Nitro-Explosives: A Practical Treatise Part 11

[Ill.u.s.tration: FIG. 31.--MR M'ROBERTS' MIXER FOR GELATINE EXPLOSIVES.]

The best way to keep the temperature of the water constant is to have a large tank of water raised upon a platform, some 5 or 6 feet high, outside the building, which is automatically supplied with water, and into which steam is turned. A thermometer stuck through a piece of cork and floated upon the surface of the tank will give the means of regulating the temperature.

When the jelly in the tanks has become semi-transparent and the cotton has entirely dissolved, the mixture should be transferred to the mixing machine. The mixing machines are specially designed for this work, and are built in iron, with steel or bronze kneading- and mixing-blades, according to requirements.

A suitable machine for the purpose is that known as the Nito-Universal Incorporator, shown in Fig. 30, which has been specially constructed by Messrs Werner, Pfleiderer, & Perkins, Ltd., after many years' experience in the mixing of explosive materials, and is now almost exclusively adopted in both Government and private factories. Mr George M'Roberts'[A]

mixing machine, however, which is shown in Fig. 31, is still used in some factories for dynamite jelly.

[Footnote A: See _Jour. Soc. Chem. Ind._, 1890, 267.]

If it is intended to make gelignite, or gelatine dynamite, it is at this point that the proper proportions of wood-pulp[A] and pota.s.sium nitrate should be added, and the whole well mixed for at least half an hour, until the various ingredients are thoroughly incorporated.

[Footnote A: Most of the wood-pulp used in England is obtained from pine-trees, but poplar, lime, birch, and beech wood are also used. It is chiefly imported as wood-pulp. The pulp is prepared as follows:--The bark and roots are first removed, and the logs then sawn into boards, from which the knots are removed. The pieces of wood are afterwards put through a machine which breaks them up into small pieces about an inch long, which are then crushed between rollers. These fragments are finally boiled with a solution of sodium bisulphite, under a pressure of about 90 lbs. per square inch, the duration of the boiling being from ten to twelve hours.

Sulphurous acid has also been used. Pine-wood yields about 45 per cent.

and birch about 40 per cent. of pulp when treated by this process. The pulp is afterwards bleached and washed, &c.

Birch. Beech. Lime. Pine. Poplar.

Cellulose 55.52 45.47 53.09 56.99 62.77 per cent.

Resin 1.14 0.41 3.93 0.97 1.37 "

Aqueous extract 2.65 2.47 3.56 1.26 2.88 "

Water 12.48 12.57 10.10 13.87 12.10 "

Lignine 28.21 39.14 29.32 26.91 20.88 "]

The following a.n.a.lysis of woods is by Dr H. Muller:--These mixing machines can either be turned by hand, or a shaft can be brought into the house and the machine worked by means of a belt at twenty to thirty revolutions per minute. The bearings should be kept constantly greased and examined, and the explosive mixture carefully excluded. When the gelatine mixture has been thoroughly incorporated, and neither particles of nitrate or wood meal can be detected in the ma.s.s, it should be transferred to wooden boxes and carried away to the cartridge-making machines to be worked up into cartridges.

[Ill.u.s.tration: FIG. 32.--PLAN OF THE BOX CONTAINING THE EXPLOSIVE, IN M'ROBERTS' MACHINE.]

The application of heat in the manufacture of the jelly from collodion- cotton and nitro-glycerine is absolutely necessary, unless some other solvent is used besides the nitro-glycerine, such as acetone, acetic ether, methyl, or ethyl-alcohol. (They are all too expensive, with the exception of acetone and methyl-alcohol, for use upon the large scale.) These liquids not only dissolve the nitro-cellulose in the cold, but render the resulting gelatine compound less sensitive to concussion, and reduce its quickness of explosion (as in cordite). They also lower the temperature at which the nitro-glycerine becomes congealed, i.e., they lower the freezing point[A] of the resulting gelatine.

