Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
  • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
  • C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B25/00—Compositions containing a nitrated organic compound
  • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine

Definitions

• the explosive composition' can further comprise optional physical property modifying additives, such as desensitizing agents, thickening'and gelling agents, freezing point depressants, and waterproofing agents; Also presented are methods of preparation of the compositions, including the preparation of pre-mixed non-explosive components, a first such component being hydrazine or like liquid containing a nonexplosive amount of the oxidizer salt(s), and a second such component being essentially the additional oxidizer salt(s).
• optional physical property modifying additives such as desensitizing agents, thickening'and gelling agents, freezing point depressants, and waterproofing agents
• Relative percentages by weight of the significant ingredients are as follows: Aluminum particles, from about 2% to about 45%; NH -and'-NH from 0% to about 18%; N H 'and N H +,-from about 6% to about 75%; NO;, or equivalent anion, from about 14% to about'70%.
• minor proportions of the nitrate or equivalent anion can be present in the form of certain CROSS REFERENCES TO RELATED APPLICATIONS
• This application is a continuation-impart of Bridgforth and Sutherland US. application Ser. No. 340,127, entitled Stable, High Energy Compositions, and filed Jan. 27,
• the invention pertains to explosive compositions and methods, characterized by a hydrazinium nitrate/hydrazine/aluminum explosive system, together with labile equilibrium amounts of ammonium nitrate and ammonia in some instances, and together with various physi-.
• cal property modifiers-to provide appropriate stability, density, viscosity, and freezing point characteristics in the composition.
• Explosive and propellant compositions are generally known which involve mixtures of hydrazine and hydrazinium nitrate (also known as hydrazine nitrate or hydrazine mononitrate) such as are disclosed in Audrieth US. Pat.
• a hydrazine-hydrazinium nitrate system is noted as having a characteristically low freezing point and having utility for use as a fuel in conjunction with conventional oxidizers such as hydrogen peroxide, fuming nitric acid and liquid oxygen, the hydrazine-hydrazinium nitrate in this instance including at least about 18% hydrazine by weight, and optimally about 50% or more by 'weight of hydrazine, to provide a freezing point for the fuel of some 50 C.
• conventional oxidizers such as hydrogen peroxide, fuming nitric acid and liquid oxygen
• the proportionation of the hydrazinehydrazinium nitrate mix is determined solely by consideration of freezing point depression, andnot by any consideration of stoichiometrie balance or maximal efiiciency as an explosive composition, and more particularly does not involve any consideration of stoichiometric balance or maximal efficiency in the situation where the hydrazinehydrazinium nitrate mix is employed in conjunction with an uncombined metal reducer constituent such as aluminum, as in the case of the present invention.
• ammonium nitrate containing ammonium nitrate, together with a hydrogen-containing solvent therefor, such as liquid ammonia or ammoniacal ammonium nitrate solutions, and with a metallic fuel constituent such as aluminum or magnesium particles
• a hydrogen-containing solvent therefor such as liquid ammonia or ammoniacal ammonium nitrate solutions
• metallic fuel constituent such as aluminum or magnesium particles
• the ammonia or like solvent for the ammonium nitrate is present in a proportion of from about 2% to about 35% by Weight, as compared with the ammonium nitrate present in the proportion of about 10% to about 83% by weight, and the metal constituent is present in the amount of from about 15% to about 60% by Weight.
• the particle size of the metal constituent is stated to be essentially greater than 20 US. standard sieve, in order that the composition be satisfactorily insensitive from the point of view of avoidance of premature detonation during handling.
• Hradel presents a general statement as to the hydrogen-containing solvent for the ammonium nitrate being either liquid ammonia, water, ammonium hydroxide, or hydrazine (with all examples presented involving ammonia in aqueous solution as the solvent)
• Hradel makes no distinction with regard to various solvents, nor any comprehension as to any particularly advantageous physical properties or detonation characteristics of particular combinations of hydrazine or hydrazine containing solvent with a nitrate or the like oxidizer dissolved therein and in the presence of aluminum particles, such as characterizes the present invention.
• the hydrazinium nitrate/hydrazine/aluminum explosive system of the invention has free hydrazine present which, even if present in excess, is peculiarly non-deleterious to the explosive reaction, since it of itself decomposes to gaseous products with energy release, whereas the ammonia or ammonia and water liquid constituent of Hradel requires energy for decomposition and thus detracts from the explosive energy release.
• hydrazine is much more than a simple solvent in the explosive system of the present invention, since it also forms unique intermediate reaction products (theorized to include AlN, for example) which result in a higher and more rapid energy release.
