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Nitro-Explosives: A Practical Treatise
by P. Gerald Sanford
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Mr Prentice says: "I may point out that while the ordinary process of making nitric acid is one of fractional distillation by time, mine is fractional distillation by space." "Instead of the operation being always at the same point of space, but differing by the successive points of time, I arrange for the differences to take place at different points of space, and these differences exist at one and the same points of time." It is possible with this plant to produce the full product of nitric acid of a gravity of 1.500, or to obtain the acid of varying strengths from the different still-heads. One of these stills, capable of producing about 4 tons of nitric acid per week, weighs less than 2 tons. It is claimed that there is by their use a saving of more than two-thirds in fuel, and four- fifths in condensing plant. Further particulars and illustrations will be found in Mr Prentice's paper (Journal of the Society of Chemical Industry, 1894, p. 323).



CHAPTER III.

NITRO-CELLULOSE, &c.

Cellulose Properties—Discovery of Gun-Cotton—Properties of Gun-Cotton— Varieties of Soluble and Insoluble Gun-Cottons—Manufacture of Gun-Cotton— Dipping and Steeping—Whirling out the Acid—Washing—Boiling—Pulping— Compressing—The Waltham Abbey Process—Le Bouchet Process—Granulation of Gun-Cotton—Collodion-Cotton—Manufacture—Acid Mixture used—Cotton used, &c.—Nitrated Gun-Cotton—Tonite—Dangers in Manufacture of Gun-Cotton— Trench's Fire-Extinguishing Compound—Uses of Collodion-Cotton—Celluloid— Manufacture, &c.—Nitro-Starch, Nitro-Jute, and Nitro-Mannite.

The Nitro-Celluloses.—The substance known as cellulose forms the groundwork of vegetable tissues. The cellulose of the woody parts of plants was at one time supposed to be a distinct body, and was called lignine, but they are now regarded as identical. The formula of cellulose is (C{6}H{10}O{6}){X}, and it is generally assumed that the molecular formula must be represented by a multiple of the empirical formula, C{12}H{20}O{10} being often regarded as the minimum. The assumption is based on the existence of a penta-nitrate and the insoluble and colloidal nature of cellulose. Green (Zeit. Farb. Text. Ind., 1904, 3, 97) considers these reasons insufficient, and prefers to employ the single formula C{6}H{10}O{5}. Cellulose can be extracted in the pure state, from young and tender portions of plants by first crushing them, to rupture the cells, and then extracting with dilute hydrochloric acid, water, alcohol, and ether in succession, until none of these solvents remove anything more. Fine paper or cotton wool yield very nearly pure cellulose by similar treatment.

Cellulose is a colourless, transparent mass, absolutely insoluble in water, alcohol, or ether. It is, however, soluble in a solution of cuprammoniac solution, prepared from basic carbonate or hydrate of copper and aqueous ammonia. The specific gravity of cellulose is 1.25 to 1.45. According to Schulze, its elementary composition is expressed by the percentage numbers:—

Carbon 44.0 per cent. 44.2 per cent. Hydrogen 6.3 " 6.4 " Oxygen 49.7 " 49.4 "

These numbers represent the composition of the ash free cellulose. Nearly all forms of cellulose, however, contain a small proportion of mineral matters, and the union of these with the organic portion of the fibre or tissue is of such a nature that the ash left on ignition preserves the form of the original. "It is only in the growing point of certain young shoots that the cellulose tissue is free from mineral constituents" (Hofmeister).

Cellulose is a very inert body. Cold concentrated sulphuric acid causes it to swell up, and finally dissolves it, forming a viscous solution. Hydrochloric acid has little or no action, but nitric acid has, and forms a series of bodies known as nitrates or nitro-celluloses. Cellulose has some of the properties of alcohols, among them the power of forming ethereal salts with acids. When cellulose in any form, such as cotton, is brought into contact with strong nitric acid at a low temperature, a nitrate or nitro product, containing nitryl, or the NO_{2} group, is produced. The more or less complete replacement of the hydroxylic hydrogen by NO_{2} groups depends partly on the concentration of the nitric acid used, partly on the duration of the action. If the most concentrated nitric and sulphuric acids are employed, and the action allowed to proceed for some considerable time, the highest nitrate, known as hexa-nitro- cellulose or gun-cotton, C_{12}H_{14}O_{4}(O.NO_{2})_{6}, will be formed; but with weaker acids, and a shorter exposure to their action, the tetra and penta and lower nitrates will be formed.[A]

[Footnote A: The paper by Prof. Lunge, Jour. Amer. Chem. Soc., 1901, 23[8], 527-579, contains valuable information on this subject.]

Besides the nitrate, A. Luck[A] has proposed to use other esters of cellulose, such as the acetate, benzoate, or butyrate. It is found that cellulose acetate forms with nitro-glycerine a gelatinous body without requiring the addition of a solvent. A sporting powder is proposed composed of 75 parts of cellulose nitrate (13 per cent. N.) mixed with 13 parts of cellulose acetate.

[Footnote A: Eng. Pat. 24,662, 22nd November 1898.]

The discovery of gun-cotton is generally attributed to Schoenbein (1846), but Braconnot (in 1832) had previously nitrated starch, and six years later Pelouse prepared nitro-cotton and various other nitro bodies, and Dumas nitrated paper, but Schoenbein was apparently the first chemist to use a mixture of strong nitric and sulphuric acids. Many chemists, such as Piobert in France, Morin in Russia, and Abel in England, studied the subject; but it was in Austria, under the auspices of Baron Von Lenk, that the greatest progress was made. Lenk used cotton in the form of yarn, made up into hanks, which he first washed in a solution of potash, and then with water, and after drying dipped them in the acids. The acid mixture used consisted of 3 parts by weight of sulphuric to 1 part of nitric acid, and were prepared some time before use. The cotton was dipped one skein at a time, stirred for a few minutes, pressed out, steeped, and excess of acid removed by washing with water, then with dilute potash, and finally with water. Von Lenk's process was used in England at Faversham (Messrs Hall's Works), but was given up on account of an explosion (1847).

Sir Frederick Abel, working at Stowmarket and Waltham Abbey, introduced several very important improvements into the process, the chief among these being pulping. Having traced the cause of its instability to the presence of substances caused by the action of the nitric acid on the resinous or fatty substances contained in the cotton fibre, he succeeded in eliminating them, by boiling the nitro-cotton in water, and by a thorough washing, after pulping the cotton in poachers.

Although gun-cottons are generally spoken of as nitro-celluloses, they are more correctly described as cellulose nitrates, for unlike nitro bodies of other series, they do not yield, or have not yet done so, amido bodies, on reduction with nascent hydrogen.[A] The equation of the formation of gun-cotton is as follows:—

2(C{6}H{10}O{5}) + 6HNO{3} = C{12}H{14}O{4}(NO{3}){6} + 6OH{2}. Cellulose. Nitric Acid. Gun-Cotton. Water.

The sulphuric acid used does not take part in the reaction, but its presence is absolutely essential to combine with the water set free, and thus to prevent the weakening of the nitric acid. The acid mixture used at Waltham Abbey consists of 3 parts by weight of sulphuric acid of 1.84 specific gravity, and 1 part of nitric acid of 1.52 specific gravity. The same mixture is also used at Stowmarket (the New Explosive Company's Works). The use of weaker acids results in the formation of collodion- cotton and the lower nitrates generally.

[Footnote A: "Cellulose," by Cross and Bevan, ed. by W.R. Hodgkinson, p. 9.]

The nitrate which goes under the name of gun-cotton is generally supposed to be the hexa-nitrate, and to contain 14.14 per cent. of nitrogen; but a higher percentage than 13.7 has not been obtained from any sample. It is almost impossible (at any rate upon the manufacturing scale) to make pure hexa-nitro-cellulose or gun-cotton; it is certain to contain several per cents. of the soluble forms, i.e., lower nitrates. It often contains as much as 15 or 16 per cent., and only from 13.07[A] to 13.6 per cent. of nitrogen.

[Footnote A: Mr J.J. Sayers, in evidence before the court in the "Cordite Case," says he found 15.2 and 16.1 per cent. soluble cotton, and 13.07 and 13.08 per cent. nitrogen in two samples of Waltham Abbey gun-cotton.]

A whole series of nitrates of cellulose are supposed to exist, the highest member being the hexa-nitrate, and the lowest the mono-nitrate. Gun-cotton was at one time regarded as the tri-nitrate, and collodion-cotton as the di-nitrate and mono-nitrate, their respective formula being given as follows:—

Mono-nitro-cellulose C{6}H{9}(NO{2})O{5} = 6.763 per cent. nitrogen. Di-nitro-cellulose C{6}H{8}(NO{2}){2}O{5} = 11.11 " " Tri-nitro-cellulose C{6}H{7}(NO{2}){3}O{5} = 14.14 " "

But gun-cotton is now regarded as the hexa-nitrate, and collodion-cotton as a mixture of all the other nitrates. In fact, chemists are now more inclined to divide nitro-cellulose into the soluble and insoluble forms, the reason being that it is quite easy to make a nitro-cellulose entirely soluble in a mixture of ether-alcohol, and yet containing as high a percentage of nitrogen as 12.6; whereas the di-nitrate[A] should theoretically only contain 11.11 per cent. On the other hand, it is not possible to make gun-cotton with a higher percentage of nitrogen than about 13.7, even when it does not contain any nitro-cotton that is soluble in ether-alcohol.[B] The fact is that it is not at present possible to make a nitro-cellulose which shall be either entirely soluble or entirely insoluble, or which will contain the theoretical content of nitrogen to suit any of the above formulae for the cellulose nitrates. Prof. G. Lunge gives the following list of nitration products of cellulose:—

[Footnote A: The penta-nitrate C_{12}H_{15}O_{5}(NO_{3})_{5} = 12.75 per cent. nitrogen.]

[Footnote B: In the Cordite Trial (1894) Sir F.A. Abel said, "Before 1888 there was a broad distinction between soluble and insoluble nitro- cellulose, collodion-cotton being soluble (in ether-alcohol) and gun-cotton insoluble." Sir H.E. Roscoe, "That he had been unable to make a nitro-cotton with a higher nitrogen content than 13.7." And Professor G. Lunge said, "Gun-cotton always contained soluble cotton, and vice versa." These opinions were also generally confirmed by Sir E. Frankland, Sir W. Crookes, Dr Armstrong, and others.]

