Nitro-Explosives: A Practical Treatise

CELLUL

scovery of Gun-Cotton-P

Insoluble Gun-Cottons-M

hirling out the Acid-W

Abbey Process-Le Bouch

tton-Manufacture-Acid M

n-Tonite-Dangers in Ma

ing Compound-Uses of Col

ro-Starch, Nitro-Jut

ust 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

solution of cuprammoniac solution, prepared from basic carbonate or hydrate of copper and aqueous ammonia. The specific gr

per cent. 44

en 6.3

49.7

tters, 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

h 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 t

Amer. Chem. Soc., 1901, 23[8], 527-579, con

is found that cellulose acetate forms with nitro-glycerine a gelatinous body without requiring the addition of a solvent. A sp

Pat. 24,662, 22n

n 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 sulphur

ng. 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 contai

lulose nitrates, for unlike nitro bodies of other series, they do not yield, or have not yet done so, amid

}H_{14}O_{4}(NO_{3}){6} + 6OH{2}. Cell

tric 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

by Cross and Bevan, ed.

.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 t

e Case," says he found 15.2 and 16.1 per cent. soluble cotton, and 13.07

rate, and the lowest the mono-nitrate. Gun-cotton was at one time regarded as the tri-nitrate, and c

6}H_{9}(NO_{2})O_{5} = 6

C_{6}H_{8}(NO_{2}

C_{6}H_{7}(NO_{2})

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

e C_{12}H_{15}O_{5}(NO_{3})_{

uble (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. Lu

C_{24}H_{28}O_{20}(NO_{

old tri-nit

C{24}H_{29}O_{20}(NO_{2

rog

{24}H_{30}O_{20}(NO_{2

rog

C{24}H_{31}O_{20}(NO_{

rog

{24}H_{32}O_{20}(NO_{2

old di-nitr

C{24}H_{33}O_{20}(NO_{

rog

{24}H_{34}O_{20}(NO_{2

rog

C{24}H_{35}O_{20}(NO_{

rog

C{24}H_{36}O_{20}(NO_{

old mono-ni

gth of acids may be used, and whatever temperature or other conditions may be present during the nitrat

er 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° 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

ather to form a t

, 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 slig

acids, and allowed to remain in contact with them for a very short time (twenty minutes). They cannot be separated from one

un-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

shall refer to them under their better known names of gun-cotton and collodion-cotton. The f

C_{12}H_{14}O_{4}(NO_

rog

C{12}H_{15}O_{5}(NO_

rog

C{12}H_{16}O_{6}(NO_

rog

C{12}H_{17}O_{7}(NO_

rog

{12}H_{18}O_{8}(NO_{

rog

C{12}H_{19}O_{9}(N

rog

a of cellulose; and M. Vieille regards the highest nitrate as

tly 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

t 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 p

on 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

nated gun-cotton may be expres

_{3}){6} = 18CO + 6CO

y 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 gela

.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 detonat

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 tim

mation 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 experime

s and their Power," tra

handles, combs, &c. Celluloid is very plastic when heated towards 150° 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° C., celluloid decomposes quickly. In an experiment (made by M. Berthelot) in a closed

d 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 remo

he New Explosi

Royal Gunpo

sintegrate; 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, wa

hod 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

C. at Waltham Abbey, in a speci

n: FIG. 10.-

he 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 t

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

ric 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° C., and c

n order to combine with the water that is liberated in the reaction, and thus to maint

6HNO_{3} = C_{12}H_{14

8 = 59

se. Gun

however, this is never obtained, and 1.6 lb. from 1 lb. of cellulose is very good working. The mix

: (594 x 1)

IG. 11.-TANK FOR

FIG. 12.-THE

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

FIG. 13.-COTTON

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° and 19° C. is the highest

: FIG. 14.-HY

,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

chine is stopped. It occurs more often in damp weather. Dr Schüpphaus, of Brooklyn, U.S.A., proposes to treat the waste acids from the nitration of cellulo

ch 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 th

. 15_a_.-THE BEATE

table 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 subs

FIG. 15_b_.-W

ls. 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 whee

16_a_.-POACHER FOR

IG. 16_b_.-PLAN

G. 16_c_.-ANOTHER

as 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

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 distin

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° C.) in the water oven at 100° 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 th

IG. 17.-OLD METH

G. 18.-NEW METHOD

er 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

-A 4-CWT. BLOCK OF GUN-

ULIC

n 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° 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 i

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 t

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

levated on iron standards to allow room for the small gauge tanks and moulding apparatus below. It holds the contents of one poa

cement 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 a

n and W.T. Thomson propose by use of alcohol to replace the water, used in washing

nd its accessories is given. In Fig. 20 is shown in sectional elevation one of the trough devices

Outlet; e, Grid; f, Troughs, with Aprons g; h, Pipe, with Branches h', leading to Troughs, f; k', Outlet Pipe of the Sulphuri

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 th

1.-PLAN OF THOMSON'S

bs; e, Grid; f, Trou

s f; k, Sulphuric A

o, Perforations of Tro

id

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, i

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.