• Hydrazine also serves as a uniquely effective working fluid in the present explosive system, resulting in more energy contribution to the mixture as it reacts to gaseous end products, adding substantially more gas per initial unit weight of the composition.
• the ammonia/ammonium nitrate/aluminum or magnesium explosive system of Hradel with the hydrazine/hydrazinium nitrate/aluminum explosive system of the present invention is the consideration that the Hradel liquor (the normally liquid portion of the composition, i.e. ammonium nitrate dissolved in ammoniacal aqueous solution) is not detonable in the absence of the metal constituent, whereas the liquor of the present invention (e.g.
• ammonium nitrate dissolved in hydrazine to form an ionic equilibrium of hydrazinium and ammonium cations and nitrate anions along with substantial amounts of free hydrazine and also free ammonia being present) is of itself explosive without the metal (aluminum) constituent.
• the explosive system of the present invention is consequently theorized to provide what may be termed a two-stage explosive system, with the initial explosive shock wave being caused primarily by the reaction of the oxidizer and the hydrazine, with the reaction of the metal constituent apparently occurring in two stages to provide an after shock.
• optimized formulations characteristic of the present invention demonstrably provide about twice the air shock of TNT, whereas the air shock performance of the Hradel explosive system is about the same as that of TNT.
• ammonium nitrate/aluminum/water explosive system is theorized as reacting as follows:
• the nitrate ion or equivalent can be present in one or more compounds selected from the group consisting of nitrate(s) and mixtures thereof with minor amounts of perchlorate(s).
• the oxidizer salt can also include minor amounts of one or more oxidizer salts having certain metallic cations in lieu of a stable hydronitrogen type caton, i.e.
• the oxidizer salt(s) can include a minor proportion of an oxidizer salt selected from the group consisting of alkali metal nitrates, calcium nitrate, aluminum nitrate, hydrazinium perchlorate, alkali metal perchlorates, calcium perchlorate, and mixtures thereof.
• an oxidizer salt selected from the group consisting of alkali metal nitrates, calcium nitrate, aluminum nitrate, hydrazinium perchlorate, alkali metal perchlorates, calcium perchlorate, and mixtures thereof.
• an oxidizer salt selected from the group consisting of alkali metal nitrates, calcium nitrate, aluminum nitrate, hydrazinium perchlorate, alkali metal perchlorates, calcium perchlorate, and mixtures thereof.
• the presence of a minor amount of metallic cation offers no advantage and to an extent detracts from the explosive efficiency of the composition in that the metallic cation forms a solid
• the explosive compositions of the present invention in general can be formulated either by mixing ammonium nitrate and hydrazine with subsequent aluminum particle addition, or by mixing hydrazinium nitrate with hydrazine with subsequent aluminum particle addition.
• the nitrate is present in the final mix in the form of hydrazinium nitrate and ammonium nitrate in labile equilibrium with hydrazine and ammonia.
• the nitrate ion is present essentially in the form of hydrazinium nitrate without substantial ammonium nitrate being present.
• the mixing of ammonium nitrate and hydrazine can proceed at elevated temperature and/ or under vacuum to remove evolved gaseous ammonia.
• type of explosive composition resulting from the first above-discussed mode of preparation i.e.
• the explosive compositions according to the invention include the following constituents in the following approximate percentages:
• Thickening and/ or gelling agents are usually added to the explosive compositions of the invention to maintain the finely divided aluminum in substantially uniform distribution in the explosive mix, which is otherwise in many instances a liquid slurry by reason of the hydrazine containing solvent and dissolved oxidizer constituents being in liquid or liquid slurry form.
• Thickening or gelling of the composition can be accomplished by a variety of additional agents, generally known per se for the purpose, added in desired amounts up to about 20% by weight.
• Typical thickening and gelling agents are Cab-O-Sil (a finely divided SiO- thickening agent, suitably usable in proportions up to about 10% by weight) and Guartec 503 (a cross linking gelling agent, suitably used in proportions up to about by weight).
• Gelling agents are commonly furnished in the form of a powder, and such hydrazine at room temperature. When this solution had normalized, the remainder of the ammonium nitrate and the thickening agent .'were added with stirring to cause substantially complete dissolution of the nitrate in the hydrazine.
• the aluminum powder (Reynolds atomized powder can be added to the liquid mix or a liquid con- 5 aluminum A 15ll, vvith particle sizes predominantly in stituent prior to addition of one or more of the other the range of 3 040 microns) was then progressively explosive constituents.
