Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00

Definitions

• This invention relates to safe-handling explosive mixtures. More particularly, this invention is directed to means for rendering perchloric acid containing explosive compositions less sensitive to friction and shock so that they can be used without danger. This invention is further directed to compositions containing perchlorate explosives in a mixture of solvents therefor.
• the present invention relates to safehandling explosive mixtures containing salts of perchloric acid which are explosive and sensitive to impact and shock.
• the explosive, impact-and shocksensitive salts of perchloric acid such as hydrazine perchlorate, methyl and dimethyl hydrazine perchlorate, mono-, diand trimethylamine perchlorate, ethanolamine perchlorate, ethylene diamine diperchlorate, onitroaniline perchlorate and pyridine perchlorate, for example, are high-energy explosives usually having an excellent detonatability. In practice, however, they are not used, on account of their great sensitivity to friction and shock. Even in explosives containing water, such as slurry explosives, they cannot be used without danger, although in this case they may be present in the dissolved state and hence in phlegmatized form. During storage, however, a portion of the water may evaporate from these explosives and the above-mentioned salts or perchloric acid might crystallize, resulting in an undersirable loss of safety against impact and shock.
• perchloric acid such as hydrazine perchlorate
• the hazardous salts of perchloric acid are in high concentration in the aqueous solution of the explosive, they might even crystallize upon the lowering of the temperature of the explosive.
• this invention contemplates an explosive composition containing a perchlorate explosive and a solvent therefor.
• this invention contemplates an explosive composition containing a salt of perchloric acid and a high-boiling solvent therefor.
• salts of perchloric acid useful as explosives can be rendered safe and useful as explosives by dissolving the perchlorate containing explosive compositions in a solvent therefor, preferably a high-boiling solvent for the explosive composition.
• the solvent is one in which the perchlorate explosive is highly soluble.
• the solvent is a high boiling point boiling at a temperature of at least I50C, preferably 190C determined at 1 atmospheric. It is desirable that the solvent have a high boiling point to maintain the solubility product constant, a measure of the solubility of the explosive composition in the solvent, at desirable levels.
• the perchlorate explosive composition will crystallize out.
• the solvent is desirably a high boiling or non-volatile solvent, the danger of the evaporation of the solvent is diminished.
• crystallization of the salt of perchloric acid does not occur even after the explosive composition in the solvent is stored for extensive periods oftime at elevated temperatures, for example, 20 50C.
• the concentration of the salts of perchloric acid in the high boiling or non-volatile solvent is preferably selected in such a manner that no crystallization can occur in the climatic zone in which the explosive is to be used,.even at the lowest temperature which occurs in that zone. If other soluble salts, such as ammonium nitrate, are present in the explosive mixture, it is advantageous to determine whether the increase of the salt concentration in the solvent will result in the crystallization of the hazardous salts of perchloric acid or in the crystallization of salts of perchloric acid which are insensitive to impact and shock. such as ammonium perchlorate.
• a test for this can be performed by determining the impact sensitivity after subjecting the explosive mixture to varying temperatures.
• the concentration of the perchloric acid salts in the high boiling or non-volatile solvent is chosen such that no crystallization is obtained at the lowest temperature.
• the salt of perchloric acid is dissolved in the solvent in an amount between 1 and 50wt. percent, based on the weight of the solvent but preferably between 10 and 20 percent of the solubility product constant for the solute in the solvent under the applicable conditions of temperature and pressure.
• High boiling solvents which can dissolve the explosive perchlorates and which can be used in accordance with the invention are polyvalent alcohols, amines and amides whose boiling point is above 150C. but preferably about lC, and which are able to dissolve the perchlorates, examples being l,2-ethanediol, 1,2- propanedrol, 1,2,3-propanetriol, the butanediols, or liquid aliphatically derived glycols of molecular weight between 76 and 2000.
• An example of a polyvalent ,amine is pentamethylenediamine.
• Formamide can also be used as a solvent according to the invention.
• ammonium nitrate is preferably used as the inorganic, orygen-yielding salt, and it can be replaced partially or even entirely by other alkali or alkaline earth nitrates or perchlorates.
• Additional inorganic, oxygen-yielding salts can be used in the non-volatile solvents employed pursuant to the invention.
• the combustible compounds which lower the solidification point of these salts include the nitrates and perchlorates of amines and derivatives of ammonia.
