US1428011A - Process of increasing the sensitiveness and power of explosive compositions and product thereof - Google Patents

Description

Patented Sept. 5, 1922.

TENT 10* QE.

WILLIAM M. DEHN, OF SEATTLE, WASHINGTON.

PROCESS OF INCREASING THE SENSITIVENESS AND POWER OF EXPLOSIVE COMPOSI- TIONS LAND PRODUCT THEREOF.

.No Drawing.

To all whom it may concern:

Be. it known that I, WILLIAM M. DEHN. a citizen of the United States, residing in Seattle, county of King, and State of Washingtomhave invented certain new and useful Improvements in Processes of Increasing the Sensitiveness and Power of Explosive Compositions and Product There of, of which the following is a specification.

This invention relatesto the use of diazodinitrophenol 1, (S -dinitro-Q-diazophenol) as an explosive and as an ingredient in explosive compositions.

Diazodinitrophenol, the preparation of which by Peter Griess is indicated in the Annalen der Chemie und Pharmacie, 113,201; 120,126, and an improved method of manufacture whereof is disclosed by my application, Serial No. 343,592, filed Dec. 9, 1919, has been found by tests I have made to be highly suitable as an explosive substance and as an ingredient of explosive compositions.

Though known by Griess and others that diazodinitrophenol has explosive properties, their experiments did not reveal the fact that it possesses exceptional explosive properties, so that it has not hitherto been introduced into the explosive art,

Diazodinitrophenol being a diazo compound, it has apparently been assumed that it does not possess suflioient stability for commercial use as an explosive.

Such assumption is not well founded. Though detonated by spark or by percussion, diazodinitrophenol possesses sufiicient stability to insure its safe manufacture, storage, and use an an explosive. urthermore, I-have found that its stability can be Varied to any practical degree by mixing it either with active bases or with water and other materials.

The formula assigned to diazodinitrophenol is:

Though possessing the vdiazo structure, it may be observed that the compound possesses an exceptional diazo structure, hence possesses exceptional properties as compared with other diazo compoun s.

That the compound has been studied only Application filed August 20, 1920. Serial No. 4045 51.

slightlyis apparent from a view of the following description of its pro erties, heretofore regarded as com lete. n iazodinitrophenol consists of bright yellow leaflets, slightly soluble in water, ether, benzene, and alcohol. It is very soluble in acetic acid, possesses little taste and tinctorial power and is stable is decomposed by hot concentrated sulphuric acid, and by cold solutions of alkalies. It explodes violently when heated. Its percentage of nitrogen is 26.68. (This is a higher value than that of the respective other organic nitro compounds heretofore employed in the manufacture of ex losive com ositions.)

I have discovered the followin additional properties. Diazodinitropheno dissolves without decomposition in warm nitrobenzone and in acetone. It crystallizes as yellow transparent rectangular plates from cooled nitrobenzene solutions, or from acetone solutions treated with ether or with hydrocarbon oils. It darkens in direct sunlight but is stable in diffused 1i ht. It is decomposed by many organic so vents. It melts and explodes violently above 150C. It possesses little or no noxious properties, hence difl'ers from most organic compounds used in the explosive art.

I hav e found that diazodinitrophenol can be stored under water at room temperatures for months without change of color and without loss of sensitiveness to explode.

Furthermore, I have found that when finely divided and wet with water it cannot be exploded by a N0. 8 detonating cap. Thus its practical stability in handlin is demonstrated. On the other hand I ave found that. diazodinitrophenol, when pure and dry, can be detonated by fuse, by spark, by percussion, or by friction. It can be subjected to great pressure without explodin and all compressed samples can be exploded in the different ways just mentioned. I have found that diazodinitrophenol is less sensitive to shock and to friction than the fulminates and that it possesses substantially 25 to 50% more power of demolition than mercury fulminate.

Its sensitiveness to combustion and to explosion, its great power of demolition, and its capacity in mixtures to increase the explosibility and brisance of the charge are its exceptional and valuable properties as an explosive.

in cold mineral acids. It,

Detonating explosives themselves are comparatively rare. Detonatin explosives, which on the one hand possessliigh power of demolition and on the other hand are inexpensive and are free from metals are practically unknown. Diazodinitrophenol answers to these qualification. Such an explosive can, therefore,. be used not only as an initiator of explosions but also as a bursting charge. Furthermore it can be mixed with a great variety of explosive materlals and can impart to such compositions greater sensitiveness and power of explosion. This property, to vivify and to impart brisance to common explosives, is a most valuable property of diazodinitrophenol. Especially when-it is in the crystalline form and is mixed with the explosive material,without fusing, does it function in the manner described.

I have found that. diazodinitrophenol in explosive compositions does 'not impart greater .power merely by adding its own power to that of'the other components of the charge, but by its capacity, as a relay of detonation, to sustain the explosive wave. For example, with 1g. charges consisting of ammonium nitrate with the indicated percentages of diazodinitrophenol and exploded by No. 6 caps, the following values were ob tained in the sand bomb:

Without the use of. diazodinitrophenol in sufficient concentration, the explosion of ammonium nitrate falls ofi, owing to loss of heat and owing to unfavorable conditions of moisture, density, confinement and size of crystals. With the powerful detonator diazodinitrophenol, however, the explosive wave is focally and progressively sustained, so that, for example, in the case of ammonium nitrate, with 1% of diazodinitrophe n01 an increase of 260% in effective power is obtained as compared with ammonium nitrate alone.