Dodeca-nitro-cellulose C_{24}H_{28}O_{20}(NO_{2})_{12} = 14.16 per cent. nitrogen. (= old tri-nitro-cellulose) Endeca-nitro-cellulose C_{24}H_{29}O_{20}(NO_{2})_{11} = 13.50 per cent. nitrogen. Deca-nitro-cellulose C_{24}H_{30}O_{20}(NO_{2})_{10} = 12.78 per cent. nitrogen. Ennea-nitro-cellulose C_{24}H_{31}O_{20}(NO_{2})_{9} = 11.98 per cent. nitrogen. Octo-nitro-cellulose C_{24}H_{32}O_{20}(NO_{2})_{8} = 11.13 per cent. nitrogen. (= old di-nitro-cellulose) Hepta-nitro-cellulose C_{24}H_{33}O_{20}(NO_{2})_{7} = 10.19 per cent. nitrogen. Hexa-nitro-cellulose C_{24}H_{34}O_{20}(NO_{2})_{6} = 9.17 per cent. nitrogen. Penta-nitro-cellulose C_{24}H_{35}O_{20}(NO_{2})_{5} = 8.04 per cent. nitrogen. Tetra-nitro-cellulose C_{24}H_{36}O_{20}(NO_{2})_{4} = 6.77 per cent. nitrogen. (= old mono-nitro-cellulose)

It is not unlikely that a long series of nitrates exists. It is at any rate certain that whatever strength of acids may be used, and whatever temperature or other conditions may be present during the nitration, that the product formed always consists of a mixture of the soluble and insoluble nitro-cellulose.

Theoretically 100 parts of cotton by weight should produce 218.4 parts of gun-cotton, but in practice the yield is a good deal less, both in the case of gun-cotton or collodion-cotton. In speaking of soluble and insoluble nitro-cellulose, it is their behaviour, when treated with a solution consisting of 2 parts ether and 1 of alcohol, that is referred to. There is, however, another very important difference, and that is their different solubility in nitro-glycerine. The lower nitrates or soluble form is soluble in nitro-glycerine under the influence of heat, a temperature of about 50 deg. C. being required. At lower temperatures the dissolution is very imperfect indeed; and after the materials have been left in contact for days, the threads of the cotton can still be distinguished. The insoluble form or gun-cotton is entirely insoluble in nitro-glycerine. It can, however, be made to dissolve[A] by the aid of acetone or acetic ether. Both or rather all the forms of nitro-cellulose can be dissolved in acetone or acetic ether. They also dissolve in concentrated sulphuric acid, and the penta-nitrate in nitric acid at about 80 deg. or 90 deg. C.

[Footnote A: Or rather to form a transparent jelly.]

The penta-nitrate may be obtained in a pure state by the following process, devised by Eder:—The gun-cotton is dissolved in concentrated nitric acid at 90 deg. C., and reprecipitated by the addition of concentrated sulphuric acid. After cooling to 0 deg. C., and mixing with a larger volume of water, the precipitated nitrate is washed with water, then with alcohol, dissolved in ether-alcohol, and again precipitated with water, when it is obtained pure. This nitrate is soluble in ether-alcohol, and slightly in acetic acid, easily in acetone, acetic ether, and methyl-alcohol, insoluble in alcohol. Strong potash (KOH) solution converts into the di-nitrate C_{12}H_{18}O_{8}(NO_{3})_{2}. The hexa-nitrate is not soluble in acetic acid or methyl-alcohol.

The lower nitrates known as the tetra- and tri-nitrates are formed together when cellulose is treated with a mixture of weak acids, and allowed to remain in contact with them for a very short time (twenty minutes). They cannot be separated from one another, as they all dissolve equally in ether-alcohol, acetic ether, acetic acid, methyl-alcohol, acetone, amyl acetate, &c.

As far as the manufacture of explosive bodies is concerned, the two forms of nitro-cellulose used and manufactured are gun-cotton or the hexa- nitrate (once regarded as tri-nitro-cellulose), which is also known as insoluble gun-cotton, and the soluble form of gun-cotton, which is also known as collodion, and consists of a mixture of several of the lower nitrates. It is probable that it chiefly consists, however, of the next highest nitrate to gun-cotton, as the theoretical percentage of nitrogen for this body,. the penta-nitrate, is 12.75 per cent., and analyses of commercial collodion-cotton, entirely soluble in ether-alcohol, often give as high a percentage as 12.6.

We shall only describe the manufacture of the two forms known as soluble and insoluble, and shall refer to them under their better known names of gun-cotton and collodion-cotton. The following would, however, be the formulae[A] and percentage of nitrogen of the complete series:—

Hexa-nitro-cellulose C_{12}H_{14}O_{4}(NO_{3})_{6} 14.14 per cent. nitrogen. Penta-nitro-cellulose C_{12}H_{15}O_{5}(NO_{3})_{5} 12.75 per cent. nitrogen. Tetra-nitro-cellulose C_{12}H_{16}O_{6}(NO_{3})_{4} 11.11 per cent. nitrogen. Tri-nitro-cellulose C_{12}H_{17}O_{7}(NO_{3})_{3} 9.13 per cent. nitrogen. Di-nitro-cellulose C_{12}H_{18}O_{8}(NO_{3})_{2} 7.65 per cent. nitrogen. Mono-nitrocellulose C_{12}H_{19}O_{9}(NO_{3}) 3.80 per cent. nitrogen.

[Footnote A: Berthelot takes C{24}H{40}O{20} as the formula of cellulose; and M. Vieille regards the highest nitrate as (C{24}H{18}(NO{3}H){11}O{9}). Compt. Rend., 1882, p. 132.]

Properties of Gun-Cotton.—The absolute density of gun-cotton is 1.5. When in lumps its apparent density is 0.1; if twisted into thread, 0.25; when subjected, in the form of pulp, to hydraulic pressure, 1.0 to 1.4. Gun-cotton preserves the appearance of the cotton from which it is made. It is, however, harsher to the touch; it is only slightly hygroscopic (dry gun-cotton absorbs 2 per cent. of moisture from the air). It possesses the property of becoming electrified by friction. It is soluble in acetic ether, amyl acetate, and acetone, insoluble in water, alcohol, ether, ether-alcohol, methyl-alcohol, &c. It is very explosive, and is ignited by contact with an ignited body, or by shock, or when it is raised to a temperature of 172 deg. C. It burns with a yellowish flame, almost without smoke, and leaves little or no residue. The volume of the gases formed is large, and consists of carbonic acid, carbonic oxide, nitrogen, and water gas. Compressed gun-cotton when ignited often explodes when previously heated to 100 deg. C.

Gun-cotton kept at 80 deg. to 100 deg. C. decomposes slowly, and sunlight causes it to undergo a slow decomposition. It can, however, be preserved for years without undergoing any alteration. It is very susceptible to explosions by influence. For instance, a torpedo, even placed at a long distance, may explode a line of torpedoes charged with gun-cotton. The velocity of the propagation of the explosion in metallic tubes filled with pulverised gun-cotton has been found to be from 5,000 to 6,000 mms. per second in tin tubes, and 4,000 in leaden tubes (Sebert).

Gun-cotton loosely exposed in the open air burns eight times as quickly as powder (Piobert). A thin disc of gun-cotton may be fired into from a rifle without explosion; but if the thickness of the disc be increased, an explosion may occur. The effect of gun-cotton in mines is very nearly the same as that of dynamite for equal weights. It requires, however, a stronger detonator, and it gives rise to a larger quantity of carbonic oxide gas. Gun-cotton should be neutral to litmus, and should stand the Government heat test—temperature of 150 deg. F. for fifteen minutes (see page 249). In the French Navy gun-cotton is submitted to a heat test of 65 deg. C. (= 149 deg. F.) for eleven minutes. It should contain as small a percentage of soluble nitro-cotton and of non-nitrated cotton as possible.

The products of perfectly detonated gun-cotton may be expressed by the following equation:—

2C_{12}H_{14}O_{4}(NO_{3})_{6} = 18CO + 6CO_{2} + 14H_{2}O + 12N.

It does not therefore contain sufficient oxygen for the complete combustion of its carbon. It is for this reason that when used for mining purposes a nitrate is generally added to supply this defect (as, for instance, in tonite). It tends also to prevent the evolution of the poisonous gas, carbonic oxide. The success of the various gelatine explosives is due to this fact, viz., that the nitro-glycerine has an excess of oxygen, and the nitro-cotton too little, and thus the two explosives help one another.

In practice the gases resulting from the explosion of gun-cotton are— Carbonic oxide, 28.55; carbonic acid, 19.11; marsh gas (CH_{4}), 11.17; nitric oxide, 8.83; nitrogen, 8.56; water vapour, 21.93 per cent. The late Mr E.O. Brown, of Woolwich Arsenal, discovered that perfectly wet and uninflammable compressed gun-cotton could be easily detonated by the detonation of a priming charge of the dry material in contact with it. This rendered the use of gun-cotton very much safer for use as a military or mining explosive.

As a mining explosive, however, gun-cotton is now chiefly used under the form of tonite, which is a mixture of half gun-cotton and half barium nitrate. This material is sometimes spoken of as "nitrated gun-cotton." The weight of gun-cotton required to produce an equal effect either in heavy ordnance or in small arms is to the weight of gunpowder in the proportion of 1 to 3, i.e., an equal weight of gun-cotton would produce three times the effect of gunpowder. Its rapidity of combustion, however, requires to be modified for use in firearms. Hence the lower nitrates are generally used, or such compounds as nitro-lignose, nitrated wood, &c., are used.

The initial pressure produced by the explosion of gun-cotton is very large, equal to 18,135 atmospheres, and 8,740 kilogrammes per square centimetre for 1 kilo., the heat liberated being 1,075 calories (water liquid), or 997.7 cals. (water gaseous), but the quantity of heat liberated changes with the equation of decomposition. According to Berthelot,[A] the heat of formation of collodion-cotton is 696 cals. for 1,053 grms., or 661 cals. for 1 kilo. The heat liberated in the total combustion of gun-cotton by free oxygen at constant pressure is 2,633 cals. for 1,143 grms., or for 1 kilo. gun-cotton 2,302 cals. (water liquid), or 2,177 cals. (water gaseous). The heat of decomposition of gun- cotton in a closed vessel, found by experiment at a low density of charge (0.023), amounts to 1,071 cals. for 1 kilo. of the substance, dry and free from ash. To obtain the maximum effect of gun-cotton it must be used in a compressed state, for the initial pressures are thereby increased. Wet gun-cotton s much less sensitive to shock than dry. Paraffin also reduces its liability to explode, so also does camphor.

[Footnote A: "Explosives and their Power," trans. by Hake and M'Nab.]

