JP3981356B2 - Solid pyrotechnic composition with low moisture uptake and method for producing the same - Google Patents
Solid pyrotechnic composition with low moisture uptake and method for producing the same Download PDFInfo
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- JP3981356B2 JP3981356B2 JP2003526862A JP2003526862A JP3981356B2 JP 3981356 B2 JP3981356 B2 JP 3981356B2 JP 2003526862 A JP2003526862 A JP 2003526862A JP 2003526862 A JP2003526862 A JP 2003526862A JP 3981356 B2 JP3981356 B2 JP 3981356B2
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- pyrotechnic composition
- solid pyrotechnic
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- solid
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- 239000000203 mixture Substances 0.000 title claims description 168
- 239000007787 solid Substances 0.000 title claims description 113
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims description 140
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 84
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 62
- 239000007800 oxidant agent Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 45
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 39
- 150000003839 salts Chemical class 0.000 claims description 38
- 239000004323 potassium nitrate Substances 0.000 claims description 31
- 235000010333 potassium nitrate Nutrition 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- 230000001590 oxidative effect Effects 0.000 claims description 29
- 229920005596 polymer binder Polymers 0.000 claims description 19
- 239000002491 polymer binding agent Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 18
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003610 charcoal Substances 0.000 claims description 13
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 12
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 12
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 8
- 239000011118 polyvinyl acetate Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920001778 nylon Polymers 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000020 Nitrocellulose Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920001220 nitrocellulos Polymers 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims 4
- 239000003513 alkali Substances 0.000 claims 1
- HHEFNVCDPLQQTP-UHFFFAOYSA-N ammonium perchlorate Chemical class [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 16
- 229910052796 boron Inorganic materials 0.000 description 16
- 238000009472 formulation Methods 0.000 description 14
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 229920002274 Nalgene Polymers 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- -1 phenol compound Chemical class 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- APAJFZPFBHMFQR-UHFFFAOYSA-N anthraflavic acid Chemical compound OC1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 APAJFZPFBHMFQR-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 210000001508 eye Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
- C06C9/00—Chemical contact igniters; Chemical lighters
-
- 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
- C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
- C06B31/08—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a metal oxygen-halogen salt, e.g. inorganic chlorate, inorganic perchlorate
-
- 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
- C06B31/30—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with vegetable matter; with resin; with rubber
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Air Bags (AREA)
Description
本出願は２００１年１月１２日に米国特許商標庁に出願された米国仮出願番号６０／２６１１１１号の優先権の利益を請求する。この出願の全開示がここに参照によって組み込まれる。
本発明は、新規な黒色火薬代替物及びホウ素／硝酸カリウム代替物の組成物を含む、固体の火工品用組成物に関する。本発明はまた、該固体火工品用組成物を製造するための方法に関する。
This application claims the benefit of priority of US Provisional Application No. 60/261111, filed with the US Patent and Trademark Office on January 12, 2001. The entire disclosure of this application is hereby incorporated by reference.
The present invention relates to a solid pyrotechnic composition comprising a novel black powder substitute and a boron / potassium nitrate substitute composition. The present invention also relates to a method for producing the solid pyrotechnic composition.
黒色火薬及びホウ素／硝酸カリウム（B/KNO3）は、２種の古典的な点火薬配合物であり、種々の用途において現在広い用途を有する。黒色火薬は７２〜７５重量％の硝酸カリウム、１５〜１８重量％の炭、及び１０重量％の硫黄から成る。この基本的な黒色火薬配合物の変形物は既知である。黒色火薬のための最適の配合は一般に、７５重量％の硝酸カリウム、１５重量％の炭、及び１０重量％の硫黄からなると一般的に受容されている。この配合物の黒色火薬は１０００ｐｓｉにおいて１９５０Ｋの予想火炎温度を有する。一方、最適の配合においてホウ素／硝酸カリウムは７５重量％の硝酸ナトリウム及び２５重量％のホウ素から成る。黒色火薬と比較して、ホウ素／硝酸カリウムは１０００ｐｓｉにおいて３０３４Ｋの有意に高い火炎温度を有する。 Black powder and boron / potassium nitrate (B / KNO 3 ) are two classic igniter formulations and currently have wide application in various applications. Black powder consists of 72-75% by weight potassium nitrate, 15-18% by weight charcoal, and 10% by weight sulfur. Variations on this basic black powder formulation are known. The optimum formulation for black powder is generally accepted as consisting of 75 wt% potassium nitrate, 15 wt% charcoal, and 10 wt% sulfur. The black powder of this formulation has an expected flame temperature of 1950K at 1000 psi. On the other hand, in the optimum formulation, boron / potassium nitrate consists of 75% by weight sodium nitrate and 25% by weight boron. Compared to black powder, boron / potassium nitrate has a significantly higher flame temperature of 3034 K at 1000 psi.
黒色火薬とホウ素／硝酸カリウムの火炎温度が有意に異なるので、これらの点火薬組成物が使用される用途は幾分異なる。黒色火薬は２種の組成物のうちではるかに低価格であり、より低い火炎温度を有し、そしてホウ素／硝酸カリウムよりもスラグ形成が少ない。これらの理由から、黒色火薬はしばしば、多用途ハードウエア（種々の大きさ及び用途の銃を含む）の点火系列においてホウ素／硝酸カリウムを超えてしばしば選択される。ホウ素／硝酸カリウムは通常、迅速で再現性のある点火のためにより高い温度が重要である用途において利用される。例えば、Ｂ／ＫＮＯ３のための通常の用途は、ロケット類、おとり照明(decoy flares)、及び自動車用二次安全拘束手段又は「エアバッグ」装置のガス発生装置を含む。しかし、ホウ素／硝酸カリウムはＢＫＮＯ３の経費及び高いＢＫＮＯ３炎温度（これは再使用可能なハードウエアの時期尚早の腐食を引き起し得る）によって、多用途ハードウエア中に同様にしばしばには用いられない。 Because the flame temperatures of black powder and boron / potassium nitrate are significantly different, the applications in which these igniter compositions are used are somewhat different. Black explosives are much less expensive of the two compositions, have lower flame temperatures, and have less slag formation than boron / potassium nitrate. For these reasons, black powder is often selected over boron / potassium nitrate in the firing series of versatile hardware (including guns of various sizes and applications). Boron / potassium nitrate is typically utilized in applications where higher temperatures are important for rapid and reproducible ignition. For example, typical applications for B / KNO 3 include gas generators for rockets, decoy flares, and secondary safety restraints for automobiles or “airbag” devices. However, boron / potassium nitrate by cost and high BKNO 3 flame temperature of BKNO 3 (which can cause premature corrosion of the reusable hardware), likewise often used in versatile hardware I can't.
