US1849355A - Explosive and process of making same - Google Patents

Description

1 peratures.

- consisting of Patented Mar. l5, i932 UNETED TATEfi smear FFEQE ARTHUR S. ONEIL AND WESTERN CARTRIDGE DELAWARE ILLINOIS, ASSIG-NORS To A CORPORATION OF EXPLOSIVE AND PROCESS OF MAKING SAME No Drawing.

This invention relates to explosives and more particularly to explosives employing a tetra-nitro-anilin.

Tetra-nitro-anilin is not only one of the most powerful explosives known, but its characteristics also adapt it ideally for explosive purposes. It combines the stability of an aromatic nitro derivative with the explosive power of analiphatic nitro ether, while it has comparatively high resistance to heat and mechanical influences. It is inert chemically and has no action upon the metal of caps, shells, etc. It is non-hygroscopic and moisture has no effect on it at all at ordinary tem- Its cost is, however, prohibitive to enable its use in considerable quantities where the explosive must be sold in competition with other and cheaper explosives even though of less power.

One of the objects of this invention, therefore, is to develop an explosive in which a tetra-nitro-anilin may be economically employed, and more particularly adapted for various commercial uses.

Another object is to develop an explosive in which the tetra-nitro-aniline is employed as a sensitizer in connection with less sensitive explosives.

Another object is to develop a powerful explosive in which the percentage of tetra-nitroanilin is small.

After the conclusion there was and is now on of smokeless powder;

of the World War hand large quantities this powder in its available form has practically no peace time utility and has, therefore, a low commercial value. It is in the form of a dense colloided intro-cellulose and may be coated or impregnated' with a deterrent to render it progressive burning.

Another object of this invention, therefore, is to sensitize such a nitro-cellulose so as to enable it to be more readily detonated.

Another object is to provide an explosive nitro-cellulose compounded with a tetra-nitro-aniline in such a manner as to enable the same to be commercially emploved.

Further objects will appear from the detail description ill-Which the various embodi- Application filed March 12, 1925. Serial No. 15,120.

ments of this invention will be described; it is, however, to be understood that the invention is susceptible of various other embodiments.

In accordance with this invention a small percentage of the tetra-nitro-anilin is intimately mixed with a larger percentage of a less sensitive or cheaper nitro-hydrocarbon, and this is preferably accomplished by dissolving the brisant tetra-nitro-anilin in the less sensitive component. Suitable solvents of tetra-nitro-anilin adapted for this purpose are aromatic nitro-compounds, of which trinitrotoluene, di-nitro-toluene, tri-nitro-benzene, di-nitro-benzene, etc., as well as picric acid are examples. Furthermore mixtures of nitro-hydrocarbons may be used; these mixtures are of special advantage when the nitrohydrocarbons have high melting points, for by using mixtures of such compounds in molecular proportions the melting points are depressed. Suitable mixtures, in molecular proportions, are: tri-nitro-toluene and tri-nitro-benzene, tri-nitro-toluene and dinitro-benzene, tri-nitro-toluene and picric acid, etc. Whether a single nitro-hydrocarbon or mixtures of nitro-hydrocarbons are used, the tetra-nitro-anilin is dissolved in the molten solvent. This can be accomplished by heating the tetra-nitro-anilin and the less sensitive nitro-hydrocarbon, in the desired proportions, in a suitable container until the solution of the tetra-nitro-anilin in the nitrohydrocarbon is complete; solution takes place at a temperature from 85 C.-86 C. c.

We have found that even a small percentage of a tetra-nitro-anilin added to or dissolved in'a less sensitive nitro-hydrocarbon sensitizes the latter to such a degree that it is much more easily and completely detonated and requires only a small quantity of a brisant initiator, such as fulminate of mercury, to initiate detonation. The detonation of even a small quantity of the powerful tetra-nitro-anilin will set up an explosive wave which will propagate throughout the mass of the less sensitive nitro-hydrocarbon so as to secure complete detonation thereof. Where such an intimate mixture or solution employing even a small percentage of a tetranitro-a-nilin is detonatedby an initiator, such as fulminat'e of mercury, upon ignition of the initiator and the detonation of the same, it will set up an initiating wave of detonation which will detonate the very sensitive tetra-nitro-anilin; the detonation of the latter will set up a supplementary wave of detonation; the two waves will combine so. as to produce a resultant wave whose amplitude is higher than that of either the initiating or supplementary wave. The combined or resultant wave will, therefore, serve to detonate the less sensitive nitro-hydrocarbon. Due to this principle of,action, not only can the quantity of initiator be reduced to a minimum, but a powerful explosive can be produced by the employment of a very small percentage of the tetra-nitro-anilin intimately mixed with a much larger percentage of the less sensitive nitro-hydrocarbon. Since this less sensitive nitro-hydrocarbon can be in a cheap form and since the quantity of the more highly priced tetra-nitro-anilin can be made so small, a cheap but powerful explosive can be produced. The above described properties and characteristics togetherwith the fact that such-a mixture can be made stable, chemically inert and nonhygroscopic renders the same very suitable as an explosive.