The substance known as celluloid, a variety of nitro-cellulose nearly corresponding to the formula C_{24}H_{24}(NO_{3}H)_{8}O_{12}, to which camphor and various inert substances are added, so as to render it non-sensitive to shock, may be worked with tools, and turned in the lathe in the same manner as ivory, instead of which material celluloid is now largely used for such articles as knife handles, combs, &c. Celluloid is very plastic when heated towards 150 deg. C., and tends to become very sensitive to shock, and in large quantities might become explosive during a fire, owing to the general heating of the mass, and the consequent evaporation of the camphor. When kept in the air bath at 135 deg. C., celluloid decomposes quickly. In an experiment (made by M. Berthelot) in a closed vessel at 135 deg. C., and the density of the charge being 0.4, it ended in exploding, developing a pressure of 3,000 kilos. A large package of celluloid combs also exploded in the guard's van on one of the German railways a few years ago. Although it is not an explosive under ordinary circumstances, or even with a powerful detonator, considerable care should be exercised in its manufacture.

The Manufacture of Gun-Cotton.—The method used for the manufacture of gun-cotton is that of Abel (Spec. No. 1102, 20. 4. 65). It was worked out chiefly at Stowmarket[A] and Waltham Abbey,[B] but has in the course of time undergone several alterations. These modifications have taken place, however, chiefly upon the Continent, and relate more to the apparatus and machinery used than to any alteration in the process itself. The form of cellulose used is cotton-waste,[C] which consists of the clippings and waste material from cotton mills. After it has been cleaned and purified from grease, oil, and other fatty substances by treatment with alkaline solutions, it is carefully picked over, and every piece of coloured cotton rag or string carefully removed. The next operation to which it is submitted has for its object the opening up of the material. For this purpose it is put through a carding machine, and afterwards through a cutting machine, whereby it is reduced to a state suitable for its subsequent treatment with acids, that is, it has been cut into short lengths, and the fibres opened up and separated from one another.

[Footnote A: The New Explosive Co. Works.]

[Footnote B: Royal Gunpowder Factory.]

[Footnote C: Costs from L10 to L25 a ton. In his description of the "Preparation of Cotton-waste for the Manufacture of Smokeless Powder," A. Hertzog states that the German military authorities require a cotton which when thrown into water sinks in two minutes; when nitrated, does not disintegrate; when treated with ether, yields only 0.9 per cent. of fat; and containing only traces of chlorine, lime, magnesia, iron, sulphuric acid, and phosphoric acid. If the cotton is very greasy, it must be first boiled with soda-lye under pressure, washed, bleached with chlorine, washed, treated with sulphuric acid or HCl, again washed, centrifugated, and dried; if very greasy indeed a preliminary treatment with lime-water is desirable. See also "Inspection of Cotton-Waste for Use in the Manufacture of Gun-cotton," by C.E. Munro, Jour. Am. Chem. Soc., 1895, 17, 783.]

Drying the Cotton.—This operation is performed in either of two ways. The cotton may either be placed upon shelves in a drying house, through which a current of hot air circulates, or dried in steam-jacketed cylinders. It is very essential that the cotton should be as dry as possible before dipping in the acids, especially if a wholly "insoluble" nitro-cellulose is to be obtained. After drying it should not contain more than 0.5 per cent. of moisture, and less than this if possible. The more general method of drying the cotton is in steam-jacketed tubes, i.e., double cylinders of iron, some 5 feet long and 1-1/2 foot wide. The cotton is placed in the central chamber (Fig. 10), while steam is made to circulate in the surrounding jacket, and keeps the whole cylinder at a high temperature (steam pipes may be coiled round the outside of an iron tube, and will answer equally well). By means of a pipe which communicates with a compressed air reservoir, a current of air enters at the bottom, and finds its way up through the cotton, and helps to remove the moisture that it contains. The raw cotton generally contains about 10 per cent. of moisture and should be dried until it contains only 1/2 per cent. or less. For this it will generally have to remain in the drying cylinder for about five hours. At the end of that time a sample should be taken from the top of the cylinder, and dried in the water oven (100 deg. C.[A]) for an hour to an hour and a half, and re-weighed, and the moisture then remaining in it calculated.

[Footnote A: It is dried at 180 deg. C. at Waltham Abbey, in a specially constructed drying chamber.]



It is very convenient to have a large copper water oven, containing a lot of small separate compartments, large enough to hold about a handful of the cotton, and each compartment numbered, and corresponding to one of the drying cylinders. The whole apparatus should be fixed against the wall of the laboratory, and may be heated by bringing a small steam pipe from the boiler-house. It is useful to have a series of copper trays, about 3 inches by 6 inches, numbered to correspond to the divisions in the steam oven, and exactly fitting them. These trays can then be taken by a boy to the drying cylinders, and a handful of the cotton from each placed in them, and afterwards brought to the laboratory and weighed (a boy can do this very well), placed in their respective divisions of the oven, and left for one to one and a half hours, and re-weighed.

When the cotton is found to be dry the bottom of the drying cylinder is removed, and the cotton pushed out from the top by means of a piece of flat wood fixed on a broom-handle. It is then packed away in galvanised- iron air-tight cases, and is ready for the next operation. At some works the cotton is dried upon shelves in a drying house through which hot air circulates, the shelves being of canvas or of brass wire netting. The hot air must pass under the shelves and through the cotton, or the process will be a very slow one.

Dipping and Steeping.—The dry cotton has now to be nitrated. This is done by dipping it into a mixture of nitric and sulphuric acids. The acids used must be strong, that is, the nitric acid must be at least of a gravity of 1.53 to 1.52, and should contain as little nitric oxide as possible. The sulphuric acid must have a specific gravity of 1.84 at 15 deg. C., and contain about 97 per cent. of the mono-hydrate (H{2}SO{4}). In fact, the strongest acids obtainable should be used when the product required is gun-cotton, i.e., the highest nitrate.

The sulphuric acid takes no part in the chemical reaction involved, but is necessary in order to combine with the water that is liberated in the reaction, and thus to maintain the strength of the nitric acid. The reaction which takes place is the following:—

2(C_{6}H_{10}O_{5}) + 6HNO_{3} = C_{12}H_{14}(NO_{3})_{6} + 6 H_{2}O. 324 378 = 594 108. Cellulose. Gun-Cotton.

Theoretically,[A] therefore, 1 part of cellulose should form 1.8 part of gun-cotton. Practically, however, this is never obtained, and 1.6 lb. from 1 lb. of cellulose is very good working. The mixture of acids used is generally 1 to 3, or 25 per cent. nitric acid to 75 per cent. sulphuric acid.

[Footnote A: (594 x 1)/324= 1.83.]



The dipping is done in cast-iron tanks (Fig. 11), a series of which is arranged in a row, and cooled by a stream of cold water flowing round them. The tanks hold about 12 gallons, and the cotton is dipped in portions of 1 lb. at a time. It is thrown into the acids, and the workman moves it about for about three minutes with an iron rabble. At the end of that time he lifts it up on to an iron grating, just above the acids, fixed at the back of the tank, where by means of a movable lever he gently squeezes it, until it contains about ten times its weight of acids (the 1 lb. weighs 10 lbs.). It is then transferred to earthenware pots to steep.



Steeping.—The nitrated cotton, when withdrawn from the dipping tanks, and still containing an excess of acids, is put into earthenware pots of the shape shown in Figs. 12 and 13. The lid is put on, and the pots placed in rows in large cooling pits, about a foot deep, through which a stream of water is constantly flowing. These pits form the floor of the steeping house. The cotton remains in these pots for a period of forty-eight hours, and must be kept cool. Between 18 deg. and 19 deg. C. is the highest temperature desirable, but the cooler the pots are kept the better. At the end of forty-eight hours the chemical reaction is complete, and the cotton is or should be wholly converted into nitro-cellulose; that is, there should be no unnitrated cotton.



Whirling Out the Acid.—The next operation is to remove the excess of acid. This is done by placing the contents of two or three or more pots into a centrifugal hydro-extractor (Fig. 14), making 1,000 to 1,500 revolutions per minute. The hydro-extractor consists of a machine with both an inner cylinder and an outer one, both revolving in concert and driving outwardly the liquid to the chamber, from which it runs away by a discharge pipe. The wet cotton is placed around the inner cone. The cotton, when dry, is removed, and at once thrown into a large tank of water, and the waste acids are collected in a tank.[A]

[Footnote A: Care must be taken in hot weather that the gun-cotton does not fire, as it does sometimes, directly the workman goes to remove it after the machine is stopped. It occurs more often in damp weather. Dr Schuepphaus, of Brooklyn, U.S.A., proposes to treat the waste acids from the nitration of cellulose by adding to them sulphuric anhydride and nitric acid. The sulphuric anhydride added converts the water liberated from the cellulose into sulphuric acid.]

Washing.—The cotton has now to be carefully washed. This is done in a large wooden tank filled with water. If, however, a river or canal runs through the works, a series of wooden tanks, the sides and bottoms of which are pierced with holes, so as to allow of the free circulation of water, should be sunk into a wooden platform that overhangs the surface of the river in such a way that the tanks are immersed in the water, and of course always full. During the time that the cotton is in the water a workman turns it over constantly with a wooden paddle. A stream of water, in the form of a cascade, should be allowed to fall into these tanks. The cotton may then be thrown on to this stream of water, which, falling some height, at once carries the cotton beneath the surface of the water. This proceeding is necessary because the cotton still retains a large excess of strong acids, and when mixed with water gives rise to considerable heat, especially if mixed slowly with water. After the cotton has been well washed, it is again wrung out in a centrifugal machine, and afterwards allowed to steep in water for some time.



Boiling.—The washed cotton is put into large iron boilers with plenty of water, and boiled for some time at 100 deg. C. In some works lead-lined tanks are used, into which a steam pipe is led. The soluble impurities of unstable character, to which Sir F.A. Abel traced the liability of gun- cotton to instability, are thereby removed. These impurities consist of the products formed by the action of nitric acid on the fatty and resinous substances contained in the cotton fibres. The water in the tanks should be every now and again renewed, and after the first few boilings the water should be tested with litmus paper until they are no longer found to be acid.



Pulping.—The idea of pulping is also due to Abel. By its means a very much more uniform material is obtained. The process is carried out in an apparatus known as a "Beater" or "Hollander" (Fig. 15, a, b). It consists of a kind of wooden tank some 2 or 3 feet deep of an oblong shape, in which a wheel carrying a series of knives is made to revolve, the floor of the tank being sloped up so as to almost touch the revolving wheels. This part of the floor, known as the "craw," is a solid piece of oak, and a box of knives is fixed into it, against which the knives in the revolving wheel are pressed. The beater is divided into two parts—the working side, in which the cotton is cut and torn between the knife edges in the revolving cylinder and those in the box; and the running side, into which the cotton passes after passing under the cylinder. The wheel is generally boxed in to prevent the cotton from being thrown out during its revolution. The cotton is thus in constant motion, continually travelling round, and passing between the knives in the revolving cylinder and those in the box fixed in the wooden block beneath it. The beater is kept full of water, and the cotton is gradually reduced to a condition of pulp. The wheel revolves at the rate of 100 to 150 times a minute.



