US1928206A - Detonator composition - Google Patents

Description

Sept. 26, 1933. s. B. LARGE DETONATOR' COMPOSITION Filed NOV. 18, 1931 INVENTOR ATTORNEY Patented Sept.- 26, 1933 UNITED STATES Pa nn'roNA'ron coMrosrrroN Sylvester B. Large, Tamaqua, Pa., assignor to Atlas Powder Company, Wilmington, DeL, a corporation of Delaware Application November 18, 1931 Serial No. 575,929

19 Claims. (01. 52 4) My 'invention' relates to improvements in substances, less sensitive than the said polyhydric detonators, such as are used for initiating charges alcohol nitrates and therefore less sensitive than of explosives. mercury fulminate and lead azide.

Its object is the production and use of new More specifically, I have produced these 5 and improved primary detonator compositions, superior primary detonator compositions, in accharacterized by excellent and reliable detonating cordance with my invention, by mixing one or efliciency; by an ideal physical form for charging, more solid nitric esters of polyhydric alcohols 01 by low cost, and by being, toward friction, imthe general formula CnHn+2(OH)n, of which pact and heat, as safe or safer than any primary nitromanniteand nitrodulcite are examples, with 10 detonator composition-heretofore known or used. one or more other types of solid organic nitrates, Further objects are the reduction of hazard to of which nitrolactose and nitropentaerythrite are a life, limb and equipment, in the manufacture examples, and/or with one or more solid organic of detonators and the increase of safety for the nitro-bodies of which tetryl is an example. users of detonators, as well as for children, in I have found that these mixtures are rendered 15 whose hands they may accidentally fall. Still satisfactory for use as primary detonator 7 further objects will be evident from the descripcharges, in accordance with my invention, when tion of y e ion they are either admixed in a dry, moist or wet Primary detonator compositions are'characterstate or precipitated together from solution. ized or defined as those which are capable of Also in accordance with my present invention, it 20, advancing from simple ignition to detonation, is necessary to employ a hot flame ignition, in almost instantaneously, when charged into the conjunction with my novel type of primary detconfines of a suitable container or shell. Due to onator compositions, which may be any one of this characteristic, they are suitable for use either several general contemplated forms, as for eX- as the entire charges for so-called simple deample; (1) an unusually hot safety-fuse end-spit 25 tonators or as the initiator, primer or booster to ignite the primary detonator charge directly; charges for so-called compound detonators, in (2) a pre-formed electric fuse or match-head which are employed explosive base charges, usual- (several types of which are already well known) 1y of the non-primary detonating type. for direct ignition; (3) a flash composition placed In my copending application No. 502,559, I upon the primary charge for indirect ignition by 30 have disclosed that solid explosives of the genmeans of ordinary safety-fuse or an electric fuse eral formula CnHn+2(N03)n are adaptable for or match-head; (4) a flash composition, loosely use as primary detonator charges in compound placed upon the primary charge, for indirect detonators; ignition by means of an electrically heated I pointed outthat this new and improved type bridge-wire imbedded in the loose flash composi- 35 of primary detonator composition was particution; etc.

larly advantageous in impound detonators, Further, it is most desirable, although not abwherein base charges of cheaper explosive subsolutely essential to my invention, that my novel stances are employed, although it was understood type of primary detonator composition be pressed that they might also be used as the entire charges under an inner capsule, and/ or otherwise con- 40 for simple detonators. I also pointed out that it fined in order to make for increased detonator was preferable to confine this new and improved reliability as well as to decrease the amount of type of primary detonator compound under an primary charge, required to completely detonate inner capsule and to ignite or initiate it with a the usual types of detonator secondary charges hot flame tongue, as for example;- by an unwhen and if used therewith.

45 usually hot safety-fuseend-spit or by an electric The primary detonator compositions of the fuse, or match head in accordance with the inventype described in my copending applications tion disclosed in copending application Serial Serial Nos. 502,559 and 502,560 are much im- No. 502,560. proved by mixing with one or more of the speci- The present invention relates to the iurther fied polyhydric alcohol nitric esters by the conr improvement of detonators of this general charcurrent precipitation method various proportions acter and is based upon my discovery that superior of one or more solid explosive substances, less primary detonator compositions are obtained by sensitive than mercury fulminate and lead azide. mixing one or more solid nitration products of For example, a nitrodisaccharide, such as nitrorr polyhydric alcohols of the. general formula lactose, and a polyhydric alcohol nitrate, such CnHn+2(OH)n with one or more solid explosive as nitromannite, when concurrently precipitated higher densities, better physical forms, lower ingredient costs, decreased rather than increased sensitivities to friction and impact, etc. Higher densities and better physical forms are actual advantages since they contribute such advantageous effects, as for example, greater ease and uniformity of charging into the detonator shells; smaller occupied spaces in the shells; permitting the use of smaller shells; less susceptibilities to being dead-pressed to an extent where complete detonation will not take place 'upon ignition, etc.