黒色火薬を製造するための方法は本技術において既知である。例えば、炭及び硫黄をボールミルで粉砕して、押出機内に供給するための均質な混合物とする。ボールミル粉砕はまた、炭の粒子サイズを減じるために役立つ。硝酸カリウムは乾燥され、そして同様にロッドミルを通して処理されて、平均粒子サイズを約５０ミクロンに減じる。グラファイトが所望によって静電放電感度（ＥＳＤ）を下げる目的のためにロッドミル内に導入され得る。粉砕された炭、硫黄及び硝酸カリウム、及び所望によりグラファイトを次に周知の方法に従って配合する。 Methods for producing black powder are known in the art. For example, charcoal and sulfur are pulverized with a ball mill to form a homogeneous mixture for feeding into an extruder. Ball milling also helps to reduce the charcoal particle size. The potassium nitrate is dried and similarly processed through a rod mill to reduce the average particle size to about 50 microns. Graphite can be introduced into the rod mill for the purpose of reducing electrostatic discharge sensitivity (ESD) if desired. The ground charcoal, sulfur and potassium nitrate, and optionally graphite are then compounded according to well-known methods.
黒色火薬の燃焼は過多の排出物を生じる。黒色火薬の燃焼はかなりの量の一酸化炭素、二酸化硫黄、及び硫化水素を発生すると計算される。硫化カリウムが燃焼生成物の２０％より多くを構成すると予想される。火炎温度において、硫化硫黄は液状で生成され、そして大気酸素による後燃焼を受けて多量の二酸化硫黄を生じやすい。一酸化炭素及び硫化水素も後燃焼を受けやすく、ニ酸化炭素及び二酸化硫黄をそれぞれ生じる。 Black powder combustion produces excessive emissions. It is calculated that the combustion of black powder generates significant amounts of carbon monoxide, sulfur dioxide, and hydrogen sulfide. It is expected that potassium sulfide will constitute more than 20% of the combustion products. At flame temperatures, sulfur sulfide is produced in a liquid state and is susceptible to post combustion with atmospheric oxygen to produce large amounts of sulfur dioxide. Carbon monoxide and hydrogen sulfide are also susceptible to post-combustion, producing carbon dioxide and sulfur dioxide, respectively.
二酸化硫黄は粘膜の組織、上部呼吸管、眼及び皮膚に極端に害がある。吸入は、喉頭及び気管支の発作、炎症、及び浮腫、化学品肺炎、肺浮腫を起こす。従って、二酸化硫黄への暴露は重大な健康上の問題に、長期間の暴露の場合には死につながり得る。 Sulfur dioxide is extremely damaging to mucosal tissues, upper respiratory tract, eyes and skin. Inhalation causes laryngeal and bronchial attacks, inflammation, and edema, chemical pneumonia, pulmonary edema. Thus, exposure to sulfur dioxide can lead to serious health problems and death in the case of prolonged exposure.
黒色火薬の炭成分は、点火薬組成物の性能にある程度の非予測性を付与する。炭は、木材の炭化によって製造される。米国特許第５３２０６９１号に記述されるように、木材の化学的物理的性質は、木の種類、土壌の組成、及び木材が得られた環境条件に依存して大きく変化する。木材の本来の変動及び炭化処理における変動によって、炭の性質はバッチ間で変化する傾向にある。これらの変動は黒色火薬の性能の一貫性に影響し得る。 The charcoal component of the black powder imparts some degree of unpredictability to the performance of the igniter composition. Charcoal is produced by carbonization of wood. As described in US Pat. No. 5,320,691, the chemical and physical properties of wood vary greatly depending on the type of tree, the composition of the soil, and the environmental conditions from which the wood was obtained. Due to the inherent variation of wood and variations in the carbonization process, the nature of the charcoal tends to change from batch to batch. These variations can affect the consistency of black powder performance.
黒色粉末に関連した他の問題はその吸湿性である。黒色火薬は２４時間で、２１．１℃（７０°Ｆ）において７５％相対湿度で約１．５重量％の水分を吸収する。もし黒色火薬が十分な量の水分を取り込むと、黒色粉末が速く燃焼しない可能性がある。点火薬又は黒色火薬を含む他の装置は高い相対湿度における規格まで、実現できないかもしれない。また、水が硝酸カリウムを黒色火薬粉末から外へ移行させ、そして装置の金属部分を腐食させる原因となる。
明細書中で複数として表現していなくても、その文脈が明らかに他の方法で説明していない限り複数の形態を含む。例えば、用語「有機結晶質化合物」は、その単一の有機結晶質化合物のみならず、２種以上の有機結晶質化合物の組合せも包含する。 Where the specification does not express as plural, it includes plural forms unless the context clearly dictates otherwise. For example, the term “organic crystalline compound” encompasses not only a single organic crystalline compound but also a combination of two or more organic crystalline compounds.
用語「ポリマー」は、ホモポリマー、コポリマー、及びターポリマーを包含する。ターポリマーは３種又はそれより多いモノマーから製造されるポリマーを意味する。
ここで使用するとき、用語「有機結晶質化合物」は、文脈で他の方法で明らかに説明していない限り、塩として存在するのではない有機化合物を意味する。
The term “polymer” includes homopolymers, copolymers, and terpolymers. Terpolymer means a polymer made from three or more monomers.
As used herein, the term “organic crystalline compound” means an organic compound that is not present as a salt, unless the context clearly indicates otherwise.
ここで使用するとき、用語「有機結晶質化合物の塩」は、有機化合物の負電荷を相殺する金属カチオン又はアンモニウムカチオンにイオン的に結合した負に帯電した有機化合物を意味する。例はフェノールフタレイン2カリウムである。 As used herein, the term “salt of an organic crystalline compound” means a negatively charged organic compound that is ionically bonded to a metal cation or ammonium cation that counteracts the negative charge of the organic compound. An example is phenolphthalein dipotassium.
本発明の目的は、火炎温度を有し、かつ黒色火薬に匹敵する弾道性能を示す固体火工品組成物（好ましくは（必須ではないが）炭も硫黄も含まない様に処方されている）を提供することである。 The object of the present invention is a solid pyrotechnic composition having a flame temperature and exhibiting ballistic performance comparable to black powder (preferably (although not required) formulated to contain no char or sulfur) Is to provide.
本発明の一面において、固体火工品組成物を構成する黒色火薬代替品は、上記及び他の目的を達成するために提供される。本組成物は約４０重量％〜約９０重量％の、約３０ミクロン以下の平均粒径を有する酸化剤粒子を含む。酸化剤粒子は（ａ）アルカリ金属硝酸塩及び硝酸アンモニウムより成る群から選択される少なくとも１種、及び（ｂ）アルカリ金属過塩素酸塩及び過塩素酸アンモニウムより成る群から選択される少なくとも１種を含む。好ましいアルカリ金属はカリウムである。固体の火工品組成物はさらに、有機結晶質粒子及び所望により有機結晶質粒子の塩を含む。有機結晶質粒子及び所望による有機結晶質粒子の塩は好ましくは約３０ミクロン以下の平均粒径を有し、そして好ましくは固体火工品組成物の全重量の約１０〜約６０重量％を構成する。有機結晶質粒子は好ましくはフェノールフタレインを含む。 In one aspect of the present invention, a black powder substitute constituting a solid pyrotechnic composition is provided to achieve the above and other objects. The composition comprises from about 40 wt% to about 90 wt% oxidizer particles having an average particle size of about 30 microns or less. The oxidant particles include (a) at least one selected from the group consisting of alkali metal nitrates and ammonium nitrate, and (b) at least one selected from the group consisting of alkali metal perchlorates and ammonium perchlorate. . A preferred alkali metal is potassium. The solid pyrotechnic composition further comprises organic crystalline particles and optionally a salt of the organic crystalline particles. The organic crystalline particles and optionally the salt of the organic crystalline particles preferably have an average particle size of about 30 microns or less and preferably constitute from about 10 to about 60% by weight of the total weight of the solid pyrotechnic composition. To do. The organic crystalline particles preferably contain phenolphthalein.