• the gelling agent added while the mixture was stirred with a Lightening suitably can be added to the hydrazine along With and mixer (1750 r.p.m.) and agitation was continued until as a pre-mixed addition to the solid ammonium nitrate. 10 the viscosity of the mixture was sufficient to prevent the The addition of Guartec 503 to the explosive is also adaluminum particles from settling out.
• Carbon black i 15 were boosted with 50 gram tetryl pellets and initiated with also efiective thickening agent, and typifies agents of this D t SSS seismograph blasting caps EB, with the type which functi n
• ut 21150 being a g g g detonator-booster assemblies packaged in a polyethylene
• the crater depth in inches to solid ground at the center of the Proportion of desensitize! can be P to about 20% of crater, and in terms of average diameter of the crater, the t tal eXP103iVe y Weight-I11 the case of a Solid the average diameter being determined by the average of but liquidifiable desensitize! Such as Wax, the desensitizer four diameters across the crater.
• Cratering performance of is suitably heated and mixed in the composition at elevated the various Examples 1 5 and h comparison Example X temperature, resolidifyihg and contributing to the thicken were as shown in the above tabulation.
• the improvement i g of the Composition 1113011 Cooling thereof- In general in cratering performance of all of the examples, in comany non-volatile material which exhibits storage stability parison with the cast TNT charge (Example X) is in adm With the hydrazine/hydrazine Salt Compof parent.
• the propor- DeHtS Ofthe explosive can act as a desensitizertion of aluminum is not particularly critical (comparing some explosive compositions centemplated by the P about 20% aluminum in Example 3 with about 32.7% ent invention have a freezing point near normal tempera: l i in Example 1), and that presence of a b ture and thus make it desirable to have included therein a ma amount f Water (about 5% in Example 5 does not freezing Point depressing agent Ahvexample of a compatl' 40 materially change the cratering performance (comparing ble freezing point depressant for the purpose is hy- Examples 1 and 5) drazinium thiocyanate' (N H S CN).
• E l 6 The abpve and .other physlcal Property .modlfiers are To further characterize the properties of typical exi dlscilssed r.el.atlon to ydrazlmuln. hyplosive compositions, the explosive of Example 1, prepared drazlmllm filtrate cqntafmng exploslve composltlons m the 40 as above indicated, was determined to have a density of aforesald apphcatlon 1.61 at 69 F. and a sensitivity of 70 kg./cm.
• Example 6 For com- T the i here Pertinent dlsclqsurqs 9 Sald apparison purposes, an Example 6 composition was formuphcatlon and Sa1q?atent.havmg to 1th snmlzir hydralated, involving the same ingredient proportions as in u hydrazm.lum y m t exploslv? Example 1 (except for 3 parts Cab-O-Sil), the hydrazine posmons havmg to do W1 th Vanous properiles and in this instance being preheated to 150 F.
• a first nonexplosive liquid component was first prepared by dissolving about 5 parts of the ammonium nitrate in the 75 ample 1 plus 21% glycerin by weight. Performance tests 3 parts Cab-O-Sil) was compared with an Example 7 explosive composition containing the ingredients of Exshowed this mixture was markedly desensitized but still detonatable. Specifically, the Example 1 composition yielded cratering 36 inches deep and 115 inches in diameter, while the desensitized composition yielded craten'ng 26 inches deep and 68 inches in diameter. Related tests involving variation of glycerin proportion from 16% to 22% indicated none of the compositions were cap sensitive but Were rifle impact sensitive in rubber lined cast iron pipe, with lO'W order detonations at 20% glycerin and below.
• Example 8 To further examine cratering performance of a desensitized explosive composition, an Example 8 composition was prepared incorporating with the formulation of Example 1 5% by Weight of stove oil and an Example 9 composition was also prepared which included stove oil with the formulation of Example 1.
• Example 8 proved to be both rifie bullet (.30-06) impact sensitive and cap sensitive, whereas Example 9 proved both rifle impact insensitive and cap insensitive.
• Boosted with 50 grams tetryl both Examples 8 and 9 proved detonable, and Example 9 produced a crater 42 /2 inches deep and 94 inches in diameter, as compared with an Example 1 formulation crater 43 /2 inches depth and 114 inches diameter.
• Example 10 The formulation of Example 1 compounded with 0.1% by weight Guartec 503 and 4 parts Cab-O-Sil gave a composition with a creamy consistency low enough in viscosity to pour like a thick syrup and high enough to prevent the aluminum settling out.
• Examples 11 and 12 To further investigate cratering performance of explosives characteristic of the present invention as comparted with known aluminum containing explosives, a series of test shots was conducted involving like amounts of the explosives of Example 1 (with 5 parts Cab-O-Sil) and Example 2, tested in like ground along with like amounts of Navy 'I-I6 explosive and tritonal explosive.