• Primary, secondary and tertiary alkyl especially C,C alkyl groups and aryl amines e.g., single nucleus aryl amines, fused ring aryl amines and aryl amines containing two aryl groups joined at single carbon atoms e.g., a biphenyl amine.
• Examples of such amines include in particular ethylamine, aniline, phenylenediamine.
• cyclic amines e.g., hexamethylenetetramine, alkanolamines especially C -C alcohol amines or polyvalent amines e.g., ethylenediamine, hexamethylenediamine or tetraethylenepentamine, can be used as amines.
• the derivatives of ammonia include hydrazine, urea and its substitution products, urethanes, guanidines, and quaternary ammonium compounds, such as tetramethylammonium chloride,
• ammonium salts of aliphatic carboxylic and sulfonic acids especially those of aliphatic acids having between I and 8 carbon atoms, such as ammonium formate, ammonium acetate, ammonium sulfamate and the amides of these acids, such as formamide, and acetamide, urea and its derivatives such as urethanes and ureides, and carbamic acid.
• Ammonium thiocyanate, ammonium hypophosphite, ammonium thiosulfate, anhydrous sodium acetate and monoand oligosaccharides are also suitable as combustible compounds which lower the freezing point.
• swelling agents in quantities of0.l to 10 wt. percent, preferably l to 5 wt. percent, can be added to the eutectic mixtures serving as solvents.
• the swelling agents protect the perchlorate explosives made therefrom both against separation and against the penetration of water.
• Oligo-or polysaccharides are examples of swelling agents. The following are named as examples: guar flour, carob bean flour, agaragar, starch, cellulose derivatives (e.g., cellulose esters, ethers and glycolates), albuminous substances and gelatins, gum arabic, tragacanth or gum and alginates.
• Thickening agents such as polyacrylamide, polyacrylic acids, polyvinyl alcohol and polyoxymethylene can also serve as swelling agents; inert, finely divided thickening agents can also be used, such as bentonitcs, silicic acid and silicates such crystalline aluminosilicates especially those having pores.
• the swelling agents may also be crosslinked.
• the swelling agents may be preserved by the addition of antibacterial agents, such as salicylic acid.
• perchlorate explosive compositions which can be used in accordance with this invention generally include all of the known perchloric acids or perchlorate containing explosive compositions. Generally these are salts of perchloric acid and include the following:
• EXAMPLE 2 An explosive composed of:
• guar flour 25.0% aluminum 44.9% ammonium nitrate in which the eutectic mixture consists of:
• the explosive mixtures were prepared in the followmg manner:
• the aqueous solution of ethanolamine and methylamine was neturalized with the corresponding amount of nitric acid and perchloric acid, respectively.
• the water was removed by distillation in vacuo.
• the guar flour was stirred into the liquid, eutectic mixture at 80C. After cooling, the gelatines were mixed in the usual manner with aluminum and ammonium nitrate.
• EXAMPLE 3 In this example it is shown how the detonatability of slurry-like, safe-handling explosives is improved by the addition of small amounts of the hazardous salts of perchloric acid. Table 2 gives the compositions and Trauzl lead block distensions for three explosive mixtures:
• An explosive composition containing an explosive salt of perchloric acid which is sensitive to impact and shock and a solvent therefor, which solvent has a boiling point above C, said explosive salt of perchloric acid being dissolved in said solvent, said composition being such that the ingredients are present in such amount so that the solvent at 20C contains said explosive salt in dissolved liquid form, said composition exploding when detonated.
• composition according to claim 1 wherein said solvent is an alcohol, an amine or an amide having a boiling point above 150C.
• composition according to claim 2 wherein said solvent has a boiling point above C.
• composition according to claim 3 wherein said solvent is selected from the group consisting of 1,2- ethanediol, 1,2,3-propanetriol, butanediols, polyglycols, pcntamethylenediamine, and formamide.
• An explosive composition according to claim 1 wherein said explosive salt of perchloric acid is selected from the group consisting of hydrazine perchlorate, methyl hydrazine perchlorate, dimethyl hydrazine perchlorate, monomethylamine perchlorate, dimethylamine perchlorate, trimethylamine perchlorate, ethanolamine perchlorate, ethylene diamine diperchlorate, onitroanaline perchlorate and pyridine perchlorate.
• An explosive composition consisting essentially of:
• liquid solvent consisting essentially of:
• an oxygen yielding salt selected from the group consisting of ammonium nitrate, alkali metal nitrates, and alkaline earth metal nitrates;
• composition being such that the ingredients are present in such amount so that the solvent at 20C contains said explosive salt in dissolved liquid form
• a composition according to claim 8 wherein said explosive salt of perchloric acid is selected from the group consisting of hydrazine perchlorate, methyl hydrazine perchlorate, dimethyl hydrazine perchlorate, monomethylamine perchlorate, dimethylamine perchlorate, trimethylamine perchlorate, ethanolamine perchlorate.
• said explosive salt of perchloric acid is selected from the group consisting of hydrazine perchlorate, methyl hydrazine perchlorate, dimethyl hydrazine perchlorate, monomethylamine perchlorate, dimethylamine perchlorate, trimethylamine perchlorate, ethanolamine perchlorate.