[Footnote A: It has been proposed to mix dynamite with amyl alcohol for this purpose. Di-nitro-mono-chlorhydrine has also been proposed.]

The finished gelatine paste, upon entering the cartridge huts, is at once transferred to the cartridge-making machine, which is very like an ordinary sausage-making machine[A] (Fig. 33). The whole thing must be made of gun-metal or bra.s.s, and it consists of a conical case containing a shaft and screw. The revolutions of the shaft cause the thread of the screw to push forward the gelatine introduced by the hopper on the top to the nozzle, the apex of the cone-shaped case, from whence the gelatine issues as a continuous rope. The nozzle is of course of a diameter according to the size of cartridge required.

[Footnote A: G. M'Roberts, _Jour. Soc. Chem. Ind._, 31st March 1890, p.

266.]

[Ill.u.s.tration: FIG. 33.--CARTRIDGE-MAKING MACHINE FOR GELATINE EXPLOSIVES.]

The issuing gelatine can of course be cut off at any length. This is best done with a piece of hard wood planed down to a cutting edge, i.e., wedge-shaped. Mr Trench has devised a kind of bra.s.s frame, into which the gelatine issuing from the nozzle of the cartridge machine is forced, finding its way along a series of grooves. When the frame is full, a wooden frame, which is hinged to one end of the bottom frame, and fitted with a series of bra.s.s knives, is shut down, thereby cutting the gelatine up into lengths of about 4 inches.

It is essential that the cartridge machines should have no metallic contacts inside. The bearing for the screw shaft must be fixed outside the cone containing the gelatine. One of these machines can convert from 5 to 10 cwt. of gelatine into cartridges per diem, depending upon the diameter of the cartridges made.

After being cut up into lengths of about 3 inches, the gelatine is rolled up in cartridge paper. Waterproof paper is generally used. The cartridges are then packed away in cardboard boxes, which are again packed in deal boxes lined with indiarubber, and screwed down air tight, bra.s.s screws or zinc or bra.s.s nails being used for the purpose. These boxes are sent to the magazines. Before the boxes are fastened down a cartridge or so should be removed and tested by the heat test, the liquefaction test, and the test for liability to exudation. (Appendix, p. 6, Explosives Act, 1875.) A cartridge also should be stored in the magazine in case of any subsequent dispute after the bulk of the material has left the factory.

The object of the liquefaction test is to ensure that the gelatine shall be able to withstand a fairly high temperature (such as it might encounter in a s.h.i.+p's hold) without melting or running together. The test is carried out as follows:--A cylinder of the gelatine dynamite is cut from the cartridge of a length equal to its diameter. The edges must be sharp. This cylinder is to be placed on end on a flat surface (such as paper), and secured by a pin through the centre, and exposed for 144 consecutive hours to a temperature of 85 to 90 F., and during such time the cylinder should not diminish in height by more than one-fourth of an inch, and the cut edges should remain sharp. There should also be no stain of nitroglycerine upon the paper.

The exudation test consists in freezing and thawing the gelatine three times in succession. Under these conditions there should be no exudation of nitro-glycerine. All the materials used in the manufacture of gelatine explosives should be subjected to a.n.a.lytical examination before use, as success largely depends upon the purity of the raw materials. The wood-pulp, for instance, must be examined for acidity.

~Properties of the Gelatine Compounds.~--Blasting gelatine is generally composed of 93 to 95 parts nitro-glycerine, and 5 to 7 parts of nitro- cellulose, but the relative proportions of explosive base and nitro- glycerine, &c., in the various forms of the gelatine explosives do not always correspond to those necessary for total combustion, either because an incomplete combustion gives rise to a greater volume of gas, or because the rapidity of decomposition and the law of expansion varies according to the relative proportions and the conditions of application. The various additions to blasting gelatine generally have the effect of lowering the strength by reducing the amount of nitro-glycerine, but this is sometimes done in order to change a shattering agent into a propulsive force. If this process be carried too far, we of course lose the advantages due to the presence of nitro-glycerine. There is therefore a limit to these additions.[A]

[Footnote A: Mica is said to increase the rapidity of explosion when mixed with gelatine.]