• H-6 as known, is a 60/40 mixture of RDX and TNT, formulated with 5% Wax and aluminum particles, by weight.
• tritonal is an 80/20 mixture of TNT and aluminum particles. All shots were housed in steel jugs, and the charge in each instance weighed 1 pound and was buried a depth of 20 inches. Cratering performance for these shots was as follows:
• An explosive composition comprising:
• said oxidizer and said hydrazine containing liquid being present in detonatable proportions.
• An explosive composition comprising the following constituents, present in the following relative percentages by Weight:
• Aluminum particles From about 2% to about 45%.
• N H and N H From about 6% to about 75%.
• nitrate anion or equivalent is present in one or more compounds selected from the group consisting of nitrate(s) and mixtures thereof with minor amounts of perchlorate (s 3.
• the explosive composition of claim 2 at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium.
• the explosive composition of claim 2 further comprising a thickening and/or gelling agent present in an amount sufficient to provide the composition with the rheological properties of a solid and insufficient to render a composition nondetonatable.
• An explosive composition according to claim 2 further comprising a desensitizing agent, present in an amount insuflicient to render the composition nondetonatable.
• said desensitizing agent is present in an amount less than about 20% by weight and is selected from the group consisting of water, glycerin, glycol, hydrocarbon oil, wax and mixtures thereof.
• the explosive composition of claim 5 at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium, with the aluminum particles being present in substantially stoichiometric proportion with respect to the oxidizer.
• Aluminum particles From about 20% to about 35%. NH and NH,+ to about N H and N H From about to about 30%. NO or equivalent From about 25% to about 55%.
• nitrate anion'or equivalent is present in one or more compounds selected from the group consisting of nitrate(s) and mixtures thereof with minor amounts of perchlorate(s).
• the explosive composition of claim 16 at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium.
• the explosive composition of claim 16 further comprising a thickening and/or gelling agent present in an amount sufiici ent to provide the composition with the rheological properties of a solid and insufficient to render a composition nondetonatable.
• An explosive composition according to claim 16 further comprising adesensitizi'ng' agent, present in an amount insufficient to render thecomposition nondetonatable.
• An explosive composition according to claim 16 wherein the nitrate or equivalent ion is present essentially in the form of hydraziniumnitrate- 24.
• the explosive composition of claim 19, at least principally comprisingaluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium, with the aluminum particles. being present in substantially stoichiometric proportion with respect to the oxidizer.
• composition nondetonatable.
• a desensitizing agent present in an amount insufiicient to render the composition nondetonatable.
• An explosive composition comprising the following constituents, present in approximately the following relative percentages by Weight:
• the explosive composition of claim 30, at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium.
• the explosive composition of claim 32 *at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonium with the hydrazinium and ammonium ions in labile equilibnum.
• An explosive composition according to claim 36 further comprising a hydrocarbon oil desensitizing agent, present in an amount insuflicient to render the composition nondetonatable.
• the method of claim 38 comprising mixing of the hydrazine, oxidizer salt(s) and aluminum particles under elevated temperature and/or vacuum conditions for a sufiicient time to remove at least most of the free ammonia therefrom.
• the method of claim 46 comprising mixing of the hydrazine, oxidizer salt( s) and aluminum particles under elevated temperature and/or vacuum conditions for a sufficient time to remove at least most of the free ammonia therefrom.
• the first nonexplosive liquid component comprises hydrazine having dissolved therein less than about 20% ammonium nitrate by weight, and wherein said second component consists essentially of ammonium nitrate.
• the method of claim 54 comprising mixing of the hydrazine, ammonium nitrate and aluminum particles under elevated temperature and/or vacuum conditions for a sufficient time to remove at least most of the free ammonia therefrom.
• Aluminum particles 2-45 60 The method of claim 58, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:
• the method of claim 58, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

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Citations (4)

• 1968
  • 1968-12-30 US US787997A patent/US3523047A/en not_active Expired - Lifetime
• 1969
  • 1969-12-23 IL IL33590A patent/IL33590A/en unknown
  • 1969-12-29 NO NO5138/69A patent/NO122692B/no unknown
  • 1969-12-29 JP JP44105310A patent/JPS491521B1/ja active Pending
  • 1969-12-29 NL NL6919507A patent/NL6919507A/xx not_active Application Discontinuation
  • 1969-12-29 BE BE743795D patent/BE743795A/xx unknown
  • 1969-12-29 CH CH1932069A patent/CH555306A/xx not_active IP Right Cessation
  • 1969-12-30 FR FR6945423A patent/FR2027374A1/fr not_active Withdrawn

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