When the gun-cotton is judged to be sufficiently fine, the contents of the beater are run into another very similar piece of machinery, known as the "poacher" (Fig. 16, a, b, c), in which the gun-cotton is continuously agitated together with a large quantity of water, which can be easily run off and replaced as often as required. When the material is first run into the poacher from the beater, the water with which it is then mixed is first run away and clean water added. The paddle wheel is then set in motion, and at intervals fresh water is added. There is a strainer at the bottom of the poacher which enables the water to be drawn off without disturbing the cotton pulp. After the gun-cotton has been in the poacher for some time, a sample should be taken by holding a rather large mesh sieve in the current for a minute or so. The pulp will thus partly pass through and partly be caught upon the sieve, and an average sample will be thus obtained. The sample is squeezed out by hand, bottled, and taken to the laboratory to be tested by the heat test for purity. It first, however, requires to be dried. This is best done by placing the sample between coarse filter paper, and then putting it under a hand-screw press, where it can be subjected to a tolerably severe pressure for about three minutes. It is then rubbed up very finely with the hands, and placed upon a paper tray, about 6 inches by 4-1/2 inches, which is then placed inside a water oven upon a shelf of coarse wire gauze, the temperature of the oven being kept as near as possible to 120 deg. F. (49 deg. C.), the gauze shelves in the oven being kept about 3 inches apart. The sample is allowed to remain at rest for fifteen minutes in the oven, the door of which is left wide open. After the lapse of fifteen minutes the tray is removed and exposed to the air of the laboratory (away from acid fumes) for two hours, the sample being at some point within that time rubbed upon the tray with the hand, in order to reduce it to a fine and uniform state of division. Twenty grains (1.296 grm.) are used for the test. (See Heat Test, page 249.)

If the gun-cotton sample removed from the poacher stands the heat test satisfactorily, the machine is stopped, and the water drained off. The cotton is allowed some little time to drain, and is then dug out by means of wooden spades, and is then ready for pressing. The poachers hold about 2,000 lbs. of material, and as this represents the products of many hundred distinct nitrating operations, a very uniform mixture is obtained. Two per cent. of carbonate of soda is sometimes added, but it is not really necessary if the cotton has been properly washed.

Compressing Gun-Cotton.—The gun-cotton, in the state in which it is removed from the poacher, contains from 28 to 30 per cent. of water. In order to remove this, the cotton has to be compressed by hydraulic power. The dry compressed gun-cotton is packed in boxes containing 2,500 lbs. of dry material. In order to ascertain how much of the wet cotton must be put into the press, it is necessary to determine the percentage of water. This may be done by drying 2,000 grains upon a paper tray (previously dried at 100 deg. C.) in the water oven at 100 deg. C. for three hours, and re-weighing and calculating the percentage of water. It is then easy to calculate how much of the wet gun-cotton must be placed in the hopper of the press in order to obtain a block of compressed cotton of the required weight. Various forms of presses are used, and gun-cotton is sent out either as solid blocks, compressed discs, or in the form of an almost dry powder, in zinc- lined, air-tight cases. The discs are often soaked in water after compression until they have absorbed 25 per cent. of moisture.



At the New Explosives Company's Stowmarket Works large solid blocks of gun-cotton are pressed up under a new process, whereby blocks of gun- cotton, for use in submarine mines or in torpedo warheads, are produced. Large charges of compressed gun-cotton have hitherto been built up from a number of suitably shaped charges of small dimensions (Fig. 17), as it has been impossible to compress large charges in a proper manner. The formation of large-sized blocks of gun-cotton was the invention of Mr A. Hollings. Prior to the introduction of this method, 8 or 9 lbs. had been the limit of weight for a block. This process has been perfected at the Stowmarket factory, where blocks varying from the armour-piercing shell charge of a few ounces up to blocks of compressed gun-cotton mechanically true, weighing 4 to 5 cwts. for torpedoes or submarine mines, are now produced. At the same time the new process ensures a uniform density throughout the block, and permits of any required density, from 1.4 downwards, being attained; it is also possible exactly to regulate the percentage of moisture, and to ensure its uniform distribution. The maximum percentage of moisture depends, of course, upon the density. By the methods of compression gun-cotton blocks hitherto employed, blocks of a greater thickness than 2 inches, or of a greater weight than 9 lbs., could not be made, but with the new process blocks of any shape, size, thickness, or weight that is likely to be required can be made readily and safely. The advantages which are claimed for the process may be enumerated as follows:—(1.) There is no space wasted, as in the case with built-up charges, through slightly imperfect contact between the individual blocks, and thus either a heavier charge—i.e., about 15 per cent. more gun- cotton—can be got into the same space, or less space will be occupied by a charge of a given weight. (2.) The metallic cases for solid charges may be much lighter than for those built-up, since with the former their function is merely to prevent the loss of moisture from wet gun-cotton, or to prevent the absorption of moisture by dry gun-cotton. They can thus be made lighter, as the solid charge inside will prevent deformation during transport. With built-up charges the case must be strong enough to prevent damage, either to itself or to the charge it contains. For many uses a metal case, however light, may be discarded, and one of a thin waterproof material substituted. (3.) The uniform density of charges made by this process is very favourable to the complete and effective detonation of the entire mass, and to the presence of the uniform amount of moisture in every part of the charge. (4.) Any required density, from the maximum downwards, may be obtained with ease, and any required amount of moisture left in the charge. These points are of great importance in cases where, like torpedo charges, it is essential to have the centre of gravity of the charge in a predetermined position both vertically and longitudinally, and the charge so fixed in its containing case that the centre of gravity cannot shift. The difficulty of ensuring this with a large torpedo charge built up from a number of discs and segments is well known. Even with plain cylindrical or prismatic charges a marked saving in the process of production is effected by this new system. The charges being in one block they are more easily handled for the usual periodical examination, and they do not break or chafe at the edges, as in the case of discs and cubes in built-up charges. A general view of the press is given in Fig. 19. The gun-cotton in a container is placed on a cradle fixed at an angle to the press. The mould is swivelled round, and the charge pushed into it with a rammer, and it is then swivelled back into position. The mould is made up of a number of wedge pieces which close circumferentially on the enclosed mass, which is also subjected to end pressure. Holes are provided for the escape of water.



The Waltham Abbey Process.—At the Royal Gunpowder Factory, Waltham Abbey, the manufacture of gun-cotton has been carried out for many years. The process used differs but little from that used at Stowmarket. The cotton used is of a good quality, it is sorted and picked over to remove foreign matters, &c., and is then cut up by a kind of guillotine into 2-inch lengths. It is then dried in the following manner. The cotton is placed upon an endless band, which conducts it to the stove, or drying closet, a chamber heated by means of hot air and steam traps to about 180 deg. F.; it falls upon a second endless band, placed below the first; it travels back again the whole length of the stove, and so on until delivered into a receptacle at the bottom of the farther end, where it is kept dry until required for use. The speed at which the cotton travels is 6 feet per minute, and as the length of the band travelled amounts to 126 feet, the operation of drying takes twenty-one minutes. One and a quarter lb. are weighed out and placed in a tin box; a truck, fitted to receive a number of these boxes, carries it along a tramway to a cool room, where it is allowed to cool.

Dipping.—Mixed acids are used in the proportion of 1 to 3, specific gravity nitric acid 1.52, and sulphuric acid 1.84. The dipping tank is made of cast iron, and holds 220 lbs. of mixed acids, and is surrounded on three sides by a water space in order to keep it cool. The mixed acids are stored in iron tanks behind the dipping tanks, and are allowed to cool before use. During the nitration, the temperature of the mixed acids is kept at 70 deg. F., and the cotton is dipped in quantities of 1-1/2 lb. at a time. It is put into a tin shoot at the back of the dipping tank, and raked into the acids by means of a rabble. It remains in the acids for five or six minutes, and is then removed to a grating at the back, pressed and removed. After each charge of cotton is removed from the tank, about 14 lbs. of fresh mixed acids are added, to replace amount removed by charge. The charge now weighs, with the acids retained by it, 15 lbs.; it is now placed in the pots, and left to steep for at least twenty-four hours, the temperature being kept as low as possible, to prevent the formation of soluble cotton, and also prevent firing. The proportion of soluble formed is likely to be higher in hot weather than cold. The pots must be covered to prevent the absorption of moisture from the air, or the accidental entrance of water, which would cause decomposition, and consequent fuming off, through the heat generated by the action of the water upon the strong acids.

The excess of acids is now extracted by means of hydro-extractors, as at Stowmarket. They are worked at 1,200 revolutions per minute, and whirled for five minutes (10-1/2 lbs. of waste acids are removed from each charge dipped). The charge is then washed in a very similar manner to that previously described, and again wrung out in a centrifugal extractor (1,200 revolutions per minute). The gun-cotton is now boiled by means of steam in wooden tanks for eight hours; it is then again wrung out in the extractors for three minutes, boiled for eight hours more, and again wrung out; it is then sent to the beater and afterwards to the poacher. The poachers hold 1,500 gals. each, or 18 cwt. of cotton. The cotton remains six hours in the poachers. Before moulding, 500 gals. of water are run into the poacher, and 500 gals. of lime water containing 9 lbs. of whiting and 9 gals. of a caustic soda solution. This mixture is of such a strength that it is calculated to leave in the finished gun-cotton from 1 to 2 per cent. of alkaline matter.

By means of vacuum pressure, the pulp is now drawn off and up into the stuff chest—a large cylindrical iron tank, sufficiently elevated on iron standards to allow room for the small gauge tanks and moulding apparatus below. It holds the contents of one poacher (18 cwt.), and is provided with revolving arms to keep the pulp stirred up, so that it may be uniformly suspended in water.

Recently a new process, invented by J.M. and W.T. Thomson (Eng. Pat. No. 8,278, 1903), has been introduced at the Waltham Abbey Factory. The object of this invention is the removal of the acids of nitration from the nitrated material after the action has been completed, and without the aid of moving machinery, such as presses, rollers, centrifugals, and the like. The invention consists in the manufacture of nitrated celluloses by removing the acids from the nitrated cellulose directly by displacement without the employment of either pressure or vacuum or mechanical appliances of any kind, and at the same time securing the minimum dilution of the acids. It was found that if water was carefully run on to the surface of the acids in which the nitro-cellulose is immersed, and the acids be slowly drawn off at the bottom of the vessel, the water displaces the acid from the interstices of the nitro-cellulose without any undesirable rise in temperature, and with very little dilution of the acids. By this process almost the whole of the acid is recovered in a condition suitable for concentration, and the amount of water required for preliminary washing is very greatly reduced. The apparatus which is used for the purpose consists of a cylindrical or rectangular vessel constructed with a perforated false bottom and a cock at its lowest point for running off the liquid. Means are also provided to enable the displacing water to be run quietly on to the surface of the nitrating acids.[A]

[Footnote A: In a further patent (Eng. Pat. 7,269, 1903, F.L. Natham), J.M. Thomson and W.T. Thomson propose by use of alcohol to replace the water, used in washing nitro-cellulose, and afterward to remove the alcohol by pressing and centrifuging.]