The percentage of tetra-nitro-anilin required to produce the desired sensitiveness and propagation of the explosive wave, depends upon the character of explosive desired. We have found that generally stated the percentage should not be below 2% but need not be in excess of 15%. Where tri-nitro-toluene is used with tetra-nitro-anilin, the proportions of the mixture may be 2%-15% of tetra-nitro-aniline and 98%- 85% of tri-nitroetoluene. I Generally for mtro-hydrocarbons the proportions can be in that ratio, although for the more insensitive Intro-hydrocarbons the tetra-nitro-anilin content may be as high as 20%.

A solution of a small percentage of tetranitro-anilin in a nitro-hydrocarbon, and more specifically an aromatic nitro-compound such as tri-nitro-toluene, is of itself an explosive and may be used commercially as an ex plosive and has various commercial applications which will now be described.

In a primer composition for confined explosive charge such a solution performs a useful function as a fuel ingredient, since it will add considerable heat to the flame and does not lower its sensitiveness materially; In such a case the proportions are from 2%10% of the tetra-nitro-anilin dissolved with 98%90% of the nitro-hydrocarbon; we have obtained best resultswith, a solution containing 5%-7% of the tetra-nitro-anilin and 9570-9570 of trinitrostoluene. In such a composition any suitablednitiator may be used, and although fulminate of mercury has been found especially suitable, the composition has been used successfully in non-fulminate primers. The proportion of the initiator required varies with the type of priming composition; fulminate of mercury can vary from 10%40% of the total mixture.

Ina detonating or blasting cap the solution has many advantages when used as the main charge in a shell and capped by an initfiator of detonation such as fulminate of mercury. The fact that it is chemically inert obviates action upon the metal of the shell even when moist, while the fact that it is non-hygroscopic obviates any effect of moisture. Moreover its cheapness, on account of the small amount of tetra-nitro-anilin with a comparatively cheap nitro-hydrocarbon renders it commercially attractive.

Upon ignition of the initiator and the detonation of the same, it will set up a wave of detonation which will detonate the more sensitive tetra-nitro-anilin so as to setup a supplementary wave of detonation; the two Waves will combine so as to produce a resultant wave of detonation whose amplitude is high; accordingly the combined wave will, therefore, serve to detonate the less sensitive nitro-hydrocarbon. Due to this action, even a-small percentage of tetra-nitro-anilin will serve to effect complete detonation of an insensitive nitro-hydrocarbon.

The proportions of the solution adapted as a main charge in a blasting cap may generally be 5%-l5% of tetra-nitro-anilin and 95%85% of the nitro-hydrocarbon. Good results have been obtained with a solution of 5% of tetra-nitro-anilin and 95% of trinitro-toluene, although a solution containing 10% tetra-nitro-anilin gave somewhat better results. In such a blasting cap, the initiator, such as fulminate of mercury, is placed over the main charge. The solution may be used as a main charge in either the fuse or electrically ignited types.

The solution as described may also be used for filling high explosive projectiles, into which it may be cast, and many be generally used for. sensitizing commercial explosives. The proportions may be generally from 2%20% of a tetra-nitro-anilin and 98%80% of a nitro-hydrocarbon as heretofore described.

Such a solution may also be employed for coating or impregnating smokeless powder, such as dense colloided nitro-cellulose, either coated or uncoated. Thus a solution of 2%15% of tetra-nitro-anilin in tri-nitrotoluene, di-nitro-toluene, tri-nitro-benzene or di-nitro-benzene may be employed and applied in the ordinary manner, namelv by rumbling the solution with the powder iii the presence of heat, at a sufficient temperature and for a sufiicient period, to cause such coating or impregnation; thus heating at the in fulminate primers,- the melting point of the solution for about one hour will generally be found proper. In such a process the insensitive nitro-hydrocarbon, such as tri-nitro-toluene, di-nitro-toluene, etc., acts as a colloiding agent to'fix the tetra-nitro-anilin on the surface of the nitrocellulose powder. The result is that the properties of the nitro-cellulose powder are improved on account of an increase in ballistic value due to the fact that the coating is more sensitive to ignition than when only a single and rather insensitive nitro-hydrocarbon is used.