A -further. great advantage of diazodinitrophenolis its capacity in explosive compositions containin oxidants to utilize oxygen and thus to ad to its own power. This becomes obvious in the following equations:

This property may be illustrated with any the two have substantial] of the oxidizing salts used in explosive comexplosives, as indicated in thisspecification,

o with the combustibles, such as wood pulp or parafline, or with the inert materials used in explosive compositions, the sensitiveness to explode can be increased'.as desired, or may be held to any practical intermediate degree.

When mixed with infusorial earth, or with wood pulp, or with hydrocarbons, dynamites of varying lesser degrees of sensitiveness' and power can be produced. Such dyna mites, containing combustible carboneous material, can advantageously be mixed with active bases such as the nitrates or with nitro explosives, and thus ordinary dynamites containing small percentages of diazodinitrophenol can have increased brisance imparted thereto. a

' \Vhereas only mixtures with picric acid, trinitrotoluene, ammonium nitrate, and nitrocellulose are described in detail in this specification, I have found that diazodinitrophenol mixes as readily with the other common explosives, such as nitroglycerine, tet ryl, the nitrobenzenes,, and the nitronaph thalenes, and it imparts some of itscharacteristic properties to each of the same.

The properties referred to above make diazodinitrophenol highl suitable for use as an explosive substance by itself or in combinations with other compounds. It may be used, for example, as a filling for bombs, grenades, torpedoes, mines, and shells, as well as for the manufacture of primers and detonators, and also for all purposes for which explosive substances are used.

I have found that diazodinitrophenol alone, picric acid alone, and all mixtures of the same power of demolition. All mixt res of these two compounds, however, possess greatersensitiveness to explode than icric acid alone.

I have found that picric acid and diazodinitrophenol, whose melting points are 122 and above 150 respectively, can be melted in hot waterwhen their percentages are within certain limits. For example, equal weights of ,t-he two substances melt under water yielding a product whose specific gravsequently dried. Since all mixtures of the,

two components possess substantially equal strength but greater sensitiveness to explode than picric acid alone, such mixtures are very useful in the art ofexplosives.

I have found that contact of certain percentages of picric acid and diazodinitrophenol with acetone, ethyl acetate, or with other solvents yields products, which when freed from the solvent, melt below 100.

\ This method of plasticising their mixtures is also very useful in the art of explosives. Since all, such mixtures possess greater brisance than picric acid alone, diazodinitrophenol provides a vivifying ingredient of all such mixtures, and any desired quickened combustion and brisance, within the limits of brisance of the two components, can be imparted to their mixtures.

I have found .that diazodinitrophenol dissolves in trinitrotoluene when the latter is present in excess of 70% and the mixtures are heated at 100. either alone or under water. -The fused mixtures can either be poured into containers or can be poured into water in a thin stream, thus yielding a fine powder. This powder can also be obtained safely, after cooling the melt, by grinding under Water. When dried this powder is useful as a booster charge and as an ingredient of other explosive compositions. This property can be availed of to great advantage since trinitrotoluene alone is often too insensitive toward detonating charges. Substantially any desired sensitiveness to explode can be obtained by blending trinitrotoluene with diazodinitrophenol. Furthermore all such mixtures possess greater strength than trinitrotoluene itself.

I have found that diazodinitrophenol and nitrocellulose can be blended by the solvent effects of acetone and by other organic solvents and that, when freed from such solvents, the mixtures are more or less plastic, yellow, colloidal masses possessing greater sensitiveness and power than the nitrocellulose alone. These mixtures are useful in the art ofv explosives.

l have found, as indicated above, that diazodinitrophenol can advantageously be mixed with ammonium nitrate to form powders which can be used for a variety of purposes, since they are smokeless and powerful and can be made to detonate. Then the percentages of diazodinitrophenol in these powders is substantially less than 50%, oxygen available for combustibles or for nitro ex 'Diazodinitro- Materials. A B C D E F G H I J K phenol. 5 5 5 5 Ammonium nitrate Trinitrotoluene Dinitroben zene Picric acid....

R e 1 a t i v e ower Power without DDP. increased with DDP.. 25 9 It will be observed that in general percentages of increase of power are greater that the percentages of diazodinitrophenol used; and further, these mixtures containing diazodinitrophenol are more easily ignited and exploded byimpact than the corresponding compositions without the diazodinitrophenol.

My process, involving as it does a powerful distributive booster charge, reveals further advantages in that it admits of compression to greater densities, it admits of the resence of greater percentages of adventltious water or other inert material, it overcomes deficiencies in confinement, and it dispenses with special contrivances for ordinary booster charges.

I claim:

1. The process of increasing the sensitiveness and power of explosive compositions which comprises mixing diazodinitrophenol and other explosive matter under water and subsequently drying, substantially as described. I

2. The process of increasing the sensitiveness and power of explosive compositionsdiazodinitrophenol moistened with water to render it safe during incorporation therewith.

5. The process of increasing the sensitiveness and power of explosive compositions which comprises incorporating with said explosive material a lesser proportion of diazo- I dinitrophenol in the presence of water and subsequently freeing the mixture from water, substantially as described.

6. An explosive .material com rising diazodinitrophenol together with at er explosive material.

7. An explosive comprisin 'diazodinitrophenol together with ammonium nitrate.

8. An explosive comprising diazodinitro- "phenol together with other explosive material and inert material.

9. An explosive comprising diazodinitrophenoltogether with ammonium nitrate and inert material.

10. An explosive comprising diazodinitrophenol together With other explosive material and oxidantmaterial.

11. An explosive comprising diazodinitrophenol together with other explosive material, oxidant material, and inert material.

In witness whereof, I have signed my name hereto.

WILLIAM M. DEHN.