第２の面に従い、本発明の目的は火炎温度を有し、そしてホウ素／硝酸カリウムに匹敵する弾道性能を示し、そして好ましくは（必須ではない）ホウ素を含まない固体火工品組成物を提供することである。 In accordance with the second aspect, the object of the present invention is to provide a solid pyrotechnic composition having a flame temperature and exhibiting ballistic performance comparable to boron / potassium nitrate and preferably (not essential) free of boron. That is.
本発明の第２の面に従い、直前に述べた目的及び他の目的を達成するために、ホウ素／硝酸カリウム代替物を含む固体火工品組成物が提供される。この組成物は、約３０ミクロン以下の平均粒径を有する酸化剤粒子約４０〜約９０重量％を含む。酸化剤粒子は、アルカリ金属過塩素酸塩、及び過塩素酸アンモニウムより成る群から選択される少なくとも１種を含む。過塩素酸塩粒子は、組成物の全重量の約２０〜約９０重量％、さらに好ましくは組成物の全重量の３０〜９０重量％を構成する。酸化剤粒子は他の材料も含み得、これはアルカリ金属硝酸塩及び硝酸アンモニウムより成る群から選択される少なくとも１種を含む。過塩素酸塩及び硝酸塩のための好ましいアルカリ金属はカリウムである。固体の火工品組成物はさらに、有機懸想質粒子及び所望により有機結晶質粒子の塩を含む。有機結晶質粒子及び所望による有機結晶質粒子の塩は好ましくは３０ミクロン以下平均粒径を有し、そして好ましくは固体火工品組成物の全重量の約１０〜約６０重量％を構成する。有機結晶質粒子は好ましくはフェノールフタレインである。 In accordance with the second aspect of the present invention, a solid pyrotechnic composition comprising a boron / potassium nitrate substitute is provided to achieve the objectives just described and other objectives. The composition includes about 40 to about 90 weight percent oxidizer particles having an average particle size of about 30 microns or less. The oxidant particles include at least one selected from the group consisting of alkali metal perchlorates and ammonium perchlorate. The perchlorate particles comprise about 20 to about 90% by weight of the total weight of the composition, more preferably 30 to 90% by weight of the total weight of the composition. The oxidant particles may also include other materials, including at least one selected from the group consisting of alkali metal nitrates and ammonium nitrate. The preferred alkali metal for perchlorate and nitrate is potassium. The solid pyrotechnic composition further comprises organic suspended particles and optionally a salt of organic crystalline particles. The organic crystalline particles and optionally the salt of the organic crystalline particles preferably have an average particle size of 30 microns or less and preferably constitute from about 10 to about 60% by weight of the total weight of the solid pyrotechnic composition. The organic crystalline particles are preferably phenolphthalein.
これらのそれぞれの好ましい態様において、これらの新規の黒色火薬及びＢ／ＫＮＯ３代替組成物の成分の選択は、硫黄から誘導される有害な排出物の生成をかなり減じることができる。このように、本発明は、該組成物を使用する製品の燃焼及び燃焼後の清掃操作を実施する間の、環境への影響及び作業者の健康の危険性における改善を提供できる。さらに、現在好ましい態様に従う固体の火工品組成物は優秀な衝撃及び熱感受性を有し、それによって、衝撃、摩擦、熱及び／又は静電放電のような刺激に対する応答による爆発及び時期尚早な点火への、点火薬の初期の事故を減じることができる。さらに、結晶質塩の代わりに（または部分的に代わりに）有機結晶質化合物を使用すること、並びに非吸湿性バインダーを使用することは、黒色火薬粉末と比較して有意に本発明の固体火工品組成物の水分取り込みを低下できる。さらに、本発明の好ましい態様から炭を除去することは火工品組成物の弾道性能の再現性及び均一性を改善でき、並びに組成物の水分取り込みを最少化できる。 In each of these preferred embodiments, the selection of these novel black powder and B / KNO 3 alternative composition components can significantly reduce the generation of harmful emissions derived from sulfur. Thus, the present invention can provide improvements in environmental impacts and worker health risks while performing products that use the composition and post-burn cleaning operations. Furthermore, solid pyrotechnic compositions according to presently preferred embodiments have excellent impact and thermal sensitivity, thereby causing explosion and premature response in response to stimuli such as impact, friction, heat and / or electrostatic discharge. The initial accident of the igniting agent to ignition can be reduced. Furthermore, the use of an organic crystalline compound in place of (or in place of) a crystalline salt, as well as the use of a non-hygroscopic binder, is significantly more significant than the solid powder of the present invention. The water uptake of the product composition can be reduced. Furthermore, removing the charcoal from the preferred embodiment of the present invention can improve the reproducibility and uniformity of the ballistic performance of the pyrotechnic composition and minimize the moisture uptake of the composition.
黒色火薬代替物及びホウ素／硝酸カリウムを製造するための新規な方法を提供することが本発明の第３の面に従う本発明の他の目的である。
本発明のこの第３の面の原理に従い、上述の目的及び他の目的は、アルカリ金属ヒドロオキシドを少なくとも１種の有機結晶質化合物と組み合わせて有機結晶質化合物の塩を含む溶液を製造するという方法によって達成される。有機結晶質化合物は好ましくは、フェノールフタレイン並びにフェノール化合物と無水フタル酸との反応から誘導される化合物より成る群から選択される。次に溶液を、硝酸及び過塩素酸より成る群から選択される少なくとも１種の酸と組み合わせる。アルカリ金属ヒドロキシドが硝酸又は過塩素酸と反応してアルカリ金属硝酸塩粒子又はアルカリ金属過塩素酸粒子を、それぞれ形成する。さらに、酸は塩を有機結晶質化合物へ転化して戻し、同時に有機結晶質化合物の粒径を約３０ミクロン以下に減じるために役立つ。約３０ミクロン以下の平均粒径を有する追加の酸化剤粒子を追加できる。追加の酸化剤粒子は過塩素酸塩及び／又は硝酸塩粒子を含む。次に火工品組成物を乾燥する（必要か望まれる場合）。
It is another object of the present invention according to the third aspect of the present invention to provide a black powder substitute and a novel method for producing boron / potassium nitrate.