As other examples, an organic nitro-body such as tetryl may be used either in addition to or in place of the nitro-disaccharide, in the above example. more dense, less sensitive and more stable primary detonator compositions, with corresponding advantages as exemplified above.

Although I may select any one of several methods of mixing the components of my novel primary detonator compositions, in accordance with my invention, as for example dry mixing, damp mixing, wet mixing, mutual precipitation from solution, etc., I prefer to adopt the mutual precipitation method, on account of obtaining thereby a more uniform product, as to particle size, particle shape, hardness of particles, homogeneity of the mixture, etc. This method also permits of a more thorough and eiiective stabilizing treatment. So far as I am aware, I am the first to mix, by the mutual precipitation method, a solid nitration product of a polyhydric alcohol of the general formula CnHn+2 (N03) 11 and another solid explosive substance adapted to enter into a homogeneous mass with the said nitrated alcohol and especially for the purpose of producing a primary charge for detonators. I am aware of the fact that ordinarily the choice of one method of mixing the constituents of such a composition over another known method would be within the expected knowledge of those skilled in the art. However, unusual conditions exist in the present case, as for example the fiuify, crystalline and non-free-flowing character of the nitrated polyhydric alcohols (nitromannite and the like) especially in the pure state, which makes them not only extremely difficult to be charged into detonators with any practical degree of ease and uniformity by means of ordinary charging apparatus, but also makes then'rrelatively susceptible to being dead pressed to the extent that they will fail to properly advance from ignition to detonation or even fail to ignite at all with practical ignition media. By concurrently precipitating, from a mutual solution, the said nitrated polyhydric alcohols with a contaminating material of the type described, a material of an entirely different and much more desirable character is obtained, however, which is much polyhydric alcohol in such manner as to maintain the sensitivity of the latter to the greatest possible extent. The mutual precipitation meth- Such a material as tetryl makes for still Special care must be'taken to mix the diluting ingredients with the nitrated from a mutual solvent in various proportions,

0d of mixing yields results that would be impossible with ordinary methods of mixing. For example, this method yields so much greater homogeneity of the charge that a maximum amount of additive ingredients may be mixed with the nitrated polyhydric alcohol, While maintaining the maximum sensitivity of the whole with respect to the action of the igniting and detonating hot flash composition. The homogeneity referred to extends beyond mere uniformity of the respective constituents, and mere uniformity of mixing, and includes uniformity of particle size; particle shape, hardness of the particles, etc. Since this general homogeneity also provides for more thorough and uniform stabilization, it will be seen that the combining of the ingredients by mutual precipitation renders it possible to use nitromannite and its equivalents as defined herein, in a highly effective and economical Way.

Examples of solid nitration products of polyhydric alcohols of the general formula CnHn+2 (OH) in are nitromannite, nitrodulcite and nitroerythrite,

Examples of solid, explosive substances less sensitive than mercury fulminate and lead azide suitable for use with the polyhydric alcohol nitrates in the relation stated are: nitrolactose, nitropentaerythrite, tetryl, nitrostarch, nitrogalactose, nitromaltose, nitroarabinose and nitrocellulose.

Primary detonating charges of the character disclosed herein operate with particularly great efficiency when the hot flash composition is disposed in spaced relation to the said charge because this pormits the discharge of a tongue or spit of intensely hot flame upon the charge. One type of compound detonator embodying the invention is shown in the accompanying drawing where 5 designates the shell, 6 the secondary or base charge, '7 the primary or initiating charge, 8 an inner capsule and 9 a conventional type of electric match-head with lead-in wires 10 connected therewith. This drawing is submitted merely to bring out the fact that the igniting me- 7 dium, whether an electric match head or otherwith theunderstanding that they are not limit ing.

1. A charge 0.4 gram of a 50-50 mixture of nitromannite and nitrolactose, precipitated from acetone solution by pouring into water and dried, is charged into a gilding metal shell, a perforated inner capsule placed thereon and the whole pressed down into the'bottom of the shell by means of 150 pounds pressure on a metal pin. Over the pressed charge is then assembled an electric match head in the usual, well known manner.- This type of assembly, when fired, consistently yields excellent A grade lead plates and crushes an average of about 39 grams of standard 30 mesh testing sand, according to the well known U. S. Bureau of Mines standard test.

