nitrate, 131

Ketoses, physiological importance of, 9

Lange method of cellulose estimation, 18, 98

Lead compounds of nitrated carbohydrates, 49

Lignin, 100

Lignocellulose, constitution of, 133; esters of, 125; hydroxyfurfural in, 9; new type of, 135

Lignone complex, properties of, 126

'Lignorosin,' 151

'Lustra-cellulose.' _See_ Silk, artificial

Malt, pentosanes of, 122

Mather system of boiling textiles, 167

Mercerization, 22; shrinkage during, 24

Mercerised yarn, strength and elasticity of, 25, 26

Methylhydroxyfurfural, 84

Mould fungi, nitrated carbohydrates as food for, 43

Mycosin, 113

Nitrated carbohydrates, lead compounds of, 49

Nitrates of carbohydrates, 41

Nitrocellulose (_see_ Cellulose nitrates); silk, 55

'Normal' cellulose, definition of, 27

Normal paper, 160

Oxycellulose esters, 72; nitration of, 43; researches on, 71, 72, 74; _résumé_ of properties, 94

Oxygluconic acid, 117

Paper, deterioration of, 155; normal standard, 160; pulp, spinning of, 169

Peat, constituents of, 154

Pectins, 151, 152

Pentosanes, 100, 109, 144; constituents of cotton, 124; constituents of fodder, 122; estimation of, 121; of seeds during germination, 124

'Permanent tissue,' 103

Phloroglucinol, 119, 121

Plant tissues, carbohydrates of, 96, 97, 99

Plants, source of unsaturated compounds in, 145

Powders, manufacture of sporting, 52

Saccharification of cellulose and derivatives, 73

Schulze method of cellulose estimation, 18, 98

Schweizer solution, 101

Seeds, pentosanes in germinating, 124

Silica in plant tissues, 13

Silk, artificial, 54, 62, 63, 172; bibliography of, 60; from cuprammonium, 58, 64, 173; from nitrocellulose (collodion), 55, 63, 172; from viscose, 59; from zinc chloride, 59; reactions of, 64

---- natural, reactions of, 64

Straws, 101, 105

Succinic acid from furfural, 118

Sulphite waste liquors, 149, 164

'Swedish' filter paper, 14

Tissue constituents, 99, 109

Trees, composition of trunk woods, 142

Viscose and viscoid, 157, 158, 159

---- silk, 59, 175

---- ---- specific gravity of, 34 (_refer also_ Cellulose sulphocarbonate)

'Vulcanised fibre,' 20

Weende, method of cellulose estimation (crude fibre), 17, 98

Welsbach mantles, 14; Clamond type, 15

Wheat grain, insoluble carbohydrates of, 137

Wood, alcohol from, 146, 148

Wood-cellulose, waste liquors, 149

Wood-gum, 144

Wood-pulp, processes, 162

Wood, trunks of trees, 142

Yeast, carbohydrates of, 113

Zinc chloride, artificial silk, 59; solvent action of, 20