In accordance with the principles of this third aspect of the present invention, the above and other objects are that an alkali metal hydroxide is combined with at least one organic crystalline compound to produce a solution comprising a salt of the organic crystalline compound. Achieved by the method. The organic crystalline compound is preferably selected from the group consisting of phenolphthalein and compounds derived from the reaction of phenolic compounds with phthalic anhydride. The solution is then combined with at least one acid selected from the group consisting of nitric acid and perchloric acid. Alkali metal hydroxide reacts with nitric acid or perchloric acid to form alkali metal nitrate particles or alkali metal perchloric acid particles, respectively. In addition, the acid serves to convert the salt back into the organic crystalline compound, while at the same time reducing the particle size of the organic crystalline compound to about 30 microns or less. Additional oxidizer particles having an average particle size of about 30 microns or less can be added. The additional oxidizer particles include perchlorate and / or nitrate particles. The pyrotechnic composition is then dried (if necessary or desired).
本発明の追加の目的及び利点は以下の説明において記載され、そして部分的には該説明から明らかであり、又は本発明の実施によって習得することができる。本発明の目的及び利点は、特許請求の範囲に指摘した方法及び組合せによって実現され、そして得られる。 Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention will be realized and obtained by means of the methods and combinations pointed out in the appended claims.
本明細書に組み込まれ、そしてその一部を構成する添付図面は、商業的に利用されるＢ／ＫＮＯ３点火薬と本発明に従い調製される実施例１５のホウ素を含まない点火薬との点火性能の比較を示す。図面は、上述の一般的な説明と、以下の好ましい態様及び方法の詳細な説明と共に、本発明の原理を説明するために役立つ。 The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate the ignition of a commercially available B / KNO 3 igniter and the boron-free igniter of Example 15 prepared according to the present invention. A performance comparison is shown. The drawings, together with the above general description and the following detailed description of preferred embodiments and methods, serve to explain the principles of the invention.
本発明の現在好ましい態様に従い、酸化剤粒子と有機結晶質粒子を含む、黒色火薬代替物の火工品組成物が提供される。
この態様に従う酸化剤粒子は、該固体火工品組成物の全重量の約４０〜約９０重量％、さらに好ましくは６５〜８０重量％を構成する。酸化剤粒子の平均粒径は約３０ミクロン以下、好ましくは２０ミクロン以下、そしてさらに好ましくは５〜２０ミクロンの範囲である。
In accordance with the presently preferred embodiment of the present invention, there is provided a pyrotechnic composition for black powder alternative comprising oxidant particles and organic crystalline particles.
Oxidant particles according to this embodiment comprise about 40 to about 90% by weight, more preferably 65 to 80% by weight of the total weight of the solid pyrotechnic composition. The average particle size of the oxidizer particles is in the range of about 30 microns or less, preferably 20 microns or less, and more preferably 5 to 20 microns.
この態様の酸化剤粒子は少なくとも１種の硝酸塩を含む。この硝酸塩は好ましくは、アルカリ金属硝酸塩及び硝酸アンモニウムより成る群から選択される少なくとも１種をである。例示のアルカリ金属硝酸塩は硝酸カリウム、硝酸セリウム、硝酸ルビジウム、及び硝酸アンモニウムであり、硝酸カリウムが好ましい。 The oxidant particles of this embodiment include at least one nitrate. The nitrate is preferably at least one selected from the group consisting of alkali metal nitrates and ammonium nitrate. Exemplary alkali metal nitrates are potassium nitrate, cerium nitrate, rubidium nitrate, and ammonium nitrate, with potassium nitrate being preferred.
この態様の酸化剤粒子はまた、少なくとも１種の過塩素酸塩を含む。過塩素酸塩は好ましくは、過塩素酸カリウム及び過塩素酸アンモニウムより成る群から選択される少なくとも１種であり、過塩素酸カリウムが好ましい。約３０ミクロン又はそれより小さい好ましい粒径で使用される場合、過塩素酸塩は弾道性能を犠牲にすることなく火工品組成物から硫黄を削除することを可能とする。この固体火工品組成物に点火したとき、過塩素酸塩は火工品組成物の点火遅延を減じ、同時に圧力上昇を増すことができる。固体火工品組成物の全重量の０．５〜３０重量％が過塩素酸塩を構成するのが好ましい。さらに好ましくは、固体火工品組成物の５〜２０重量％が過塩素酸塩からなる。 The oxidant particles of this embodiment also include at least one perchlorate salt. The perchlorate is preferably at least one selected from the group consisting of potassium perchlorate and ammonium perchlorate, with potassium perchlorate being preferred. When used at a preferred particle size of about 30 microns or less, perchlorate allows sulfur to be removed from the pyrotechnic composition without sacrificing ballistic performance. When igniting this solid pyrotechnic composition, perchlorate can reduce the ignition delay of the pyrotechnic composition and at the same time increase the pressure rise. It is preferred that 0.5 to 30% by weight of the total weight of the solid pyrotechnic composition constitute the perchlorate. More preferably, 5 to 20% by weight of the solid pyrotechnic composition is composed of perchlorate.
この態様の有機結晶質粒子、並びに所望により存在する有機結晶質粒子の塩は、火工品組成物の全重量の約１０〜約６０、さらに好ましくは１３〜２２重量％を占める。塩が存在する場合、有機結晶質化合物の少なくとも５０重量％、さらに好ましくは少なくとも８０重量％、さらに好ましくは約９０重量％が塩でない状態で存在する。有機結晶のみを使用することが可能であり、かつ好ましく、その結果該固体火工品組成物は有機結晶質化合物の塩を含まない。有機結晶質粒子及びその所望による塩は１００ミクロン程度に大きい平均粒径を有してもよいが、それらは好ましくは約３０ミクロン以下、さらに好ましくは２０ミクロン以下、さらに好ましくは１５ミクロン以下、そしてさらに好ましくは１０ミクロン以下の平均粒径を有する。 The organic crystalline particles of this embodiment, as well as optionally present salts of organic crystalline particles, comprise from about 10 to about 60, more preferably from 13 to 22% by weight of the total weight of the pyrotechnic composition. When a salt is present, at least 50%, more preferably at least 80%, more preferably about 90% by weight of the organic crystalline compound is present in a non-salt state. It is possible and preferred to use only organic crystals, so that the solid pyrotechnic composition does not contain salts of organic crystalline compounds. Although the organic crystalline particles and their optional salts may have an average particle size as large as 100 microns, they are preferably about 30 microns or less, more preferably 20 microns or less, more preferably 15 microns or less, and More preferably, it has an average particle size of 10 microns or less.
好ましくは、有機結晶質粒子は、フェノールフタレイン、並びにフェノール化合物と無水フタル酸との間の反応から誘導される有機結晶質化合物より成る群から選択される少なくとも１種を含む。例えば、フェノール化合物の２〜６位の１つ以上、及び／又は無水フタル酸化合物の２〜５位の１つ以上が、官能基、例えば−Ｒ、−ＮＨ２、−ＮＲ１Ｈ、−ＮＲ１Ｒ２、−ＮＯ２、−ＯＲ等（Ｒ、Ｒ１、Ｒ２は例えばアルキル及びアリールから独立して選択される）によって置換されていてよい。 Preferably, the organic crystalline particles comprise at least one selected from the group consisting of phenolphthalein and organic crystalline compounds derived from the reaction between the phenolic compound and phthalic anhydride. For example, 2-6 of one or more phenolic compounds, and / or one or more 2-5 of phthalic anhydride compound, functional groups, such as -R, -NH 2, -NR 1 H , -NR 1 R 2 , —NO 2 , —OR and the like (R, R 1 , R 2 are independently selected from, for example, alkyl and aryl).