The apparatus is shown in Fig. 2O, side elevation, and in Fig. 21 a plan of the nitrating vessel and its accessories is given. In Fig. 20 is shown in sectional elevation one of the trough devices for enabling liquids to be added to those in the nitrating vessel without substantial disturbance.



In carrying out this invention a rectangular lead-lined or earthenware tank a is employed, having a false bottom b, supported by ribs c', over the real bottom c, which slopes down to a draining outlet pipe d, provided with a perforated grid or plate e, adapted to prevent choking of the outlet. Suitably supported near the top of the vessel a are provided two troughs, f having depending aprons g, a pipe h has two branches h', leading to the troughs, f. This pipe h is adapted to be connected by a rubber pipe either to the outlet pipe k' of the sulphuric acid tank k or the water supply pipe l. The nitrating acids are supplied through the pipe m. A charge of mixed nitrating acids is introduced into the vessel a say up to the level n, and the dry cellulose thrown into the acids in small quantities at a time, being pushed under the surface in the usual way.



A thin layer, say half an inch, of a suitable liquid, preferably sulphuric acid, of a gravity not exceeding that of the waste acid to be produced, is run carefully on the top of the acids by means of the troughs f, which are perforated as shown at o, so that the sulphuric acid runs down the aprons g, and floats on the nitrating acids. The whole is then allowed to stand till nitration has been completed. Water is then supplied to the troughs by way of the pipes l, h, and h', and is allowed to float very gently over the surface of the sulphuric acid, and when a sufficient layer has been formed, the cock p at the bottom of the apparatus is opened, and the acid slowly drawn off, water being supplied to maintain the level constant. It is found that the rate of displacement of the acids is a factor which exerts a considerable influence on the properties of the resulting nitro-cellulose, and affords a means of regulating the temperature of displacement. A rate of displacement which has been found suitable is about two inches in depth of the vessel per hour when treating highly nitrated celluloses, but this rate may, in some cases, be considerably increased. The flow of water at the top of the apparatus is regulated so that a constant level is maintained. By this means the water gradually and entirely displaces the acids from the interstices of the nitro-cellulose, the line of separation between the acids and the water being fairly sharply defined throughout. The flow of water is continued until that issuing at the bottom is found to be free from all trace of acid. The purification of the nitro-cellulose is then proceeded with as usual, either in the same vessel or another.

In the process above described, the object of the introduction of a small layer of sulphuric acid is mainly to prevent the fuming which would otherwise take place, and is not essential, as it is found it can be omitted without any deleterious effect. In order to use the mixed acids in the most economical manner, the waste acid from a previous operation may be used for a first nitration of the cellulose; being afterwards displaced with fresh acids which carry the nitration to the required degree before they are in turn displaced by water. The apparatus may be used merely for the removal of the acid, in which case the nitration is carried out in other vessels in the usual way, and the nitro-cellulose removed to the displacement apparatus where it is just covered with waste acid, and the displacement then proceeded with as above described. In some cases the process is carried out in an ordinary nitrating centrifugal, using the latter to effect preliminary drying after acid extraction. This gives a great advantage over the usual method of working ordinary centrifugal nitrating apparatus, because the acid being removed before the centrifugal is run, practically all danger of firing therein disappears, and a greater proportion of the waste acid is recovered.

In some cases the acids and water may be supplied by perforated pipes, lying along the edges of the nitrating vessel, and these edges may, if desired, be themselves made inclined, like the sides of the troughs f. In the case of effecting nitration in centrifugals as above, the displacing sulphuric acid and water may thus be supplied round the edges of the machines, or removal troughs such as f may be used. It will be obvious that any inert liquid of suitable specific gravity may be used instead of sulphuric acid, as a separation layer.

Moulding.—By means of the small measuring tank above referred to, the gun-cotton pulp is drawn off from the stuff chest, and run into moulds of the shapes and sizes required. Thence a large proportion of the water is drawn off by means of tubes connected with the vacuum engine, the moulds having bottoms of fine wire gauze, in order to prevent the pulp from passing through. Hydraulic pressure of about 34 lbs. on the square inch is then applied, which has the effect of compressing the pulp into a state in which it has sufficient consistency to enable it to be handled with care, and also expels a portion of the remaining water.

Compressing.—The moulded gun-cotton is now taken to the press house, which is situated at some distance from the rest of the factory. Here the moulds are subjected to powerful hydraulic pressure, from 5 to 6 tons per square inch, and is compressed to one-third of its previous bulk. The slabs or discs thus formed are kept under pressure for a short time, not exceeding a minute and a half, to give the requisite density. It should, when removed, be compact, and just sink in water, and should perceptibly yield to the pressure of the fingers. There are perforations in the press blocks, to allow of the escape of gases, if formed, by reason of sufficient heat being generated. The men working the press are placed under cover, behind strong rope mantlets having eye tubes which command a view of the press.

Packing.—The finished slabs and discs are dipped into a solution of soda and carbolic acid, and packed in special wood metal-lined cases. When it is to be sent abroad, the metal lining, which is made of tinned copper, is soldered down, but both the outer wooden and inner metal cases are fitted with air-tight screw-plugs, so that when necessary water can be added without unfastening the cases.

Reworked gun-cotton does not make such good discs as new pulped gun- cotton, probably because the fibrous tenacity of the gun-cotton has been destroyed by the amount of pressure it has previously undergone, so that when repulped it resembles fine dust, and a long time is required to press it into any prescribed form. It is generally boiled for eight hours to open up the fibre and remove alkali, then broken up by hand with wooden mallets, pulped, and then used with fresh gun-cotton in the proportion of 1 to 5 parts.

Manufacture at Le Bouchet.—At Le Bouchet gun-cotton was made thus:—200 grms. of cotton were steeped for an hour in 2 litres of a mixture of 1 volume concentrated nitric and 2 volumes sulphuric acid. The cotton was then removed and pressed, whereby 7/10ths of the waste acids was recovered. After this it was washed for one to one and a half hours in running water, strongly pressed again; allowed to lie for twenty-four hours in wood-ash lye; then well washed in running water; pressed, and finally dried on a wide linen sheet, through which was forced air heated to 60 deg. C. The average yield from 100 parts of cotton was 165 parts of gun- cotton. The strong pressings of the gun-cotton, while still impregnated with acids, caused subsequent washings to be difficult and laborious.

Granulation of Gun-Cotton.—Gun-cotton is often required in the granulated form for use either alone or with some form of smokeless powder. This is done under the patent of Sir Frederick Abel in the following manner:—The gun-cotton from the poacher is placed in a centrifugal machine, very similar to the hydro-extractors before mentioned, and used for wringing out the acids. In this machine it loses water until it only contains 33 per cent., and is at the same time reduced to a more or less fibrous state. It is then taken to the granulating room, where it is first passed through sieves or perforations, which break up the mass into little pieces like shot. The material is then transferred to a revolving drum made of wood or stout leather, which is kept constantly revolving for some time. The material is occasionally sprinkled with water. The drum in turning, of course, carries the granules partially round with it, but the action of gravity causes them to descend constantly to the lowest point, and thus to roll over one another continually. The speed of the drum must not be too rapid. None of the granules must be carried round by centrifugal force, but it must be fast enough to carry them some little distance up the side of the drum. After removal from the drum the granules are dried upon shelves in the drying house.

Gun-cotton is also dissolved in acetone or acetic ether until it has taken the form of a jelly. It is then rolled into thin sheets, and when dry cut up into little squares. In the manufacture of smokeless powders from nitro-cellulose, nitro-lignine, &c., the various substances are mixed with the gun-cotton or collodion-cotton before granulating.

Collodion-Cotton.—In the manufacture of collodion or soluble cotton the finer qualities of cotton-waste are used and the acids used in the dipping tanks are much weaker. The manufacture of collodion-cotton has become of more importance than gun-cotton, by reason of its use for the manufacture of the various forms of gelatine, such as gelatine dynamite, gelignite, forcite, &c., and also on account of its extensive use in the manufacture of many of the smokeless powders. It is also used for the manufacture of "collodion," which is a solution of collodion-cotton in ether-alcohol; for the preparation of celluloid, and many other purposes. It is less explosive than gun-cotton, and consists of the lower nitrates of cellulose. It is soluble in nitro-glycerine, and in a mixture of 2 parts of ether and 1 of alcohol; also in acetone, acetic ether, and other solvents. MM. Menard and Domonte were the first to prepare a soluble gun- cotton, and its investigation was carried on by Bechamp, who showed that its properties and composition were different to those of gun-cotton.

Manufacture.—The cotton used is cotton-waste.[A] It is thought by some that Egyptian cotton is preferable, and especially long fibre varieties. The strength of the acids used is, however, of more importance than the quality of the cotton. The percentage composition of the acid mixture which gives the best results is as follows:—Nitric acid, 23 per cent.; sulphuric acid, 66 per cent.; and water, 11 per cent; and has a specific gravity of 1.712 (about). It can be made by mixing sulphuric acid of specific gravity 1.84 with nitric acid of specific gravity 1.368 in the proportions of 66 per cent. and 34 per cent. respectively. (The production of the penta-nitro-cellulose is aimed at if the collodion-cotton is for use as an explosive.) If the acids are much weaker than this, or potassium nitrate and sulphuric acid is used, the lower nitrates will be formed. The product, while being entirely soluble in ether-alcohol or nitro-glycerine, will have a low nitrogen content, whereas a material with as high a nitrogen as 12 or 12.6 is to be aimed at.

[Footnote A: Raw cotton is often used.]