Smokeless powder is very diflicultof complete detonation, especially when in the form of a dense colloided nitro-cellulose, and more so when coated or impregnated with a deterrant, such as di-nitro-toluene, as is the case with military ammunition. In accordance with this invention the nitro-cellulose has intimately mixed therewith a tetra-nitroanilin and a less sensitive nitro-hydrocarbon as heretofore described. The mixture may either be a simple mechanical one or a partial or more complete colloid of the ingredients as hereinafter described. Furthermore the percentage of the tetra-nitro-anilin can morover be made small as compared to the percentage of the less sensitive nitro-hydrocarbon and even the nitro-cellulose as in the embodiments heretofore described.

In accordance with one embodiment of this invention the three ingredients, namely the tetra-nitro-anilin, the less sensitive nitrocompound, such as tri-nitro-toluene, and the nitro-cellulose, such as smokeless powder, are ground to the desired degree of granulation, say to pass an 80 mesh screen. They are then mixed in the proportion of 40%60% of the nitro-cellulose and 60%-40% of the tetra-nitro-anilin and the tri-nitro-toluene, the latter being in the proportion of 2%15% of the. tetra-nitro-anilin and 98%85% of the tri-nitro-toluene. The materials are mixed in any suitable mixer, using the usual precautions necessary in handling explosives. The grinding of the materials preparatory to mixing, may also be performed under water, or by passing the same through the mill with a stream of water. The mixture can be used for explosive purposes without further screening.

In accordance with another embodiment of 7 this invention the tetra-nitro-anilin is dissolved in the less sensitive nitro-hydrocarlxin in the manner and using the proportions heretofore described. The solution after cooling is then ground and screened to the. proper size and mixed with the ground and screened intro-cellulose in the proport ons as heretofore described. In this manner a more uniform distribution of the small percentage of the tetra-nitro-anilin throughout the mixture is obtained, although the mixture is still a mechanical one as far as the nitro-cellulose and the solution is concerned.

' In accordance with still another embodiment of this invention the tetra-nitro-anilin and the less sensitive nitro-hydrocarbon, such as tri-nitro-toluene, in the proportions of 5%- 20% of tetra-nitro-anilin and 95%80% of tri-nitro-toluene, are heated in a suitable container at a temperature and for a period sufficient until the solution of the tetra-nitroanilin in the tri-nitro-toluene is complete. Such solution takes place between 85 and 86 degrees centigrade. When solution is complete the nitro-cellulose, such as smokeless powder, is slowly added with continued stirring until the desired proportions have been obtained, which may be as heretofore described, namely 40%-60% of the tetra-nitroanilin-tri-nitro-toluene solution and 60%- 40% of the nitro-cellulose. There will be formed a colloidal solution of the nitro-cellulose in the tetra-nitro-anilin-tri-nitro-toluene solution. As soon as the mixture is sufficiently gelatinized it is spread out and allowed to cool; when cool, the gelatinized mixture or colloid is ground in a suitable mill to the desired granulation, which usually is 60-80 mesh.

Explosive mixtures of nitr'o-ce'llu'iose and tetra-nitro-anilin together with a less sensitive nitro-hydrocarbon can be made by using nitrated cotton in place of dense colloided nitro-cellulose. The nitrated cotton is ground and added to the molten solution of tetra-nitro-anilin in, for instance, tri-nitrotoluene as heretofore described when using dense colloided nitro-cellulose. The tetranitro-anilin and tri-nitro-toluene solution should, however, be heated slightly above its melting point and the nitrated cotton added and stirred in the hot solution until it is completely gelatinized or colloided. The mixture is then allowed to cool and solidify, when it is ground and screened. The same proportions may be used as when using dense colloided nitro-cellulose. In the preparation of this colloid the tri-nitro-toluene or other nitro-hydrocarbon forms a vehicle for the tetra-nitro-anilin, for since tetra-nitro-anilin decomposes on heating, it is necessary to apply it in a vehicle in which it is dissolved, and which vehicle acts as the medium for securing such colloiding or gelatinization.