本発明の固体火工品組成物は、フェノールフタレインとその誘導体に限定されない。本技術において既知の他の有機結晶質化合物及び未だ発見されていないものも使用できる。本発明と共に使用できる代表的な有機結晶質化合物は、Wiseらへの米国特許商標庁文書Ｈ７２に記述され、フルオレセイン、１，５−ナフタレンジオール、アントラフラビン酸、テレフタル酸を含む。 The solid pyrotechnic composition of the present invention is not limited to phenolphthalein and its derivatives. Other organic crystalline compounds known in the art and those not yet discovered can also be used. Exemplary organic crystalline compounds that can be used with the present invention are described in US Patent and Trademark Office document H72 to Wise et al. And include fluorescein, 1,5-naphthalenediol, anthraflavic acid, terephthalic acid.
本発明の固体火工品組成物は所望により、追加の成分（例えば非吸湿性ポリマーバインダーを包含する）を含み得る。本発明のこの態様において使用し得る適切な非吸湿性ポリマーバインダーは、７５％の相対湿度（２１．１℃（７０°Ｆ））で２４時間で４％未満の水分を取り込む(すなわち吸収)ものを包含する。代表的なバインダーは、ポリ（酢酸ビニル）、ポリ(酢酸ビニル−ビニルアルコール)、ナイロン、ポリ(エチレン−酢酸ビニル)、ポリエチレングリコール、アルキルセルロース（例えばエチルセルロース）、ニトロセルロース、及びある種の鎖で延長されたオキセタン(oxetanes)（例えばポリＢＡＭＯ）、グリシジルアジドポリマー（ＧＡＰ）、及び関連するポリマーを包含する。バインダーを溶解し、製造中の粘度を下げるために適切な溶媒を使用し得る。例えば、酢酸エチルはポリ（酢酸ビニル）のために適切な溶媒である。組成物がポリマーバインダーを含まない場合、混合を容易にするために水を使用し得る。例えば、必ずしも限定ではなく、バインダーは組成物中に約１０重量％以下、好ましくは３〜６重量％の濃度で存在し得る。 The solid pyrotechnic composition of the present invention can optionally include additional components, including non-hygroscopic polymer binders. Suitable non-hygroscopic polymer binders that can be used in this aspect of the invention are those that incorporate less than 4% moisture (ie, absorb) in 24 hours at 75% relative humidity (21.1 ° C. (70 ° F.)). Is included. Typical binders are poly (vinyl acetate), poly (vinyl acetate-vinyl alcohol), nylon, poly (ethylene-vinyl acetate), polyethylene glycol, alkyl cellulose (eg, ethyl cellulose), nitrocellulose, and certain chains. Includes extended oxetanes (eg, poly BAMO), glycidyl azide polymer (GAP), and related polymers. Any suitable solvent may be used to dissolve the binder and reduce the viscosity during manufacture. For example, ethyl acetate is a suitable solvent for poly (vinyl acetate). If the composition does not contain a polymer binder, water can be used to facilitate mixing. For example, but not necessarily, the binder may be present in the composition at a concentration of about 10 wt% or less, preferably 3-6 wt%.
グラファイト、金属又はメタロイド燃料及び充填剤を包含する他の成分も、固体火工品組成物の意図される用途に望まれるか必要とされる場合に許容される。
慣用の黒色火薬と比較して、非吸湿性バインダー及び結晶質化合物の使用は、本発明の固体火工品組成物の水分取り込みを下げる。好ましい態様において、固体火工品組成物の水分取り込みは、７５％の相対湿度及び２１．１℃（７０°Ｆ）において２４時間にわたり０．３重量％以下、さらに好ましくは０．２５重量％以下である。
Other components, including graphite, metal or metalloid fuels and fillers are also acceptable if desired or required for the intended use of the solid pyrotechnic composition.
Compared to conventional black explosives, the use of non-hygroscopic binders and crystalline compounds reduces the water uptake of the solid pyrotechnic composition of the present invention. In a preferred embodiment, the moisture uptake of the solid pyrotechnic composition is no more than 0.3 wt%, more preferably no more than 0.25 wt% over 24 hours at 75% relative humidity and 21.1 ° C (70 ° F). It is.
さらに、酸化剤塩及び有機結晶質化合物の比率を調節することによって、点火時に２３００Ｋ以下、好ましくは１７５０Ｋ〜２３００Ｋの理論火炎温度を有する配合物を得ることができる。一般に、過塩素酸塩の濃度を増すことは、火炎温度を増し、過塩素酸の濃度を減らすことは理論火炎温度を下げる。一方、理論火炎温度は有機結晶質化合物と逆相関関係を有する。理論火炎温度はNASA-Lewis熱化学計算によって計算される。このプログラムのコピーはオハイオ州クリーブランドのNASA Glenn Research Centerを通じて入手できる。 Furthermore, by adjusting the ratio of the oxidant salt and the organic crystalline compound, it is possible to obtain a blend having a theoretical flame temperature of 2300K or less, preferably 1750K to 2300K at the time of ignition. In general, increasing the concentration of perchlorate increases the flame temperature, and decreasing the concentration of perchloric acid decreases the theoretical flame temperature. On the other hand, the theoretical flame temperature has an inverse correlation with the organic crystalline compound. The theoretical flame temperature is calculated by NASA-Lewis thermochemical calculation. A copy of the program is available through the NASA Glenn Research Center in Cleveland, Ohio.
本発明の現在好ましい態様において、黒色火薬代替物（ＢＰＳ）組成物は６１．６重量％の１５ミクロン硝酸カリウム、１５重量％の２０ミクロン過塩素酸カリウム、１８．９重量％の６ミクロンフェノールフタレイン、及び４．５重量％の５０００００分子量のポリ（酢酸ビニル）を含む。
In a presently preferred embodiment of the present invention, a black powder substitute (BPS) composition comprises 61.6% by weight 15 micron potassium nitrate, 15% by
本発明の他の態様に従い、過塩素酸塩酸化剤粒子及び有機結晶質粒子を含む、Ｂ／ＫＮＯ３の代替火工品組成物が提供される。
本発明のこの態様のために適切な過塩素酸塩及び有機結晶質粒子は、黒色火薬代替組成物と関連して上述し列挙したものから選択できる。一般に、ホウ素／硝酸カリウムは比較的高い理論火炎温度、好ましくは少なくとも２３００Ｋ、さらに好ましくは２３００Ｋ〜３０００Ｋの範囲で燃焼する。そのような高い火炎温度を、比較的高い過塩素酸塩含量、例えば固体火工品組成物の全重量を基準として約２０重量％〜約９０重量％、さらに好ましくは３０〜９０重量％を使用することによって得ることが可能である。過塩素酸塩は、理論火炎温度を上昇させるために硝酸塩のような他の酸化剤より大きい効果を有することが発見された。一般に、理論火炎温度を調節するために、有機結晶質化合物と所望のバインダーと比較して、低めの含量の過塩素酸塩と高めの含量の他の酸化剤（例えば硝酸塩）を組み合わせる。一方、有機結晶質粒子及び所望のバインダーと比較して、高めの含量の過塩素酸が低い含量の他の酸化剤と組み合わされる。
In accordance with another aspect of the present invention, there is provided an alternative pyrotechnic composition of B / KNO 3 comprising perchlorate oxidant particles and organic crystalline particles.
