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United States Patent Office Patented Dec 3,419,443 United States Patent Office Patented Dec. 31, 1968 2 3,419,443 metallic fuel constituent such as aluminum particles, such HYDRAZINE CONTAINING EXPLOSVE as disclosed in Hradel U.S. Patent No. 3,124,495. In COMPOSTIONS these compositions the liquid ammonia or like solvent Michel E. Maes, Bellevue, Wash., assignor to Explosives for the ammonium nitrate is present in a proportion of Corporation of America, Issaquah, Wash., a corpora 5 from about 2% to about 35% by weight, as compared tion of Washington with the ammonium nitrate present in the proportion of No Drawing. Filed Apr. 17, 1967, Ser. No. 631,123 about 10% to about 83% by weight, and the metal con 31 Claims. (Cl 149-1) stituent present in the amount from about 15% to about 60% by weight. In the Hradel explosive composition, as 10. will be observed, the principal fuel constituent is the par ABSTRACT OF THE DISCLOSURE ticulated metal ingredient, and the particle size of the Explosive compositions characterized by a nominally metal in the Hradel composition is stated to be essen liquid condition and a very high detonation velocity, and tially greater than 20 U.S. standard seive, in order that with low freezing point, low viscosity and low impact the composition be satisfactorily insensitive from the point sensitivity characteristics, said explosive composition 5 of view of avoidance of premature detonation during comprising as essential ingredients an at least principally handling. In addition to the sensitivity problem when hydrazinium oxidizer salt (e.g., hydrazinium nitrate and using a metallic particle fuel in conjunction with a nitrate mixtures thereof with hydrazinium perchlorate), hydra or like oxidizer constituent, it is a well known disadvan zine, and ammonia, and comprising as optional additives tage of explosives incorporating metallic fuel particles various compatible desensitizers, gelling agents, wetting 20 that such create substantial smoke upon detonation, and agents, self-sterilizing components, freezing point depres are difficult to maintain uniformly dispersed in a liquid sants, low gas producing substituents, and waterproofing system, particularly if of a sufficient particle size to have agents. Also presented are modes of preparation of the a reasonably tolerable insensitivity to impact detonation. compositions, involving either premix of the ingredients, Also the substantial presence of metal particles constitutes or mixing thereof in place at the situs of use. Relative a sacrifice in detonation velocity and brisance. Further, proportions by weight of the essential ingredients are as with regard to the Hradel explosive system, which is basically an ammonium nitrate solution in conjunction follows: NHNO, from about 40% to about 92%; with contained metal particles, and while Hradel presents N2H5CIO, from 0% to about 40%; NH4, from about a general statement as to the hydrazine-containing solvent 6% to about 15%; and NH, from about 2% to about 30 for the ammonium nitrate being either liquid ammonia, 15%. Optionally, minor proportions of the nitrate and water, ammonium hydroxide, or hydrazine (with all ex perchlorate salts can be metallic salts. amples presented involving ammonia as the solvent), Hradel makes no distinction with regard to various sol BACKGROUND OF THE INVENTION vents, nor any comprehension of any particularly ad 35 vantageous physical properties or detonation character Field of the invention istics of particular combinations of ammonia and hydra The invention pertains to low impact sensitivity, high zine with a nitrate and in the absence of metallic particles, detonation velocity explosive compositions containing such as characterizes the present invention. hydrazine in admixture with a hydrazinium salt, together SUMMARY OF THE INVENTION with a controlled amount of ammonia, the latter func 40 tioning primarily as a modifying agent with regard to the In general, explosive compositions according to the physical properties of the composition, namely the den present invention at least principally comprise a prefer sity, viscosity, and freezing point thereof. ably substantially stoichiometric combination of a hydra zinium salt as the oxidizer reactant, coupled with hydra Description of the prior art 45 zine which functions as an exothermically decomposable constitutents, yielding decomposition products which in Explosive and propellant compositions are generally turn coact as reducer reactants and undergo explosive de known which involve mixtures of hydrazine and hydrazin compositions with the oxidizer reactant upon detonation ium nitrate, also known as hydrazine nitrate or hydra of the composition, such oxidizer-reducer system further zine mononitrate, such as disclosed in Audrieth et al. U.S. 50 including