The cotton should not be allowed to remain in the dipping tanks for more than five minutes, and the acid mixture should be kept at a temperature of 28 deg. C. or thereabouts; and the cotton should be removed after a few minutes, and should not be pressed out, as in the case of gun-cotton, but at once transferred to the pots and allowed to steep for forty-eight hours. (Some prefer twenty-four hours, but there is more chance in this case of the product containing non-nitrated cellulose.) When the nitration is complete, the collodion-cotton is removed from the pots, and treated in exactly the same manner as described under gun-cotton. The produce should be entirely soluble in ether-alcohol and nitro-glycerine, and contain as near 12.7 per cent. of nitrogen as possible. The theoretical nitrogen is for the penta-nitro-cellulose 12.75 per cent. This will, however, seldom if ever be obtained. The following are some of the results I have obtained from different samples:—

Nitrogen. (1.) (2.) (3.) German make 11.64 11.48 11.49 per cent. Stowmarket 12.57 12.60 11.22 " Walsrode 11.61 12.07 11.99 " Faversham 12.14 11.70 11.60 "

and the following was the analysis of a sample (No. 1) of German-made collodion-cotton, which made very good blasting gelatine:—

Soluble cotton (collodion) 99.118 per cent. Nitrogen = 11.64 per cent. Gun-cotton 0.642 " Non-nitrated cotton 0.240 " Total ash 0.25 "

It should contain as little non-nitrated or unconverted cotton and as little gun-cotton as possible, as they are both insoluble in nitro- glycerol. The quality and composition of any sample of collodion-cotton can be quickly inferred by determining the percentage of nitrogen by means of the nitrometer and the use of the solubility test.[A] A high nitrogen content coupled with a high solubility is the end to be aimed at; a high nitrogen with a low solubility shows the presence of gun-cotton, and a low nitrogen, together with a low solubility, the presence of unnitrated cotton. Where complete solubility is essential and the percentage of nitrogen less important, Dr Lunge recommends nitration with a mixture of equal parts of sulphuric and nitric acids containing from 19 to 20 per cent. of water.

[Footnote A: See Analysis of Explosives.]

Mr T.R. France claims to have invented some improvements in the manufacture of soluble nitro-cellulose. His object has been to produce an article as uniform as possible. His explanation of the imperfect action of the acids is that, however uniform the mixed acids may be in strength and proportions, and however carefully the operations of nitrating, &c., may be conducted, there are variable elements found in different samples of cotton. The cotton fibre has for its protection a glazed surface. It is tubular and cellular in structure, and contains a natural semi-fluid substance composed of oil or gum, which varies in nature according to the nature of the soil upon which the cotton is grown. The tubes of the fibre seem to be open at one end only when the fibre is of normal length. When, therefore, the cotton is subjected to the action of the mixed acids, the line of least resistance seems to be taken by them, viz., the insides of the tubes constituting the fibre of the cotton, into which they are taken by capillary attraction, and are subject to change as they progress, and to the increased resistance from the oil or gum, &c., in their progress, and therefore to modified action, the result of which is slower and slower action, or chemical change. He also thinks it is possible that the power of capillary attraction is balanced in the tubes by air contained therein, after a little, sufficiently so to prevent the acids from taking full effect. To get over this, Mr France uses his cotton in a fine state, almost dust, in fact, and then nitrates in the usual mixture of acids at 40 deg. to 90 deg. F., the excess of acids being removed by pressure. He says he does not find it necessary to wash this fine cotton dust in an alkaline solution previous to nitration. His mixed acids consist of 8 parts HNO_{3} = 42 deg. B., and 12 parts H_{2}SO_{4} = 66 deg. B., and he stirs in the dipping tank for fifteen minutes, the temperature being 50 deg. F. to 100 deg. F., the temperature preferred being 75 deg. F.

"Nitrated" Gun-Cotton.—The nitrates that are or have been mixed with gun-cotton in order to supply oxygen are potassium nitrate, ammonium nitrate, and barium nitrate (tonite). The total combustion of gun-cotton by potassium nitrate corresponds to the equation:—

10[C_{24}H_{18}(NO_{3}H)_{11}O_{9}] + 82KNO_{3} = 199CO_{2} + 41K_{2}CO_{3} + 145H_{2}O + 96N_{2},

or 828 grms. of nitrate for 1,143 grms. of gun-cotton, or 42 per cent. nitrate and 58 per cent. gun-cotton. The explosive made at Faversham by the Cotton Powder Company, and known as tonite No. 1, consists of very nearly half gun-cotton and half barium nitrate. The relations by weight of total combustion would be 51.6 of gun-cotton to 48.4 of barium nitrate. The average composition of tonite I have found by analysis to be 51 per cent. gun-cotton to 49 per cent. barium nitrate. The heat liberated is practically the same as for an equivalent weight of KNO_{3}; but the barium nitrate mixture weighs 2,223 grms. instead of 1,971 grms., or one-eighth more. The advantage in mixing a nitrate with gun-cotton is that it supplies oxygen, and by converting all the carbon into carbonic acid, prevents the formation of the poisonous gas carbonic oxide (CO). The nitrates of potassium and barium are also used admixed with nitro- cellulose in several of the sporting smokeless powders.

The Manufacture of Tonite.—The explosive tonite was patented by Messrs Trench, Faure, and Mackie, and is manufactured at Faversham and Melling at the works of the Cotton Powder Company, and at San Francisco by the Tonite Powder Company. It consists of finely divided and macerated gun-cotton incorporated with finely ground nitrate of barium which has been carefully recrystallised. It is made by acting upon carbonate of barium[A] with nitric acid. The wet and perfectly purified, finely pulped gun-cotton is intimately mixed up between edge runners with about the same weight of nitrate, and the mixing and grinding continued until the whole has become an intimately mixed paste. This paste is then compressed into cartridges, formed with a recess at one end for the purpose of inserting the detonator. The whole is then covered with paraffined paper.

[Footnote A: Witherite, BaCO{3} + 2HNO{3} = Ba(NO{3}){2} + CO{2} + H{2}O.]

The tonite No. 2 consisted of gun-cotton, nitrates of potash and soda, charcoal and sulphur. Tonite No. 3[A] is composed as follows:—Gun-cotton, 19 per cent.; di-nitro-benzol, 13 per cent.; and barium nitrate, 68 per cent. or similar proportions. It is a yellowish colour, and being slower in its explosive action, is better adapted for blasting soft rock.

[Footnote A: Tonite No. 1 was patented by Messrs Trench, Faure, and Mackie, and tonite Nos. 2 and 3 by Trench alone.]

Tonite is extensively used in torpedoes and for submarine blasting, also for quarries, &c. Large quantities were used in the construction of the Manchester Ship Canal. Among its advantages are, that the English railways will take tonite on the same footing as gunpowder; it is a very dense material; if wetted it can easily be dried in the sun; it very readily explodes by the use of a proper detonator; while it burns very slowly and without the least danger; the cartridges being waterproofed, it can be employed in wet bore holes, and it can be tamped with water; and finally, as it contains sufficient oxygen to oxidise the carbon, no carbonic oxide (CO) gas is formed, i.e., its detonation is perfect. It is a very safe explosive to use, being little susceptible to either blows or friction.

Not long ago, a committee, composed of Prof. P. Bedson, Drs Drummond and Hume, Mr T. Bell, one of H.M. Inspectors of Coal Mines, and others, in considering the problem whether the fumes produced by the combustion of tonite were injurious to health, carried out a series of experiments in coal mines for this purpose. The air at the "intake" was analysed, also the air of the "return," and the smoky air in the vicinity of the shot holes. The cartridge was surrounded by the flame-extinguishing mixture, and packed in a brown paper bag. During the first experiment nineteen shots were fired (= 6.29 lbs. tonite). The "return" air showed only a trace of carbonic oxide gas (CO). At the second experiment thirteen shots were fired (= 4.40 lbs. tonite), and analysis of the air of the "return" showed that CO was present in traces only, whilst the fumes contained only 1.9 to 4.8 parts per 10,000.

Dangers in connection with the Manufacture of Guncotton, &c.—Of all the nitro compounds, the least dangerous to manufacture are gun-cotton and collodion-cotton. The fact that the Stowmarket Factory is within five minutes' walk of the town shows how safe the manufacture of this explosive is regarded. With the exception of the nitration and the compression into blocks or discs, the whole process is worked with a large excess of water, and the probability of an explosion is thus reduced to a minimum. Among the precautions that should, however, be taken, are—first, the careful extraction of the resinous and soluble substances from the cotton before nitration, as it was shown many years ago by Sir F.A. Abel that the instability of the gun-cotton first manufactured in England and Austria was chiefly due to these compounds. They are generally removed by boiling the cotton in a soda solution.

The actual nitration of cotton is not a dangerous operation, but the operations of wringing in the hydro-extractors, and washing the nitro- cotton after it leaves the first centrifugal machine, are somewhat so. Great care should be taken that the wrung-out nitro-cotton at once comes in contact with a large excess of water, i.e., is at once immersed entirely in the water, since at this stage it is especially liable to decomposition, which, once started, is very difficult to stop. The warmer the mixture and the less water it contains, the more liable it is to decomposition; hence it is that on warm and damp days the centrifugal machines are most likely to fire. The commencement of decomposition may be at once detected by the evolution of red fumes. Directly the gun-cotton is immersed in the large quantity of water in the beater and poacher it is safe.

In order that the final product may be stable and have good keeping qualities, it is necessary that it should be washed completely free from acid. The treatment in the beater and poacher, by causing the material to assume the state of a fine pulp, in contact with a large quantity of water, does a good deal to get rid of the free acid, but the boiling process is absolutely necessary. It has been proposed to neutralise the free acid with a dilute solution of ammonia; and Dr C.O. Weber has published some experiments bearing upon this treatment. He found that after treatment with ammonia, pyroxyline assumed a slightly yellowish tinge, which was a sure sign of alkalinity. It was then removed from the water, and roughly dried between folds of filter paper, and afterwards dried in an oven at 70 deg. C. After three hours, however, an explosion took place, which entirely destroyed the strong copper oven in which the nitro- cotton (about one oz.) had been drying. The explosion was in some respects remarkable. The pyroxyline was the di-nitro-cellulose (or possibly the penta-nitro?), and the temperature was below the igniting point of this material (40 deg. C. would have been a better temperature). Dr Weber determined the ignition point of his di-nitro-cellulose, and found it to be 194 deg. to 198 deg. C., and he is therefore of opinion that the explosion was due to the treatment of the partially washed material with ammonia. A certain quantity of ammonium nitrate was probably formed, and subsequently dried upon the nitro-cellulose, in a state of very fine subdivision. The faintest trace of acid would then be sufficient to bring about the explosive ignition of the ammonium nitrate.

The drying of gun-cotton or collodion-cotton is also a somewhat dangerous operation. A temperature of 40 deg. C. (104 deg. F.) should not be exceeded, and thermometers should be placed in the nitro-cotton, and the temperature frequently observed. An electric alarm thermometer is also a useful adjunct to the cotton drying house. Great care must also be taken that there are no exposed hot-water pipes or stoves in the drying house, as the fine gun-cotton dust produced by the turning or moving of the material upon the shelves would settle upon such pipes or stoves, and becoming hot, would be very sensitive to the least friction. The floor also should be covered with linoleum or indiarubber. When hot currents of air are made to pass over the surface of gun-cotton, the gun-cotton becomes electrified. It is important, therefore, to provide some means to carry it away. Mr W.F. Reid, F.I.C., was the first to use metal frames, carriers, and sieves, upon which is secured the cloth holding the gun-cotton, and to earth them.