Suitable perchlorate and organic crystalline particles for this aspect of the invention can be selected from those listed and listed above in connection with the black powder replacement composition. In general, boron / potassium nitrate burns at relatively high theoretical flame temperatures, preferably at least 2300K, more preferably in the range of 2300K to 3000K. Such a high flame temperature is used at a relatively high perchlorate content, for example from about 20% to about 90% by weight, more preferably from 30 to 90% by weight, based on the total weight of the solid pyrotechnic composition. Can be obtained. It has been discovered that perchlorate has a greater effect than other oxidants such as nitrate to raise the theoretical flame temperature. In general, to adjust the theoretical flame temperature, a lower content of perchlorate and a higher content of other oxidants (eg, nitrates) are combined as compared to the organic crystalline compound and the desired binder. On the other hand, a higher content of perchloric acid is combined with a lower content of other oxidants compared to the organic crystalline particles and the desired binder.
黒色火薬及びホウ素／硝酸カリウム組成物を製造するための慣用の方法が、本発明の固体火工品組成物を製造するために実施し得る。例えば、Dillehayらへの米国特許第５６７００９８号に記述されるツインスクリュー押出機が使用し得る。同様に、ボールミリング、ミュラーミリング、及び他のミリング技術が使用し得る。これらの方法は本技術において既知であり、文献に記載されている。 Conventional methods for producing black gunpowder and boron / potassium nitrate compositions can be implemented to produce the solid pyrotechnic compositions of the present invention. For example, a twin screw extruder described in US Pat. No. 5670098 to Dillehay et al. Can be used. Similarly, ball milling, Muller milling, and other milling techniques may be used. These methods are known in the art and are described in the literature.
本発明と共に使用することが企図される１つの例の方法に従って、バインダーをホバート(Hobert)ミキサー内で適切な溶媒中に溶解し、そして有機結晶質粒子（例えばフェノールフタレイン）をこの溶解したバインダーに加える。次に、酸化剤粒子をホバートミキサーに加える。酸化剤粒子は同時に又は互いに異なった時に加え得る。１種より多い酸化剤粒子を使用する場合には、粒子は予備混合する必要はない。溶媒を例えば真空又は蒸発等で除去するときに、材料を小球にするまで成分をホバートミキサー内でブレンドする。小球を適切な大きさに、例えばストークスグラニュレーターで細粒化する。次に細粒を適切な条件下、例えば１３５°Ｆの対流オーブン内でアルミニウムトレー上で乾燥する。乾燥後、追加の細粒化を実施して凝集物を粉砕することができる。この技術は単に例示である。多くの修正をこの技術になし得る。例えば、溶媒を加える前に、バインダーを有機結晶質粒子と予備ブレンドし得る。同様の条件及び工程を、ツインスクリュー押出機で処理するために使用し得る。 In accordance with one example method contemplated for use with the present invention, a binder is dissolved in a suitable solvent in a Hobert mixer, and organic crystalline particles (eg, phenolphthalein) are dissolved in the dissolved binder. Add to. Next, the oxidant particles are added to the Hobart mixer. Oxidant particles can be added simultaneously or at different times. If more than one oxidizer particle is used, the particles need not be premixed. When the solvent is removed, such as by vacuum or evaporation, the ingredients are blended in a Hobart mixer until the material is globuled. The small spheres are refined to an appropriate size, for example, with a Stokes granulator. The granules are then dried on aluminum trays under appropriate conditions, for example in a 135 ° F. convection oven. After drying, additional atomization can be performed to grind the agglomerates. This technique is merely exemplary. Many modifications can be made to this technique. For example, the binder can be preblended with the organic crystalline particles prior to adding the solvent. Similar conditions and processes can be used for processing in a twin screw extruder.
所望により、もし細粒がペレットにプレス加工されるべきであれば、細粒と適切な処理助剤、例えばステアリン酸カルシウムとのブレンドを実施することができる。好ましくは、ステアリン酸カルシウムコーティングは粒子の約０．５重量％を構成する。ペレットはそのまま使用、あるいはさらに処理して（例えばグラインディングによって）細粒化黒色火薬に匹敵する弾道性を有する高密度グラニュールを作ることができる。 If desired, if the granules are to be pressed into pellets, blending of the granules with a suitable processing aid such as calcium stearate can be performed. Preferably, the calcium stearate coating comprises about 0.5% by weight of the particles. The pellets can be used as is or further processed (eg by grinding) to produce high density granules with ballistic properties comparable to finely divided black powder.
本発明の方法の好ましい面において、アルカリ金属ヒロドキシド、例えば水酸化カリウムを少なくとも１種の有機結晶質化合物（例えばフェノールフタレイン又はフェノールフタレイン誘導体）と組み合わせて有機結晶質化合物の塩を含む溶液を製造する。この溶液を硝酸又は過塩素酸と混合、又は望まれるのであればこれらの酸の組合せと混合する。アルカリ金属ヒドロキシドが硝酸又は過塩素酸と反応してアルカリ金属硝酸塩粒子又はアルカリ金属過塩素酸塩粒子をそれぞれ形成する。さらに、酸は、塩を有機結晶質化合物に転化して戻すのに役立ち、同時に、好ましくは有機結晶質化合物の粒径を約３０ミクロン以下、さらに好ましくは２０ミクロン以下に減じる。約３０ミクロン以下の平均粒径を有する追加の酸化剤粒子を添加し得る。この添加又は組合せ工程は、その場で、アルカリ金属ヒドロキシドと硝酸又は過塩素酸の反応によって酸化剤粒子を形成することによってなし得る。酸化剤粒子は硝酸塩及び／又は過塩素酸塩を含む。火工品組成物は、必要か又は望まれる場合には、次に乾燥され得る。例として、そして限定なしに、乾燥は減圧又は周囲圧下で実施でき、そして室温又は高温で実施し得る。乾燥方法は本技術において周知である。 In a preferred aspect of the method of the present invention, a solution comprising a salt of an organic crystalline compound in combination with an alkali metal hydroxide, such as potassium hydroxide, in combination with at least one organic crystalline compound (eg, phenolphthalein or a phenolphthalein derivative). To manufacture. This solution is mixed with nitric acid or perchloric acid or, if desired, with a combination of these acids. Alkali metal hydroxide reacts with nitric acid or perchloric acid to form alkali metal nitrate particles or alkali metal perchlorate particles, respectively. In addition, the acid serves to convert the salt back into an organic crystalline compound, while at the same time preferably reducing the particle size of the organic crystalline compound to about 30 microns or less, more preferably 20 microns or less. Additional oxidant particles having an average particle size of about 30 microns or less may be added. This addition or combination step can be accomplished in situ by forming oxidant particles by reaction of alkali metal hydroxide with nitric acid or perchloric acid. The oxidant particles include nitrate and / or perchlorate. The pyrotechnic composition can then be dried if necessary or desired. By way of example and without limitation, drying can be performed under reduced or ambient pressure and can be performed at room temperature or elevated temperature. Drying methods are well known in the art.