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 ma

ater 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 s

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 f

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

ssure 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

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 lin

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 t

nto thin sheets, and when dry cut up into little squares. In the manufacture of smokeless powders from nitro-cellul

lignite, 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

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 collod

Raw cotton is

d 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

rog

(2.

1.64 11.48 11

12.57 12.

11.61 12.

12.14 11

mple (No. 1) of German-made collodion-cott

on) 99.118 per cent.| N

tton 0

ted cotto

ash

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 lo

See Analysis

l 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 attrac

der to supply oxygen are potassium nitrate, ammonium nitrate, and barium nitrate (tonit

] + 82KNO_{3} = 199CO_{2} + 41K_

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 m

n-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 sa

BaCO_{3} + 2HNO_{3} =

{2

ed as follows:-Gun-cotton, 19 per cent.; di-nitro-benzol, 13 per cent.; and barium nitrate, 68 per cent. or similar pr

. 1 was patented by Me

te Nos. 2 and 3

wder; 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 hol

s 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

ed. 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 th

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 decomposit

t 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° 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 i

lso 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 ind

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 w

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

2.-TRENCH'S FIRE-EXTI

s 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 plaste

o "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

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 ma

ogues; 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, t

he finished product. Mr W. Allen, M.P., of Gateshead, proposed to use celluloid for cartridge cases, and thus to lighten ammunit

gly 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 so

he 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

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 was

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

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° for twenty-four hours. The thick cakes are once more cut into plates of the desired thickness, and placed in a chamber

ut 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 ap

duction improved methods of manufacture have been invented. A series of interesting papers upon the manufacture of pyroxyline has been publi

o. 7, 1894; Vol. xvi., No. 8, 1894. Figs. 19, 20

ids, 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.

are fit for nitrating. Paper made from the pulps of sulphite and sulphate processes is capable of yielding a very soluble pyroxyline. It ca

ation 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 th

m 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

an acid product which cannot be washed neutral. The fibre must be dry before nitration; an

d cut into 1-inch squares, is nitrated by the Celluloid Manufacturing Company, and the same paper, left in long

tube, flared at the lower end, and immersed in the mixed acids. The centrifugal force of the revolving tu

e 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

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 ap

23.-VESSEL FOR NITRA

ation is from 30° to 35° C., but would not be true if the temperature were raised to 50° to 55° 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 ca

G. 24.-CENTRAL PE

5.-THE CAGE. WHITE AN

ARA

IG. 26.-CELLULOI

n: FIG. 27.-

28, 29.-PLUNGE TANK,

d, and the temperature at which the nitration will be worked. Practically there are three formul? 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 hour

cid 66 part

acid

r 17

ion, 30° C. Time, twe

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 mixt

, sp. gr. 1

d, sp. gr. 1.

on 1

n, 60° C. Time of immer

e acids together. The cotton is allowed to remai

n 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 di

er 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

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. | |

solved in the more volatile solvents methyl-alcohol and alcohol-ether, were much the best solvents for producing a plastic, as they are less volatile, and develop greater solvent action under the influence of heat. Nitro-benzene gives a solution that is granular; it seems to merely convert the pyroxylin

nd stearone in alcohol solution, also alpha- and beta-naphthol, with alcohol and anthraquinone (diphenylene diketone)

tones,[A] methyl-ethyl, methyl-propyl, methyl-butyl, methyl-amyl, and ethyl-butyl ketones are active solven

cal. They thus resemble aldehydes in constitution. The best-known ketone is acetone CH_{3}CO.CH_{3}. Mixed ketones are obtained

}H_{5}

CH_

d of heat or solution in alcohol; second, those that are solvents when dissolved in alcohol. These solvents a

nd mixed ketones of the fatty acid series. These four classes include the greater number of the solvents of pyroxyline. Those not included are as follows:-Amyl-nitrate and nitrite

aphtha to hasten the drying qualities of the varnish, so that it would set on the article to be varnished before it had a chance to run off. It is, however, the non-hygroscopic character of the so

ss and Bevan assign to it the formula C_{18}H_{26}O_{16}. It dissolves in concentrated sulphuric acid, and with nitric acid forms a nitro body of the formula C_{18}H_{23}O_{16}3(NO_{2}), which is prepared as follows:-The gelatinous oxy-cellulose is washed with strong nitric acid until free from water, and is then diffused through a mixture of equal

xidation of Cellulose,

Chem. Soc.,

OUS NITRO-

to make this explosive upon the manufacturing scale. Nitro-starch has been known since 1883, when Braconnot discovered it, and called it xylo

1/2}O_{2-1/2}(N

_{7}O_{4}(N

the molecule

rog

C_{12}H_{16}O_{6}(ONO_

rch C{12}H_{15}O_{5

ch C{12}H_{14}O_{4}(

residue O.NO_{2} thus appearing to be replaced by the sulphuric acid residue. On treatment with a solution of ferrous chloride, ni