The compression of gun-cotton into blocks, discs, &c., is also attended with considerable risk. Mr O. Guttmann, in an interesting paper upon "The Dangers in the Manufacture of Explosives" (Jour. Soc. Chem. Ind., No. 3, vol. xi., 1892), says: "The compression of gun-cotton into cartridges requires far more care than that of gunpowder, as this is done in a warm state, and gun-cotton even when cold, is more sensitive than gunpowder. When coming out of the centrifugal machines, the gun-cotton should always pass first through a sieve, in order to detect nails or matches which may by chance have got into it. What has been said as to gunpowder presses applies still more to those for gun-cotton, although the latter are always hydraulic presses. Generally the pistons fit the mould perfectly, that is to say, they make aspiration like the piston of a pump. But there is no metal as yet known which for any length of time will stand the constant friction of compression, and after some time the mould will be wider in that part where the greatest compression takes place. The best metal for this purpose has proved to be a special steel made by Krupp, but this also is only relatively better; for pistons I prefer hard cast iron. If the position of the moulds and pistons is not exactly the same in all cases, what the Germans call 'Ecken' (English 'binding') will take place, viz., the mould will stand obliquely to the piston, and a dangerous friction will result." "Of course, it is necessary to protect the man working the hydraulic valves during compression. At Waltham Abbey they have a curtain made of ship's hawsers, which is at the same time elastic and resistant." Mr Guttmann has found that a partition wall 12 inches thick, made of 2-inch planks, and filled with ground cinders, gives very effective protection. A door in this partition enables the workman to get to the press, and a conical tube penetrates the wall, enabling the man to see the whole work from a safe standpoint. The roof, or one side of the building, should be of glass, so as to give the explosion a direction.

Trench's Fire-extinguishing Compound is manufactured by the Cotton Powder Company at Faversham, and is the invention of Mr George Trench, F.C.S., the manager of the Company. The object of the invention is to surround the cartridges of tonite, when used in coal mines, with a fire- extinguishing compound. If a charge of tonite, dynamite, or gelatine dynamite is put inside a few ounces of this mixture, and then fired, not the least trace of flame can be observed, and experiments appear to show that there is no flame at all. The compound consists of sawdust impregnated with a mixture of alum and chlorides of sodium and ammonia. Fig. 22 shows the manner of placing the tonite cartridge in the paper bag, and surrounding it with the fire-extinguishing compound, aa. The attachment of the fuse and detonator is also shown.



The following report (taken from the Faversham News, 22nd Oct. 1887) of experiments conducted in the presence of several scientific and mining men will show its value:—"A large wrought-iron tank, of 45 cubic feet capacity, had been sunk level with the ground in the middle of the yard; to this tank the gas had been laid on, for a purpose that will be explained later on. The charges were fired by means of electricity, a small dynamo firing machine being placed from 30 to 40 yards away from the 'mine.'" Operations were commenced by the top of the tank being covered over and plastered down in order to make it air-tight; then a sufficient quantity of coal gas was placed in it to make it highly inflammable and explosive, the quantity being ascertained by a meter which had been fixed specially for the purpose. Whilst the gas was being injected the cartridge was prepared.

The first experiment was to try whether a small charge of tonite—fired without the patent extinguisher—would ignite the gas. The gas having been turned on, a miner's lamp was placed in the "tank," but this was extinguished before the full quantity of gas had gone through the meter. However, the gas being in, the charge of 1-1/4 oz. tonite was placed in the "mine," the detonator was connected by means of long wires to the dynamo machine, and the word was given to "fire." With a tremendous report, and a flash of fire, the covering of the mine flew in all directions, clearly showing that the gas had exploded. The next cartridge (a similar charge) was prepared with the patent compound. First of all a brown paper case of about 2 inches diameter was taken, and one of the tonite cartridges was placed in the centre of it, the intervening space between the charge and-the case being packed with the "fire-extinguishing compound." The mine having had another supply of gas injected, the protected cartridge was placed inside and fired. The result was astonishing, the explosion not being nearly so loud, whilst there was not the least flash of fire. "Protected" and "unprotected" charges were fired at intervals, gas being turned into the tank on each occasion. Charges of tonite varying from 1 to 6 oz. were also used with the compound. The report was trifling, whilst no flash could be seen.

Uses of Collodion-Cotton.—The collodion or soluble gun-cotton is used for a variety of purposes. The chief use is, however, for the manufacture of the various explosive gelatine compounds, of which blasting gelatine is the type. It is also very extensively used in the manufacture of smokeless powders, both military and sporting—in fact, very few of them do not contain it. In some, however, nitro-lignose or nitrated wood is used instead. This, however, is chemically the same thing, viz., nitro- cellulose, the cellulose being derived from the wood fibre. It is more used in this connection than the higher nitrate gun-cotton. Another use to which it has been applied very extensively, of recent years, is in the manufacture of "celluloid." It is used in photography for the preparation of the films on the sensitised plates, and many other purposes. Dissolved in a solution of two parts ether and one of alcohol, it forms the solution known as collodion, used for a variety of purposes, such as a varnish, as a paint for signals; in surgery, for uniting the edges of wounds.

Quite lately, Mr Alfred Nobel, the well-known inventor of dynamite, has patented the use of nitro-cellulose, hydro- or oxy-cellulose, as an artificial substitute for indiarubber. For this purpose it is dissolved in a suitable non-volatile or slightly volatile "solvent," such as nitro- naphthalene, di-nitro-benzene, nitro-toluene, or its homologues; products are obtained varying from a gelatinous consistency to the hardness of ebonite. The proportions will vary from about 20 per cent. of nitro- cellulose in the finished product, forming a soft rubber, to 50 per cent. nitrating celluloid, and the "solvent" chosen will depend on the use to which the rubber substitute is to be put, the liquids giving a more elastic substance, whilst mixtures of solids and liquids may be employed when the product is to be used at high temperatures. By means of rollers steam heated, the incorporation may be accomplished without the aid of a volatile liquid, or the nitro-cellulose may be employed wet, the water being removed after "solution."

It is advisable to use the cellulose nitrated only just enough to render it suitable, in order to reduce the inflammability of the finished product. Mr W. Allen, M.P., of Gateshead, proposed to use celluloid for cartridge cases, and thus to lighten ammunition, and prevent jambing, for the case will be resolved into gases along with the powder. Extractors will also be done away with.

Celluloid is an intimate mechanical mixture of pyroxyline (gun-cotton or collodion-cotton) with camphor, first made by Hyatt, of Newark, U.S.A., and obtained by adding the pyroxyline to melted camphor, or by strongly compressing the two substances together, or by dissolving the constituents in an appropriate solvent, e.g., alcohol or ether, and evaporating to dryness. A combination of the two latter methods, i.e., partial solution, with pressure, is now usually adapted. The pyroxyline employed is generally the tetra- and penta-nitrated cellulose, the hexa-nitrate (gun-cotton) being but seldom used on account of its explosive properties.

Care is taken to prevent the formation of the hexa-nitrate by immersing the cellulose in only moderately strong nitric acid, or in a warm mixture of nitric and sulphuric acids. The paper, either in small pieces or in sheets, is immersed for about twenty-five minutes in a mixture of 2 parts of nitric acid and 5 parts of sulphuric acid, at a temperature of about 30 deg. C., after which the nitrated cellulose is thoroughly washed with water to remove the last traces of free acid, pressed, and whilst still moist, mixed with the camphor.

In the process of Trebouillet and De Besancele, the cellulose, which may be in the form of paper, cotton, or linen, is twice nitrated—first in the acid mixture employed in a previous operation; and secondly, in a fresh mixture of 3 parts sulphuric acid of 1.83 specific gravity, and 2 parts concentrated nitric acid containing nitrous acid. After each nitration the mass is subjected to pressure, and is then carefully washed with water, to which, at the last, a small quantity of ammonia or caustic soda is added to remove the final traces of acid. The impregnation of the pyroxyline with the camphor is effected in a variety of ways.

The usual proportion of the constituents is 2 parts pyroxyline and 1 part camphor. In Trebouillet and De Besancele's process, 100 parts of pyroxyline are intimately mixed with from 40 to 50 parts camphor, and moulded together by strong pressure in a hot press, and afterwards dried by exposure to air, desiccated by calcium chloride or sulphuric acid. The usual method is, however, to dissolve the camphor in the least possible quantity of alcohol, and sprinkle the solution over the dry pyroxyline, which is then covered with a second layer of pyroxyline, and the whole again treated with the camphor solution, the addition of pyroxyline and camphor solution being repeated alternately until the requisite amount of celluloid mixture is obtained.

The mass, which sinks together in transparent lumps, is worked for about an hour between cold iron rollers, and then for the same period between rollers which can be gently heated by steam. The layer of celluloid surrounding the rollers is then cut away and again pressed, the resulting cake, which is now about 1 cm. thick, being cut into plates of about 70 cm. long and 30 cm. broad. These are placed one above the other, and strongly pressed together by hydraulic pressure at a temperature of about 70 deg. for twenty-four hours. The thick cakes are once more cut into plates of the desired thickness, and placed in a chamber heated from 30 deg. to 40 deg. for eight to fourteen days, whereby they become thoroughly dry, and are readily made into various articles either by being moulded while warm under pressure, cut, or turned. Occasionally other liquids, e.g., ether and wood spirit, are used in place of alcohol as solvents for the camphor.

Celluloid readily colours, and can be marbled for manufacturing purposes, &c. It is highly inflammable and not explosive even under pressure, and may be worked under the hammer or between rollers without risk. It softens in boiling water, and may be moulded or pressed. Its specific gravity varies slightly with its composition and with the degree of pressure it has received. It is usually 1.35. It appears to be merely a mixture of its components, since by treatment with appropriate solvents the camphor may be readily extracted, and on heating the pyroxyline burns away while the camphor volatilises.

The manufacture of pyroxyline for the purpose of making celluloid has very much increased during recent years, and with this increase of production improved methods of manufacture have been invented. A series of interesting papers upon the manufacture of pyroxyline has been published by Mr Walter D. Field, of New York, in the Journal of the American Chemical Society[A] from which the following particulars are taken:—

[Footnote A: Vol. xv., No. 3, 1893; Vol. xvi., No. 7, 1894; Vol. xvi., No. 8, 1894. Figs. 19, 20, 21, 22, and 23 are taken from Mr Field's paper.]