平均粒径の決定は、規格ISO-13320-1:1999(E), “Particle Size Analysis-Laser Diffraction Methods”に従って実施され、この開示は明確な参照によってここに組み込まれる。一般に、この規格は光の散乱角度と波長の関数としての角光散乱強度のマトリックス転化から平均粒径を導くことを説明する。適切なアルゴリズムは、フラウンフォーファー前方光散乱理論に基づいており、これは当該物及び担体媒質の両方の屈折率を組み込んでいる。 The determination of the average particle size is carried out according to the standard ISO-13320-1: 1999 (E), “Particle Size Analysis-Laser Diffraction Methods”, the disclosure of which is hereby incorporated by express reference. In general, this standard explains that the average particle size is derived from matrix conversion of angular light scattering intensity as a function of light scattering angle and wavelength. A suitable algorithm is based on Fraunhofer forward light scattering theory, which incorporates the refractive indices of both the object and the carrier medium.
MICROTRAC(R)系を使用して、再循環浴が、装置の光学セルに粒子の懸濁流れを与えるために使用される。セルの内側で、粒子の懸濁流れと、光の回折パターンをつくる小レーザー線とが衝突する。この光の回折パターンは、エネルギー分布マトリックスへの転換され、これは種々の粒径の性質、例えば強度、分布、平均直径、累積体積等を与えられた試料について生じる。 Use MICROTRAC (R) system, re-circulating bath is used to give a suspension particle flow into optical cell of the device. Inside the cell, the suspended particle flow collides with a small laser beam that creates a light diffraction pattern. This light diffraction pattern is transformed into an energy distribution matrix, which occurs for samples given various particle size properties such as intensity, distribution, average diameter, cumulative volume, and the like.
本発明の固体の火工品組成物は種々の用途（例えば開始剤、熱線と共に使用される一番点火組成物、ガス発生剤、推進薬等を含む）に有用である。本発明の固体の火工品組成物は、例えばフレア、ロケットモーター、及び乗り物内の二次拘束システム（エアバッグ装置）に使用し得る。 The solid pyrotechnic composition of the present invention is useful for a variety of applications, including, for example, initiators, primary ignition compositions used with heat rays, gas generants, propellants and the like. The solid pyrotechnic composition of the present invention may be used, for example, in flares, rocket motors, and secondary restraint systems (airbag devices) in vehicles.
以下の実施例は、本発明の態様をさらに詳細に説明するために役立つ。これらの実施例は本発明の範囲に関して網羅的であるとも排他的であるとも解釈されるべきではない。 The following examples serve to illustrate aspects of the invention in further detail. These examples should not be construed as exhaustive or exclusive with respect to the scope of the invention.
実施例１
ミニペイントシェーカー内で、５０ｍＬのNalgeneバイアル中で、3.78g(18.9重量％)の6-ミクロンフェノールフタレイン、12.32g(61.6重量％)の15-ミクロン硝酸カリウム、及び3g(15重量％)の20-ミクロン過塩素酸カリウムを1分間乾燥ブレンドした。これらの粉末に、2.92gの30.87％のポリ（酢酸ビニル）（酢酸エチル中）（4.5重量％のPVA乾燥重量）、並びに2.0gの酢酸エチルを加えた。次に成分をペイントシェーカー内で１分間混合し、その後スパチュラでNalgene容器の端部をかきとり、そしてさらに1分間ペイントシェーカー内で混合した。酢酸エチルの一部を換気フード内でときどき攪拌しながら周囲温度で蒸発させた。得られたペーストを１０、１６及び３０メッシュの篩を順次通して粒状化した。得られた細粒を73.9℃(165°F)のオーブン内で乾燥し、次に４０／＋１００メッシュにふるい分けた。弾道性能を、４５ｃｃの密閉ボンベ内で熱線で２ｇの試料を点火することによって決定した。水分取り込みデータを、21.1℃(70°F)において飽和塩化ナトリウム溶液上の密閉容器内のアルミニウム秤量皿内にほぼ３ｇの試料を置くことによって得た。
Example 1
3.78 g (18.9 wt%) 6-micron phenolphthalein, 12.32 g (61.6 wt%) 15-micron potassium nitrate, and 3 g (15 wt%) 20 in a 50 mL Nalgene vial in a mini paint shaker. -Micron potassium perchlorate was dry blended for 1 minute. To these powders were added 2.92 g of 30.87% poly (vinyl acetate) in ethyl acetate (4.5 wt% PVA dry weight), as well as 2.0 g ethyl acetate. The ingredients were then mixed for 1 minute in a paint shaker, after which the end of the Nalgene container was scraped with a spatula and mixed for an additional 1 minute in the paint shaker. A portion of ethyl acetate was evaporated at ambient temperature with occasional stirring in a fume hood. The resulting paste was granulated by passing sequentially through 10, 16, and 30 mesh screens. The resulting granules were dried in an oven at 73.9 ° C. (165 ° F.) and then screened to 40 / + 100 mesh. Ballistic performance was determined by igniting a 2 g sample with hot wire in a 45 cc sealed bomb. Moisture uptake data was obtained by placing approximately 3 g of sample in an aluminum weighing dish in a closed container on saturated sodium chloride solution at 21.1 ° C. (70 ° F.).
実施例２
７０−ミクロンのフェノールフタレインを使用したことを除き、実施例１と同じ方法で試料を調製し、そして弾道性能を試験した。水分取り込みデータを、21.1℃(70°F)において飽和塩化ナトリウム溶液上の密閉容器内の１ｇのアルミニウム秤量皿内にほぼ３ｇの試料を置くことによって得た。得られた弾道性能及び水分取り込みデータを表１に示す。
Example 2
Samples were prepared and tested for ballistic performance in the same manner as Example 1 except that 70-micron phenolphthalein was used. Moisture uptake data was obtained by placing approximately 3 g of sample in a 1 g aluminum weighing pan in a closed container over saturated sodium chloride solution at 21.1 ° C. (70 ° F.). The obtained ballistic performance and moisture uptake data are shown in Table 1.