It should further be fitted with a screw-agitator, in order to keep the nitric acid circulating freely. The charge of starch is introduced through an opening in the cover of this digesting vessel, and the proportions of acid to starch are 10 kilogrammes of starch to 100 kilos. of acid. The temperature is kept within the limits 20° to 25° C. When the solution of the starch is complete, the liquid is conducted into a precipitating apparatus, which is also provided with a cooling

essel, and of course below the filter pad. The precipitated starch is further cleansed from acid by repeated washings and by pressure, until all trace of acidity has been eliminated, and the substance exhibits a neutral reaction. The next step is to treat the nitro-starch with a 5 per cent. solution of so

ecomes electrified when rubbed; it is very stable, and soluble even in the cold in nitro- glycerine. He has also prepared a tetra-nitro-starch containing 10.58 and 10.50 per cent. of nitrogen, by

ravity 1.501, and 300 grms. of sulphuric acid, specific gravity 1.8 (some tetra-nitro-starch is also formed at the same time). After standing in contact with these mixed acids for one hour the starch has undergone a

precipitate, whilst the tetra-nitro-starch, which is formed simultaneously, remains in solution in the alcohol. As obtained by

to stand in contact for twenty-four hours; 200 grms. of this mixture are then poured into 600 c.c. of sulphuric acid of 66° B. The result of this manipulat

uric acid were less stable in character or properties than those which were precipitated by water or weak sulphuric acid. Dr Mühlh?us

of these substances prepared in differ

2° C. |121° C. |155° C. | | Stability |Stable |Stable |Unstable|Unstable|Unstable| | Per cent. of N. | 11.02 | 10.54 | 12.87 | 12.59 | 13.52 | | 96 per cent. alcohol| Sol. | Sol. | Insol. | Insol. | Insol. | | Ether |

were prepare

id and 2 parts sulphuric

. H_

rt nitric ac

tric and 3 parts

tric and 3.5 part

tric and 3 parts

with acetic ether. These ingredients are then worked together into a uniform mass, and dried at a temperature ranging between the limits 50° to 60° C. He has himself prepared such a smokeless powder, which proved to contain 11.54 per cent. of nitrogen, and was ver

d Vieille found the average velocities for nitro-starch powder, density of charge about 1.2, in a tin tube 4 mm. external diameter, to be, in two experiments, 5,222 m. and 5,674 m. In a tin tube 5.5 mm. external diameter, the velocity was 5,815 m., and in lead tube 5,006 m. (density 1.1 to 1.2). The starch powder is hygroscopic, and is insoluble in water and alcohol. When dry it is very explosive, and takes fire at about 350° F. Mr Al

pon the jute for some time. He found that with long exposure, i.e., from three to four hours in the acids, there was a disintegrating of the fibre-bundles, and the nitration was attended by secondary decomposition and conversion into products soluble in the acid mixture. Cross and Bevan's work upon this

{3} = C_{12}H_{15}O_{

tetra-nitrate appears to be the limit of nitration of jute-fibre. In other words, if we represent the ligno-cellulose molecule by a C_{12} fo

p. gr. 1.43, and H_{2}SO

3}(1.5), 1 vol.

3}(1.5), 75 vols.

154.4 grms.; 100 grms. of fibr

osure, thirty m

O_{6}(NO_{3}){3} = 9.5 per cent. and for C{12}H_{15}O_{6}(NO_{3})_{4} = 11.5 per cent. These nit

n-cellulose, or lignone constituents having been decomposed. In fact, he regards his product as cellulose penta-nitrate (C_{12}H_{16}O_{5}(ONO_{2})_{5}). The Chemiker Zeitung, xxi., p. 163, contains a further paper by Mühlh?usen on the explosive nitro-jute. After purifying

nition N

ent.

O_{3} 1. H_{2}SO_{4}

" 132.2 167

" 135.8 16

d upon the large scale, and Messrs Cross and Bevan are of opinion that there is no very obvious advantage in the use of lignified textile fibre as raw materials for explosive nitrates, seeing that a large number of raw materi

rt sugar. Its formula is C_{6}H_{8}(OH){6} and that of nitro-mannite C{6}H_{8}(NO_{3})_{6}. Mannite crystallises in needles or rhombic prisms, which are soluble in water and alcohol, and have a sweet taste. Nitro-mannite forms white needle-shaped crystals, insoluble in water, but soluble in ether or alcohol. When rapidly heated, they i

6HNO{3} = C_{6}H_{8}

ion are as shown in th

= 6CO{2} + 4H_{2}O

oxygen, 63.7 per cent. Its melting point is 112 to 113° C., and it solidifies at 93°. When carefully prepared and purifie

en nitro-glycerine and fulminate of mercury. It explodes by the shock of copper on iron or copper, and even of porcelain on porcelain, provid

upon the large scale. Among such substances are nitro-coal, which is made by the action of nitric acid on coal; nitro-colle, a prod

nitro-glucose. Nitro-molasses, which is a liquid product, has also been proposed, and nitro-saccharose, the product obtained by the nitration of sugar. It is a white, sandy, explosive substance, soluble in alcohol and ether. When made from cane sugar, it does not crystallise; but if made from milk sugar, it does. It has been used in percussion caps, being stronger and quicker than nitro-glycerine. It is, however, very sensitive and very hygroscopic, and v