An intimate mixture of nitro-cellnlose, a tetra-nitro-anilin and a less sensitive nitrohydrocarbon forms a satisfactory and powerful explosive which is adapted for peace as well as war time purposes. It .is very inert chemically and has no action upon the metal of containers or shells even when moist. lt is non-hygroscopic and moisture has no otter-t on it at all at ordinary temperature. It is also very stable as well cheap since ground smokeless powder is now cheap and even powder dust can be used.

superior to pure mechanical the small percentage of tetra-nitro-anilin is The rather insensitive nitro-cellulose is sensitized by the more sensitive tetra-nitroanilin and in the solution even by the more sensitive aromatic nitro-compoun'd, such as tri-nitro-toluene. Where such an intimate mixture or solution employing even-a small percentage of a tetra-nitro-anilin is detonated by an initiator, such as fulminate of mercury, upon ignition of the initiator and the detonation of the same, it will set up an initiating wave of detonation which will detonate the very sensitive tetra-nitro-anilin; the detonation of the latter will set up a supplementary wave of detonation; the two waves will combine so as to produce a resultant wavewhose amplitude is higher than that of either the initiating or supplementary waves. The combined or resultant wave will, therefore, serve to detonate the less sensitive trinitro-toluene or other nitro-hydrocarbon and may even detonate the even less sensitive nitro-cellulose. However, if the nitro-cellulose is not completely detonated by the resultant wave of the initial and supplementary'waves,

then the tertiary wave set up by detonation of the tri-nitro-toluene will either alone, or

in combining with .the initiating and supple mentary waves to form a final resultant wave, serve to completely detonate the insensitive nitro-cellulose. Due to thisp rinciple of action, not only can the quantity of initiator be reduced to a minimum, but a powerful explosive can be produced by the employment of a very small percentage of the tetra-nitroanilin, which percentage may be as low as 1 of the total mixture or even lower. Since the insensitive nitro-hydrocarbon, such as tri-nitro-toluen'e, is cheap and since the nitrocellulose is also cheap, and may even be a waste product, such as powder dust, and since the quantity of the higher priced tetranitro-anilin can be made so small, a cheap but powerful explosive can be produced.

Mixtures in which the tet'ra nitro-aniIin is actually dissolved'in the vehicle therefor prior to mixing with the nitro-cellulose are mixtures since more evenly distributed. Moreover the colloided or gelatinized mixture has advantages over both of the othermixtures. All components of the mixture are evenly distributed and the mixture is denser so that the particles are in closer contact; the detonating waves are, therefore, efficiently propagated. The mixture has no tendency to be fiufly or sticky;

consequently it lends itself more readily to be charged into containers and shells. Moreover I there is absolutely no possibility of segregation.

While tri-nitro-toluene is particularly adapted as a component of an explosive mixture containing also nitro-cellulose and tetranitro-anilin, especially as a vehicle for the tetra-nitr0-anilin, other nitro-hydrocarbons may be used in place of tri-nitro-toluene as these nitro-hydrocarbons may be used as heretofore described.

A mixture of nitro-cellulose, tetra-nitroanilin and a less sensitive nitro-hydrocarbon, such as tri-nitro-toluene, in the proportions and prepared as heretofore described, and especially in the colloided or gelatinized form, is especially suitable as a priming composition and especially for small arms ammunition. In case of primers for small arms ammunition, .a. mixture of these ingredients will add considerable heat to the flame. Contrary to the action of most fuel ingredients, it lowersthe sensitiveness of the primers but slightly. In non-fulminate compositions, it may even add somewhat to the sensitiveness.

Such a nitro-cellulose mixture, containing a small percentage of tetra-nitro-a-nilin together with a less sensitive nitro-hydrocarbon, such 'as tri-nitro-toluene, especially when in the colloided or gelatinized form, is especially suit-able as a main explosive charge for blasting caps or detonators, due to the fact that it is inert chemically, non-hygroscopic,

stable and cheap. It requires not only a small percentage of tetra-nitro-anilin together with a less sensitive nitro-hydroca-rbon is suitable for forminga dynamite stick. andeither a mechanical mixture or the colloided or gelatinized mixture may be employed. The proportions may be as heretofore described. namely 40%-60% nitro-cellulose 60%40% of a tetra-nitro-anilin and a less sensitive nitro-hydrocarbon, the latter being in the proportion of 2%20% of a tetra-nitroanilin and 98% 80% of the less sensitive nitro-hydrocarbon. The mixture may either be used alone or with other and usual ingredients of dynamite.

v In the employment of the less sensitive nitro-hydrocarbons such as tri-nitro-toluene, di-nitro-toulene, etc., "arious isomers may be used. The isomer of T. N. T. which is most practical is the symmetric 2.4.6. isomer. This is the ordinary commercial article. However, it as a rule contains some of the asymmetric 2.3.4. and 2.3.5. compounds and consequently mixtures of all three could be used. Meta and D. N. T; and meta D. N. B. or mixtures of all three isomers could be used. Using T. N. B. the symmetric isomer would be preferable.