Selection of the Fibre.—Cotton fibre, wood fibre, and flax fibre in the form of raw cotton, scoured cotton, paper, and rags are most generally used, and give the best results. As the fibres differ greatly in their structure, they require different methods of nitrating. The cotton fibre is a flattened hollow ribbon or collapsed cylindrical tube, twisted a number of times, and closed at one end to form a point. The central canal is large, and runs nearly to the apex of the fibre. Its side walls are membraneous, and are readily penetrated by the mixed acids, and consequently the highest nitration results. In the flax fibre the walls are comparatively thick, the central canal small; hence it is to be presumed that the nitration must proceed more slowly than in the case of cotton. The New Zealand flax gives the most perfectly soluble nitrates of any of the flaxes. Cotton gives a glutinous collodion, and calico a fluid collodion. One of the largest manufacturers of pyroxyline in the States uses the "Memphis Star" brand of cotton. This is an upland cotton, and its fibres are very soft, moist, and elastic. Its colour is light creamy white, and is retained after nitration. The staple is short, and the twist inferior to other grades, the straight ribbon-like filaments being quite numerous. This cotton is used carded, but not scoured. This brand of cotton contains a large quantity of half and three-quarter ripe fibre, which is extremely thin and transparent, distributed throughout the bulk of the cotton (Monie., Cotton Fibre, 67). Mr Field says, "This is a significant fact when it is known that from this cotton an extremely soluble pyroxyline can be produced."

Pyroxyline of an inferior grade as regards colour only can be produced from the cotton wastes of the trade. They must be scoured before they are fit for nitrating. Paper made from the pulps of sulphite and sulphate processes is capable of yielding a very soluble pyroxyline. It can be nitrated at high temperatures and still yield good results. Tissue paper made from flax fibre is also used after being cut into squares.

Mowbray (U.S.P., No. 443, 105, 3rd December 1890) says that a pure cotton tissue paper less than 1/500 inch in thickness, thin as it is, takes on a glutinous or colloid surface, and thus requires some thirty minutes to enable the nitration to take place. With a thicker paper only the surface would be nitrated. He therefore uses a fibre that has been saturated with a solution of nitrate of soda, and afterwards dried slowly, claiming that the salt crystallises in the fibre, or enters by the action termed osmose, and opens up the fibre to the action of the acid. This process would only be useful when the cotton is to be nitrated at a low temperature. At a high temperature it would be unnecessary.

Dietz and Wayne (U.S.P., No. 133, 969) use ramie, rheca, or China grass for producing a soluble pyroxyline. That made from ramie is always of uniform strength and solubility, and requires a smaller quantity of solvent to dissolve it than that made from cotton. Mr Field's experience, however, is entirely contrary to this statement. Such is the influence of the physical form of the fibre on the process of nitration, that when flax fibre and cotton fibre are nitrated with acid mixtures of exactly the same strength, and at the same temperature, the solution of the first is glutinous or thick, and the second fluid or thin. By simply nitrating at a higher temperature than the cotton, the flax will yield a pyroxyline giving an equally fluid collodion.

The presence of chlorine in the fibre must be carefully avoided, as such a fibre will yield an acid product which cannot be washed neutral. The fibre must be dry before nitration; and this is best done, according to Mr Field, by using the form of drier used in drying wool.

Nitration of the Fibre.—Mixed cotton and flax fibre in the form of paper, from 2/1000 to 3/1000 inch thick, and cut into 1-inch squares, is nitrated by the Celluloid Manufacturing Company, and the same paper, left in long strips, 1 inch wide, is used for nitration by the Xylonite Manufacturing Company, of North Adams, Mass. (U.S.A.).

The Celluloid Company introduce the cut paper into the mixed acids by means of a hollow, rapidly revolving tube, flared at the lower end, and immersed in the mixed acids. The centrifugal force of the revolving tube throws the paper towards the sides of the vessel, leaving the centre of the vessel ready for fresh paper.

The Xylonite Company simply cut the paper into long strips, and introduce it into the mixed acids by means of forks. The arrangement used by this Company for holding the mixed acids is a cylindrical vessel divided into a number of sections, the whole revolving like a turntable, thus allowing the workman to nitrate successively each lot of paper at a given point. This Company did not remove the acid from the paper after its immersion, but plunged it immediately into the water, thus losing a large proportion of the waste acid. The Celluloid Company, by using the paper in smaller pieces, and more paper to a pound of acid, and wringing the mixed acid from the paper before immersion in water, had a better process of nitration.

Other manufacturers use earthenware vessels, and glass or steel rods, hooked at one end, having small pieces of rubber hose pulled over the other end to prevent the hand from slipping. The form of vessel in general use is that given in Fig. 23. It is large enough to nitrate 1 lb. of cotton at a time. The hook at one end of the rod enables the workman to pull the pyroxyline apart, and thus ensures saturation of the fibre. In the winter the room in which the nitrating is done must be kept at a temperature of about 70 deg. F. in order to secure equality in the batches.



The nitrating apparatus of White and Schupphaus (U.S.P., No. 418, 237, 89) Mr Field considers to be both novel and excellent. The cage (Fig. 24), with its central perforated cylinder (Fig. 25), is intended to ensure the rapid and perfect saturation of the tissue paper used for nitrating. The patentees say that no stirring is required with their apparatus. This, says Mr Field, might be true when paper is used, or even cotton, when the temperature of nitration is from 30 deg. to 35 deg. C., but would not be true if the temperature were raised to 50 deg. to 55 deg. C. The process is as follows:— The paper is nitrated in the cage (Fig. 25), the bottom of which is formed by the flanged plate C, fastened to the bottom of the internal cylinder B. After nitration the cage is carried to a wringer, which forms the basket, and the acids removed. Finally, the cage is taken to a plunge tank, where the paper is removed from the cage by simply pulling out the central perforated cylinder B. Fig. 26 shows the nitrating pot, with its automatic cover. The plunge tank is shown in plan and section in Figs. 28 and 29. This apparatus is suitable for the nitration of cotton fibre in bulk at high or low temperatures. Other methods that have been patented are Mowbray's (U.S.P., No. 434, 287), in which it is proposed to nitrate paper in continuous lengths, and Hyatt's (U.S.P., No. 210, 611).



The Acid Mixture.—Various formulae have been published for producing soluble nitro-cellulose. In many instances, although the observations were correct for the single experiment, a dozen experiments would have produced a dozen different products. The composition of the acids used depends upon the substance to be nitrated, and the temperature at which the nitration will be worked. Practically there are three formulae in general use—the one used by the celluloid manufacturers; another in which the cotton is nitrated at high temperatures; and a third in which the temperature of the immersion is low, and the time of nitration about six hours. Of the three, the best method is the last one, or the one in which the cotton is immersed at a low temperature, and then the reaction allowed to proceed in pots holding from 5 to 10 lbs. of cotton. The formula used by the celluloid manufacturers for the production of the low form of nitrated product which they use is:—

Sulphuric acid 66 parts by weight. Nitric acid 17 " " Water 17 " "

Temperature of immersion, 30 deg. C. Time, twenty to thirty minutes.

The cellulose is used in the form of tissue paper 2/1000 inch thick, 1 lb. to 100 of acid mixture. The nitro-cellulose produced by this formula is very insoluble in the compound ethers and other solvents of pyroxyline, and is seemingly only converted or gelatinised by the action of the solvent. The next formula produces a mixture of tetra-and penta-nitro- celluloses hardly soluble in methyl-alcohol (free from acetone), but very soluble in anhydrous compound ethers, ketones, and aldehydes:—

Nitric acid, sp. gr. 1.435 8 lbs. Sulphuric acid, sp. gr. 1.83 15-3/4 lbs. Cotton 14 oz.

Temperature of nitration, 60 deg. C. Time of immersion, forty-five minutes.

The 60 deg. of temperature is developed by mixing the acids together. The cotton is allowed to remain in the acid until it feels "short" to the rod.

The following table, due to Mr W.D. Field, shows very plainly the great variation in the time of the immersion and the temperature by seemingly very slight causes. It extends over fourteen working days, during which time it rained four days. The formula used is that given above, except that the specific gravity of the nitric acid is somewhat lower. The product obtained differs only from that produced by using nitric acid of specific gravity 1.43 in being soluble in methyl-alcohol. From 30 to 35 lbs. of pyroxyline were produced in each of the fourteen days.

A careful examination of this table will prove very instructive. The increase in yield varies from 31 per cent. to nothing, and the loss runs as high as 10 per cent., yet care was taken to make the product uniform in quality. On the days it rained there was a loss, with the exception of the fourth day, when there was neither a loss nor a gain. On the days it was partly clear, as just before or after rain, the table shows a loss in product. We can explain this fact by reason of the moisture-absorbing qualities of the cotton. On the rainy days it would absorb the moisture from the air until, when immersed in the acids, they were weakened, and the fibre dissolved more or less in weakened acid, producing what is known as "burning" in the batch. It will also be noticed that on days which show a loss, the time of the immersion was correspondingly short, as on the a loss, the time of the immersion was correspondingly short, as on the tenth, twelfth, and seventh days.

Specific Gravity. Time. H{2}S0{4}. HNO{3}. Hours. Minutes. Hours. Minutes. 1. Clear 1.838 1.4249 ... 20 4 ... 2. " 1.837 1.4249 ... 20 2 ... 3. Cloudy 1.837 1.4226 ... 45 2 ... 4. Rain 1.837 1.420 ... 20 1 20 5. Clear 1.8377 1.42 1 15 2 ... 6. Rainy 1.8391 1.422 ... 35 1 40 7. Cloudy 1.835 1.4226 ... 20 ... 35 8. Clear 1.835 1.422 ... 35 1 10 9. Partly Clear 1.824 1.4271 ... 20 1 ... 10. " 1.83 1.4271 ... 10 ... 25 11. Cloudy 1.832 1.425 ... 10 ... 50 12. Rainy 1.822 1.425 ... 10 ... 20 13. Partly CLear 1.8378 1.4257 ... 60 1 40 14. Cloudy 1.837 1.4257 1 56 4 40 Temp., Deg. C. Percentage From To Increase. Loss. 1. Clear 57 deg. 62 deg. 31 ... 2. " 60 deg. 62 deg. 18 ... 3. Cloudy 60 deg. 62 deg. 7 ... 4. Rain 60 deg. 63 deg. 0 0 5. Clear 58 deg. 62 deg. 15 ... 6. Rainy 58 deg. 62 deg. ... 2 7. Cloudy 62 deg. 65 deg. ... 10 8. Clear 60 deg. 62 deg. 5 ... 9. Partly Clear 50 deg. 60 deg. ... 3 10. " 58 deg. 60 deg. ... 10 11. Cloudy 58 deg. 60 deg. 8 ... 12. Rainy 58 deg. 60 deg. ... 10 13. Partly CLear 50 deg. 58 deg. 20 ... 14. Cloudy 50 deg. 60 deg. 16 ...

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