The h.o.m.ogeneousness and stability of the mixture are of the highest importance. It is highly essential that the nitro-glycerine should be completely absorbed by the substances with which it is mixed, and that it should not subsequently exude when subjected to heat or damp. It is also important that there should be no excess of nitro-glycerine, as this may diminish instead of augment the strength, owing to a difference in the mode of the propagation of the explosive wave in the liquid, and in the mixture. Nitro-glycerine at its freezing point has a tendency to separate from its absorbing material, in fact to exude. When frozen, too, it requires a more powerful detonation to explode it, but it is less sensitive to shock. The specific gravity of blasting gelatine is 1.5 (i.e., nearly equal to that of nitro-glycerol); that of gun-cotton (dry) is 1.0.

Blasting gelatine burns in the air when unconfined without explosion, at least in small quant.i.ties and when not previously heated, but it is rather uncertain in this respect. It can be kept at a moderately high temperature (70 C.) without decomposition. At higher temperatures the nitro-glycerine will partially evaporate. When slowly heated, it explodes at 204 C. If, however, it contains as much as 10 per cent. of camphor, it burns without exploding. According to Berthelot,[A] gelatine composed of 91.6 per cent.

nitro-glycerine and 8.4 per cent. of nitro-cellulose, which are the proportions corresponding to total combustion, produces by explosion 177CO_{2}+ 143H_{2}O + 8N_{2}.

[Footnote A: Berthelot, "Explosives and their Powers."]

He takes C_{24}H_{22}(NO_{3}H)_{9}O_{11} as the formula of the nitro- cellulose, and 51C_{3}H_{2}(NO_{3}H)_{3} + C_{24}H_{22}(NO_{3}H)_{9}O_{11} as the formula of the gelatine itself, its equivalent weight being 12,360 grms. The heat liberated by its explosion is equal to 19,381 calories, or for 1 kilo. 1,535 calories. Volume of gases reduced temperature equals 8,950 litres. The relative value[A] of blasting gelatine to nitro- glycerine is as 1.4 to 1.45, kieselguhr dynamite being taken as 1.0.

[Footnote A: Roux and Sarran.]

CHAPTER V.

_NITRO-BENZOL, ROBURITE, BELLITE, PICRIC ACID, &c._

Explosives derived from Benzene--Toluene and Nitro-Benzene--Di- and Tri-nitro-Benzene--Roburite: Properties and Manufacture--Bellite: Properties, &c.--Securite--Tonite No. 3.--Nitro-Toluene-- Nitro-Naphthalene--Ammonite--Sprengel's Explosives--Picric Acid-- Picrates--Picric Powders--Melinite--Abel's Mixture--Brugere's Powders-- The Fulminates--Composition, Formula, Preparation, Danger of, &c.-- Detonators: Sizes, Composition, Manufacture--Fuses, &c.

~The Explosives derived from Benzene.~--There is a large cla.s.s of explosives made from the nitrated hydro-carbons--benzene, C_{6}H_{6}; toluene, C_{7}H_{8}; naphthalene, C_{10}H_{8}; and also from phenol (or carbolic acid), C_{6}H_{5}OH. The benzene hydro-carbons are generally colourless liquids, insoluble in water, but soluble in alcohol and ether.

They generally distil without decomposition. They burn with a smoky flame, and have an ethereal odour. They are easily nitrated and sulphurated; mono, di, and tri derivatives are readily prepared, according to the strength of the acids used. It is only the H-atoms of the benzene nucleus which enter into reaction.