a controlled amount of ammonia functioning Patent No. 2,943,927, wherein the hydrazine-hydrazinium prior to detonation as a modifying agent with regard to nitrate system is noted as having a characteristically low the physical properties of the composition, to reduce the freezing point and having utility for use as a fuel in con viscosity thereof, and to reduce the freezing point of junction with conventional oxidizers such as hydrogen the composition. In the absence of the ammonia, the peroxide, fuming nitric acid or liquid oxygen, the hydra 55 hydrazine-hydrazinium salt system in approximately stoi zine-hydrazinium nitrate in this instance including at least chiometric proportions has an impractically high freezing about 18% hydrazine by weight, and optimally about point and a solid form at normal temperatures of use. On 50% or more by weight of hydrazine, to provide a freez the other hand, if the proportion of ammonia present in ing point for the fuel of some -50° C. In the Audrieth the system is excessive, significant reductions in detona et al. fuel, and as above noted, the proportionation of 60 tion velocity and explosion energy result. the hydrazine-hydrazinium nitrate mix is determined In explosive compositions of the present invention, the solely by consideration of freezing point depression, and oxidizer reactant comprises either hydrazinium nitrate, not by any consideration of stoichiometric balance or or mixtures of hydrazinium nitrate with hydrazinium maximal efficiency as an explosive composition, at least perchlorate, with a cationic metal radical substituted for in part for the reasons that the fuel contemplated by 65 a minor portion of the hydrazinium radical in some in Audrieth et al. is intended for use as a fuel constituent stances. For simplicity, much of the following discussion with an external oxidizer, and because the exothermic re of the invention simply refers to the oxidizer reactant as action is one of combustion, rather than explosive detona an "oxidizer salt' or "hydrazinium salt.” However, in tion. more particular terms, it will be understood that the Also known are prior explosive compositions involving 70 oxidizer constituent contemplated by the present inven ammonium nitrate, together with a hydrogen-containing tion is selected from the group consisting of nitrate solvent therefor, such as liquid ammonia, and with a salt(s) and mixtures thereof with a minor amount of per 3,419,443 3 4. chlorate salt(s) (where the perchlorate anionic radical is point variations occurring principally as a function of desired to increase sensitivity). Further it will be under ammonia content, as illustrated in Table II: stood that such oxidizer constituent is a nitrate or nitrate/ TABLE II perchlorate salt wherein the cationic radical is either Formulation Percent Deton Freezing Viscosity hydrazinium or is a mixture of hydrazinium radical with example NH3 by Density Veloc point (F.) (cps.) a minor amount of a metal radical (where the metal Salt weight (crystal) is desired to reduce foaming during composition prepara 2 1.42 8,600 58 22 5 1.39 8,500 38 20 tion). Suitable substituent metallic salt(s) are charac 9 1.35 8,300 i5 6 teristically nonreactive when stored in admixture with 14 1.31 8, 100 -8 2 hydrazine and can be sodium nitrate, sodium perchlorate, potassium nitrate, potassium perchlorate, calcium nitrate, Viscosity also varies a function of ammonia content in calcium perchlorate, aluminum nitrate, and/or aluminum these compositions, and is typically 8 centipoises or higher, perchlorate, for example. depending on the type of viscosity modifying agent added, In general, it has been determined that considerable as discussed in more detail below. Density of the explo variation in proportions of the hydrazinium salt/hydra sive compositions is also a function of ammonia content, zine/ammonia explosive system of the present inven as also shown in Table II above. tion can be utilized, consistent with the obtainment of The explosive characteristics of the compositions are various advantageous physical properties of the explo a function of compositional makeup. In general, detona sive prior to detonation. Characteristic advantageous tion velocity is in the range of 8,000 to 8,600 meters per physical properties are; availability in liquid form, low 20 second. Detonation velocity is characteristically a func freezing point, low viscosity, low impact sensitivity, and tion of density and the variation in detonation velocity good field mixability. Characteristic advantageous detona with ammonia content are also shown in Table II above. tion characteristics are; very high detonation velocities, Detonation temperature of the explosives of the inven low detonation temperatures, detonation by conven tion is characteristically
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