.2. The same as Illustration (1), but with a charge of 0.2 gram of the 5050 nitromannitenitrola ctose mixture.

3. The same as Illustrations (1) and (2), but

with a suitable flash composition pressed on the detonator charge or charges and without the 1 base charge of 0.2 gram of tetryl and a primer electric match-head assembly; the ignition of the flash composition being eifected by means of ordinary safety-fuse inserted and crimped in the open ends of the detonators.

4. The same as Illustrations (1), (2) and (3) but with a 75-25 mixture of nitromannite and tetryl instead of the -50 mixture of nitromannite and nitrolactose.

5. The same as Illustrations (1), (2) and (3), but with a 25 mixture of nitrodulcite and tetryl instead of the 50-50 mixture of nitromannite and nitrolactose.

6. The same as Illustrations (1), (2) and (3) but with a 503515 mixture of nitromannite, nitrolactose and tetryl, respectively, instead of the 5050 mixture of nitromannite and nitrolactose.

It should be distinctly understood that the solid explosive substances-specified as necessary to my invention, may be the ordinary grades of impure products usually produced, for example by the nitration of the commercial forms of the required polyhydric acohols of the general formula CnHn+2(OH)n; the said nitrated products being prone to contain certain impure isomers, lower nitric esters, etc. They may, however, also be the chemically pure compounds, as obtained, for example, by recrystallization of impure forms, from a suitable solvent or solvents. Nitromannite, for example, may refer either to the chemically pure hexanitrate or it may include proportions of the lower nitric esters, mixed therewith.

It should also be distinctly understood that the explosive substances specified as necessary to my invention, may be stabilized in any suitable manner, by means of minor quantities of one or more stabilizing materials, without being outside the scope of my invention.

It shall further be distinctly understood that my invention anticipates and includes the use of minor proportions of various kinds of certain admixed materials, in conjunction with the types of explosive substances specified, as long as the resulting primary detonator composition will function, as such, in a satisfactory manner and without increasing the sensitivity of the composition to an appreciably hazardous degree. I contemplate, for example, the possible use of such substances as stabilizers, desensitizers, oxygen carriers, graining agents, dilutants etc. as minor ingredients of the primary detonator compositions. Additive ingredients, as exemplified above, may be precipitated or otherwise suitably mixed with the principal ingredients of my novel primary detonator compositions. I prefer, however, to use the mutual precipitation method, where possible, in order to improve the uniformity and homogeneity of the composition and to permit its more thorough and eifective stabilization.

On the other hand, I am fully aware that the use of super-sensitive explosives, as for example fulminates, azides, diazodinitrophenol, etc., admixed with the types of organic nitrates, specified in my invention, will also produce usable primary detonator compositions, but I wish to specify particularly that it is necessary to avoid appreciable amounts of these super-sensitive explosives, in order to be within the scope of my invention.

This specification is most important in that one of the main objects of my inventionis to provide and use primary detonator compositions, which are relatively safe, and safer than any that include appreciable amounts of these supersensitive types of explosives. Outside this particular class of substances, there is almost no limit to the number of substances, traces or minor proportions of which may be used either to advantage or without disadvantage, in conjunction with the two particular types of explosive substances named, viz. (1) solid nitric esters of polyhydric alcohols of the general formula CnHn+2(OH)n and (2) other solid explosive substances (less sensitive than those of group (1) and therefore less sensitive than mercury fulmihate and lead azide.

It shall still further be distinctly understood that I may employ various types of confining shells and/or capsules in the application of my invention and I may employ any suitable, electrical or other means for initiating or igniting my novel type of primary detonator compositions.

I also contemplate the use of these new and improved primary detonator compositions either as entire charges in simple detonators or associated with one or more base charges of one or more suitable explosive substances in compound detonators.

Having described my invention, what I claim 1s 1. In a detonator, a primary detonator composition consisting of a concurrently precipitated mixture of a solid nitration product of a polyhydric alcohol of the general formula CnHn+1 OH n and an additional solid explosive material that is less sensitive than mercury fulminate and lead azide.

2. In a detonator, a primary detonator composition free of all explosives as sensitive to friction and impact as mercury fulminate, lead azide and the like and including a solid nitration product of a polyhydric alcohol of the general formula CnHn+2(OH)n that has been concurrently precipitated from solution with another ingredient thereof.

3. In a detonator, a primary detonator composition consisting of a mixture of a concurrently precipitated mixture of nitromannite, and an additional solid explosive ingredient that is less sensitive to friction and impact than mercury fulminate and lead azide, and a stabilizing agent.