Benzene was discovered by Faraday in 1825, and detected in coal-tar by Hofmann in 1845. It can be obtained from that portion of coal-tar which boils at 80 to 85 by fractionating or freezing.[A] The ordinary benzene of commerce contains thiophene (C_{4}H_{4}S), from which it may be freed by shaking with sulphuric acid. Its boiling point is 79 C.; specific gravity at 0 equals 0.9. It burns with a luminous smoky flame, and is a good solvent for fats, resins, sulphur, phosphorus, &c. Toluene was discovered in 1837, and is prepared from coal-tar. It boils at 110 C., and is still liquid at 28 C.

[Footnote A: It may be prepared chemically pure by distilling a mixture of benzoic acid and lime.]

The mono-, chloro-, bromo-, and iodo-benzenes are colourless liquids of peculiar odour. Di-chloro-, di-bromo-benzenes, tri- and hexa-chloro- and bromo-benzenes, are also known; and mono-chloro-, C_{6}H_{4}Cl(CH_{3}), and bromo-toluenes, together with di derivatives in the ortho, meta, and para modifications. The nitro-benzenes and toluenes are used as explosives. The following summary is taken from Dr A. Bernthsen's "Organic Chemistry":--

SUMMARY.

____________________________________________________________________ | | | C_{6}H_{5}(N0_{2}) Nitro-benzene. Liq. B.Pt. 206 C. | | | | C_{6}H_{4}(NO_{2})_{2} Ortho-, meta-, and para- di-nitro-benzenes. | | Solid. M.P. 118, 90, and 172 C. | | | | C_{6}H_{3}(NO_{3})_{3} S.-Tri-nitro-benzene. Solid. M.P. 121 C. | |____________________________________________________________________| | | | C_{6}H_{4}(CH_{3})NO_{2} Ortho-, meta-, and para- nitro-toluenes. | | B.P. 218, 230, and 234 C, Para compound solid. | |____________________________________________________________________| | | | C_{6}H_{3}(CH_{3})_{2}NO_{2} Nitro-xylene. Liquid. | |____________________________________________________________________| | | | C_{6}H_{2}(CH_{3})_{3}NO_{2} Nitro-mesitylene. Solid. | |____________________________________________________________________| | | | C_{6}H_{3}(CH_{3})(NO_{2})_{2} Di-nitro-toluenes. | |____________________________________________________________________| | | | C_{6}H_{4}Cl(NO_{2}) Nitro-chloro-benzenes. | | | | C_{6}Br_{4}(NO_{2})_{2} Tetra-bromo-di-nitrobenzene. | |____________________________________________________________________|

The nitro compounds are mostly pale yellow liquids, which distil unchanged, and volatilise with water vapour, or colourless or pale yellow needles or prisms. Some of them, however, are of an intense yellow colour.

Many of them explode upon being heated. They are heavier than water, and insoluble in it, but mostly soluble in alcohol, ether, and glacial acetic acid.

Nitro-benzene, C_{6}H_{5}(NO_{2}), was discovered in 1834 by Mitscherlich.

It is a yellow liquid, with a melting point of +3 C. It has an intense odour of bitter almonds. It solidifies in the cold. In di-nitro-benzene, the two nitro groups may be in the meta, ortho, or para position, the meta position being the most general (see fig., page 4). By recrystallising from alcohol, pure meta-di-nitro-benzene may be obtained in long colourless needles. The ortho compound crystallises in tables, and the para in needles. They are both colourless. When toluene is nitrated, the para and ortho are chiefly formed, and a very little of the meta compound.

~Nitro Compounds of Benzene and Toluene.~--The preparation of the nitro derivatives of the hydrocarbons of the benzene series is very simple. It is only necessary to bring the hydrocarbon into contact with strong nitric acid, when the reaction takes place, and one or more of the hydrogen atoms of the hydrocarbon are replaced by the nitryl group (NO_{2}). Thus by the action of nitric acid on benzene (or benzol), mono-nitro-benzene is formed:--

C_{6}H_{6} + HNO_{3} = C_{6}H_{5}.NO_{2} +H_{2}O.

Mono-nitro-benzene.

By the action of another molecule of nitric acid, the di-nitro-benzene is formed:--