It will be understood that not only. may tetra-nitro-anilin be used as the primary sensitizer, but. the derivatives may be used. This is also true of tri-nitro-toluene, di-nitro-toluene, etc. 4 Furthermore other smokeless powder than those having dense colloided nitro-cellulose may be used.

While various compounds and mixtures employing a. tetra-nitro-anilin and suitable for explosive purposes and while various uses thereof have been described, it will be understood that this inven tion is susceptible 'of various other embodiments. It is, therefore and further, to be understood that this invention is not limited t the specific embodiments described.

While certain theories have been advanced, this has been done for the purpose of explanation it is, however, to be understood that such theories are not essential tothe employment or complete disclosure of this invention;accordingly it is to be understood that this invention is not to belimited to any advanced theory or theories.

Havin thus described the invention, what is claime is:

1. An explosive containing a tetra-nitroanilin and a tri-nitro-toluene in the proportions of 2%15% of the tetra-nitro-anilin and 98%-85% of the tri-nitro-toluene;

2. An explosive containing a tetra-nitroanilin dissolved in a tri-nitro-toluene in the proportions-of 2%15% of the tetra-nitroanilin and 98%85% of the tri-nitro toluene.

3. A primer for a confined explosive charge having a charge containing a tetra-nitro-anilin and a'tri-nitro-toluene together with an initiator.

4; A primer for a confined explosive charge having a charge containing a small percentage of a tetra-nitro-anilin dissolved in a large percentage of, a tri-nitro-toluene together with an initiator.

5. r A primer for a confined explosive charge having a charge containing 10%40% of fulminate of mercuryand 90%-60% of a tetranitro-anilin and a tri-nitro-toluene in the proportion of 2%10% of thetetra-nitro-anilin and 98%'90% of the tri-nitro-toluene.

6. Adetonating or blasting cap compr1s ing ashell containing as a combined charge a tetra-nitro-anilin and a less sensitive aromatic nitro-compound together with an initiator of detonation therefor.

7. A detonating or blasting cap comprising a shellcontainingas a combined charge a tetra-nitro-anilin and a'tri-nitro-toluene together with an initiator of detonation therefor. i I

8. A detonating or blasting cap comprising a shell containing as a combined charge a have been described,

tetra-nitro-anilin and a less sensitive aromatic nitro-compounds together with an initiator of detonation therefor.

9. An explosive containing a .substantial proportion of nitro-cellulose, a tetra-nitroanilin and an' aromatic nitro-compound.

10. An explosive containing nitro-cellulose, a tetra-nitro-anilin and a nitro-toluene.

14. An explosive containing40% 60% of nitro-cellulose and 60%40% of a tetranitro-anilin and a tri-nitro-toluene in the proportion of 2%15% of the tetra-nitro anilin and 98 of the tri-nitro-toluene. 15. An explosive containing nitro-cellulose colloided with a tetra-nitro-anilin.

16. An explosive containing nitro-cellulose colloided with a 'tetra-nitro-anilin and an aromatic nitro-compound.

17. An explosive containing nitro-cellulose colloided with a tetra-nitro-anilin and a tri-nitro-toluene.

18. An explosive containing nitro-cellu.-'

lose colloided with a small percentage of a tetra-nitro-anilin and a larger percentage of a tri-nitro-toluene.

19. A primer having a charge containing nitrocellulose, a small percentage of a tetranitro-anilin and a larger percentage of an aromatic nitro-compound together with an initiator.

20. A detonating or blasting cap comprising a shell'containing as a combined charge, nitro-cellulose, a small percentage of a tetranitro-anilin and a larger percentage of a nitro aromatic compound together with an initiator of detonation therefor.

21. An explosive containing nitro-cellulose and a small percentage of a tetra-nitroanilin. I

22. The process of sensitizing nitro-cellulose consisting in mixing therewith a small percentage of tetra-nitro-anilin.

23. The process consisting in gelatinizing nitro-cellulose with a tetra-nitro-anilin.

24. The process consisting in gelatinizing nitro-cellulose with a small percentage of a tetra-nitro-anilin.

25. The process consisting in treating ni- 'AZE sive aromatic nitro-compound and sensitized by a small percentage of a brisant nitrohydrocarbon.

28. An explosive comprising an intimate 5 mixture of dense colloided nitro-cellulose, an explosive aromatic nitro-compound and a brisant nitro-hydrocarbon.

29. An explosive comprising nitro-cellulose gelatinized with an aromatic nitro-comm pound and a brisant nitro-hydrocarbon.

In testimony whereof We affix our signatures this 2nd day of February, 1925.

ARTHUR S. ONEIL. ALFON S G. SOHURICHT.