4. In a detonator, a primary detonator composition consisting of a mixture of concurrently precipitated mixture of nitrodulcite, and an additional solid explosive ingredient that is less sensitive to friction and impact than mercury fulminate and lead azide, and a stabilizing agent.

5. In a detonator, a primary detonator composition consisting of a mixture of concurrently precipitated mixture of nitromannite and nitrodulcite, an additional solid explosive ingredient that is less sensitive to friction and impact than mercury fulminate and lead azide, and a stabilizing agent.

6. A compound detonator including a secondary or base charge, and a primary explosive charge consisting of a mixture of a solid nitration produuct of a polyhydric alcohol of the general formula CnHn+2(OH2)n and an additional solid explosive substance that isless sensitive to friction and impact than mercury fulminate and lead azide, precipitated together from solution.

7. A detonator including, in combination, a primary detonator charge consisting of a concurrently precipitated mixture of a solid nitration product of a polyhydric alcohol of the general formula CnHn+2(0H)n and an additional solid explosive substance that is less sensitive than mercury fulminate, a perforated inner capsule placed over the said primary charge, and

a heat producing element for the effective initiation of the said primary charge.

8. A primary detonator composition for detonators comprising a mixture of a concurrently precipitated mixture of nitromannite and nitrolactose, and a stabilizing agent.

9. A primary detonator composition for detonators comprising a stabilized, concurrently precipitated mixture of about of each of nitromannite and nitrolactose,

10. A primary detonator composition for detonators consisting of a concurrently precipitated mixture of about 50%, 35% and 15% of nitromannite, nitrolactose and tetryl, respectively, by

weight. v r

11. A primary detonator composition for detonators comprising a concurrently precipitated mixture of a solid nitration product of a polyhydric alcohol of the general formula CnHn+2(oH)n and a solid disaccharide nitric ester.

12. In a detonator, a primary detonator composition comprising a concurrently precipitated mixture of a predominance of one or more solid nitric esters of the general formula CnHn+2(NO3) n, and one or more solid disaccharide nitric esters.

13. In a detonator, a primary detonator composition comprising a concurrently precipitated mixture of a solid nitration product of the general formula CnHn+2 NO3) n and a-minor to equal proportion of a solid disaccharide nitric ester.

14. In a primary detonator composition as in claim 13, wherein the concurrently precipitated mixture consists of nitromannite and a minor to equal proportion of nitrolactose.

15. In a detonator, a primary detonator composition consisting of a concurrently precipitated mixture of a solid nitration product of the general formula CnHn+z(NO3) n, and minor proportions of a solid disaccharide nitric ester anda solid, explosive nitro-body that is less sensitive to friction and impact than mercury fulminate and lead azide.

Patent No.- 1,928,206.

16. In a compound detonator, a primary detonator composition free of all explosives as sensitive to friction and impact as mercury fulminate and lead azide and including a mixture of a solid nitration product of polyhydric alcohol of the general formula CnHn+2(OH)n and at least one other solid explosive ingredient not of the formula named that is less sensitive to friction and impact than mercury fulminate and lead azide.

17. In a compound detonator, a primary detonator composition consisting of a mixture of a solid nitration product of polyhydric alcohol of the general formula CnHn+2(OH)n and at least one other solid explosive ingredient not of the formula named that is less sensitive to friction and impact than mercury fulminate and lead azide.

18. In a detonator, a primary detonator composition free of all explosives as sensitive to friction and impact as mercury fulminate, lead azide and the like, and including a solid nitration product of a polyhydric alcohol of the general formula CnHn+2 OH) n admixed with at least one solid substance of the group consisting of nitrolactose, tetryl, nitrostarch, nitrogalactose, nitromaltose, nitroarabinose and nitrocellulose.

19. A detonator comprising a primary detonator composition free of all explosives as sensitive to friction and impact as mercury fulminate and lead azide and including a mixture of a solid nitration product of polyhydric alcohol of the general formula CnHn+2(OH)n and at least one other solid explosive ingredient not of the formula named that is less sensitive to friction and impact than mercury fulminate and lead azide; and a flash composition in the form of a fuse head positioned to deliver a hot semi-explosive burst of flame upon said primary detonator composition.

SYLVESTER B. LARGE.

September 26, 1933.

SYLVESTER B. LARGE It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows; Page attthe formula and insert instead 0nHn+2(OH)n;

3, line'104, claim 1, strike and line 139, claim 6, strike but the formula and insert instead CnHn+2(OH)n; and that the said Letters Patent I should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and [SEAL] sealed this 30th day of June, A. D. 1936.

HENRY VAN ARSDALE,

Acting Commissioner of Patents.

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