• ethylene diamine diperchlorate, onitroanaline perchlorate and pyridine perchlorate is selected from the group consisting of hydrazine perchlorate, methyl hydrazine perchlorate, dimethyl hydrazine perchlorate, monomethylamine perchlor
• composition according to claim 8 wherein the oxygen-yielding salt in said liquid solvent is present in the two component mixture in an amount between and 70 percent by weight.
• composition according to claim 8 wherein said combustible compounds are selected from the group consisting of nitrates of amines. perchlorates of amines and derivatives of ammonia.
• a composition according to claim 8, wherein said combustible compounds are selected from the group consisting of primary, secondary and tertiary alkyl and aryl amines, cyclic amines, alkanolamines and polyvalent amines and derivatives of ammonia.
• composition according to claim 8 wherein the combustible compounds are selected from the group consisting of primary, secondary and tertiary alkyl amines having from C -C carbon atoms in the alkyl group, aryl amines of a single nucleus, fused ring aryl groups and aryl groups wherein two aryl radicals are joined at single carbon atoms, urethanes, guanidines, quaternary ammonium compounds, alkanolamines having between 2 and 9 carbon atoms in the alkanolamine.
• the combustible compounds are selected from the group consisting of primary, secondary and tertiary alkyl amines having from C -C carbon atoms in the alkyl group, aryl amines of a single nucleus, fused ring aryl groups and aryl groups wherein two aryl radicals are joined at single carbon atoms, urethanes, guanidines, quaternary ammonium
• composition according to claim 8 wherein the combustible compound is selected from the group consisting of methylamine, ethylamine, analine, phenylenediamine, hexamethylenetetramine, ethylenediamine, hexamethylenediamine. tetraethylenepentamine, hydrazine, urea, tetramethylammonium chloride,
• tetramethylammonium sulfate tetramethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium sulfate, trimethylphenylammonium sulfate, trimethylphenylammonium chloride, tetrapropylammonium sulfate and diphenyldimethylammonium chloride.
• composition according to claim 8 wherein the combustible compound is selected from the group consisting of ammonium salts of aliphatic carboxylic acids and ammonium salts of sulfonic acids.
• ammonium salt ofthe aliphatic carboxylic acid is an ammonium salt of a carboxylic acid of an aliphatic group having between I and 8 carbon atoms.
• ammonium salt is selected from the group consisting of ammonium formate, ammonium acetate and ammonium sulfamate.
• composition according to claim 8 wherein the combustible compound is selected from the group consisting of amides of aliphatic carboxylic acids, urea, derivatives of urea and carbamic acid.
• composition according to claim 8 wherein the combustible compound is selected from the group consisting of urethanes and ureides.
• composition according to claim 8 wherein the combustible compound is selected from the group consisting of ammonium thiocyanate, ammonium hypophosphite, ammonium thiosulfate, anhydrous sodium acetate. monosaccharides and oligosaccharides.
• composition according to claim 8 wherein said composition contains a swelling agent present in amount between (H and 10 percent based on the weight of the liquid solvent.
• composition according to claim 8 wherein said composition contains a thickening agent.
• non-volatile solvents that can be used according to the invention are low-melting,. eutectic mixtures of oxygen-yielding, inorganic salts and combustible compounds, which lower the freezing point of these salts. Such eutectic mixtures have a solidification point which may be lower than -lOC; they are especially suitable as solvents which can be utilized in accordance with the invention. Generally theinorganic salt is present in such mixtures in an amount between 5 and 70% by wt. preferably between 10 and 307. by wt.
• non-volatile solvents that can be used according to the invention are low-melting, eutectic mixtures of oxygen-yielding, inorganic salts and combustible compounds which lower the freezing point of these salts 9
• Such eutectic mixtures have a solidification i t h' h p0 n w 1c may be lower than -l0C; they are especially suitable as solvents which can be utilized in accordance with the invention.
• theinorganic salt is present in such mixtures in an amount between 5 and 707. by wt. preferably between 10 and 30% by wt.

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Citations (7)

• 1971
  • 1971-05-29 DE DE2126920A patent/DE2126920C3/de not_active Expired
• 1972
  • 1972-05-26 AT AT458272A patent/AT317064B/de not_active IP Right Cessation
  • 1972-05-26 CA CA143,365A patent/CA978748A/en not_active Expired
  • 1972-05-26 US US258850A patent/US3864177A/en not_active Expired - Lifetime
  • 1972-05-26 FR FR7218957A patent/FR2139986B1/fr not_active Expired
  • 1972-05-27 IT IT50562/72A patent/IT958116B/it active
  • 1972-05-27 ES ES403264A patent/ES403264A1/es not_active Expired
  • 1972-05-29 BE BE784114A patent/BE784114A/xx not_active IP Right Cessation
  • 1972-05-30 GB GB2534172A patent/GB1364131A/en not_active Expired

Patent Citations (7)

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