実施例３
実施例１における同じ処方を５０ｇサイズにスケールアップした。１００ｍＬのプラスチックバイアル内で、9.45gの6ミクロンのフェノールフタレイン(18.9重量％)、30.8gの15ミクロン硝酸カリウム(61.6重量％)、7.5gの20ミクロン過塩素酸カリウム(15重量％)を１分間、ミニペイントシェーカー内で乾燥ブレンドした。この粉末に、7.3gの30.87%のポリ(酢酸ビニル)（酢酸エチル中）（4.5重量％のＰＶＡ乾燥重量）、並びに5.0gの酢酸エチルを加えた。実施例１のように試料を混合し、細粒化し、そして弾道性能を試験し、そして実施例２のように水分取り込みについて試験した。
Example 3
The same formulation in Example 1 was scaled up to 50 g size. In a 100 mL plastic vial, 9.45 g of 6 micron phenolphthalein (18.9 wt%), 30.8 g of 15 micron potassium nitrate (61.6 wt%), 7.5 g of 20 micron potassium perchlorate (15 wt%) Dry blend in a mini paint shaker for minutes. To this powder was added 7.3 g of 30.87% poly (vinyl acetate) in ethyl acetate (4.5 wt% PVA dry weight), as well as 5.0 g of ethyl acetate. Samples were mixed, granulated and ballistic performance tested as in Example 1 and tested for moisture uptake as in Example 2.
実施例４
水分取り込み試験を除き、実施例３を繰り返した。
実施例５〜９
黒色火薬代替物の２０ｇ試料を混合、細粒化、乾燥し、そして弾道性能について試験した。これらの配合物は異なる量の６−ミクロンフェノールフタレイン、２０−ミクロンの過塩素酸カリウム、及び１５ミクロンの硝酸カリウムを有する。酢酸エチル及び酢酸エチル中に溶解したポリ（酢酸ビニル）の量は同じままである。配合と試験データを表１にまとめる。
Example 4
Example 3 was repeated except for the moisture uptake test.
Examples 5-9
A 20 g sample of black powder substitute was mixed, granulated, dried, and tested for ballistic performance. These formulations have different amounts of 6-micron phenolphthalein, 20-micron potassium perchlorate, and 15 micron potassium nitrate. The amount of poly (vinyl acetate) dissolved in ethyl acetate and ethyl acetate remains the same. The formulation and test data are summarized in Table 1.
実施例１０〜１２
実施例２に列挙した成分に加えて硫黄が一成分である配合物も調製した。調製の方法は、７０ミクロンのフェノールフタレイン及び硫黄をペイントシェーカー上で１２５ｍＬのプラスチックバイアル内で0.635cm(0.25インチ)直径のプラスチックビーズの存在下に予備ブレンドし、その後にブレンドした材料を20gのNalgeneバイアル内の黒色火薬代替物のミックスに加えた。弾道性能データは表１中の実施例２のものと比較すべきである。これはこの配合が匹敵する粒子サイズのフェノールフタレインを有するからである。
Examples 10-12
In addition to the ingredients listed in Example 2, a formulation was also prepared in which sulfur was one component. The method of preparation involves pre-blending 70 micron phenolphthalein and sulfur in a 125 mL plastic vial on a paint shaker in the presence of 0.635 cm (0.25 inch) diameter plastic beads, after which 20 g of the blended material is added. Added to the black powder substitute mix in Nalgene vials. Ballistic performance data should be compared with that of Example 2 in Table 1. This is because this formulation has phenolphthalein of comparable particle size.
実施例１３
実施例１０〜１２と同様に、硫黄を含むこの配合物を調製し、そして実験した。ただじ６−ミクロンのフェノールフタレインを調製に使用したので、これらの弾道性能は実施例１及び３〜９と比較することができる。
Example 13
Similar to Examples 10-12, this formulation containing sulfur was prepared and tested. Since only 6 micron phenolphthalein was used in the preparation, these ballistic performances can be compared to Examples 1 and 3-9.
実施例１４
50mLのNalgeneバイアル内で、0.9gの85-90% KOHを0.9gの水に溶解した。この溶液に、2.24gのフェノールフタレインを加え、そして成分を全てのフェノールフタレインがその2カリウム塩に転化されて粘稠な紫色のシロップが生じるまで攪拌した。このシロップに2.33mLの6M硝酸を加え、そしてこの今後打つを白色のスラリーが生じるまで攪拌した。追加の4.84gのKNO3及び1.5gのKClO4を加えた。スラリーを部分的に乾燥し、そして実施例１のペーストと同様に細粒化した。弾道性能結果及び配合百分率を表１に示す。
Example 14
In a 50 mL Nalgene vial, 0.9 g of 85-90% KOH was dissolved in 0.9 g of water. To this solution was added 2.24 g of phenolphthalein and the ingredients were stirred until all the phenolphthalein was converted to its dipotassium salt resulting in a viscous purple syrup. To this syrup was added 2.33 mL of 6M nitric acid, and this future strike was stirred until a white slurry formed. An additional 4.84 g KNO 3 and 1.5 g KClO 4 were added. The slurry was partially dried and ground as in the paste of Example 1. The ballistic performance results and blend percentages are shown in Table 1.
実施例１５
５０ｍＬのNalgeneバイアル内で、2.62gのフェノールフタレインを0.5gの70%水／30%エタノールの溶液に加えた。このスラリーに、1.34gの30%の水性KOH溶液を加えた。成分を混合して紫―赤のスラリーを得、そして11.98gのKClO4を加えた。スラリーを乾燥し、そして−12メッシュへ細粒化した。自動車の安全バッグドライバー側ガス発生装置をエミュレートする再使用可能なハードウエア（図１）内で、高い炎温度点火薬の性能をB/KNO3配合物のものと比較した。具体的には、点火薬をドライバー側の自動車安全バッグの膨張機を模倣して設計された再使用可能なハードウエア内で点火した。両方の試験において利用された非アジドガス発生剤の充填量は３８ｇであった（”Metal Complexes For Use As Gas Generants”; Jerald C. Hinshaw, Daniel W. Doll, Reed J. Blau, Gary K. Lund; Patent 5,592,812(1/14/97)、5,673,935(10/7/97)、5,725,699(3/10/98)及び5,735,118(4/7/98)）。水分取り込みデータ及び成分の百分率を表２にまとめる。
Example 15
In a 50 mL Nalgene vial, 2.62 g phenolphthalein was added to 0.5 g of 70% water / 30% ethanol solution. To this slurry was added 1.34 g of 30% aqueous KOH solution. The ingredients were mixed to give a purple-red slurry and 11.98 g KClO 4 was added. The slurry was dried and granulated to -12 mesh. Within the reusable hardware (Figure 1) that emulates a car safety bag driver side gas generator, the performance of the high flame temperature igniter was compared to that of the B / KNO 3 formulation. Specifically, the igniter was ignited in reusable hardware designed to mimic the expander of a driver's car safety bag. The loading of the non-azide gas generant used in both tests was 38 g (“Metal Complexes For Use As Gas Generants”; Jerald C. Hinshaw, Daniel W. Doll, Reed J. Blau, Gary K. Lund; Patent 5,592,812 (1/14/97), 5,673,935 (10/7/97), 5,725,699 (3/10/98) and 5,735,118 (4/7/98)). The moisture uptake data and component percentages are summarized in Table 2.
実施例１６〜２１
配合物を実施例１５のものと同様に混合した。バインダーを酸化剤と同時に加えた。水分の取り込みを実施例２に記述したように決定した。データを表２にまとめる。
Examples 16-21
The formulation was mixed as in Example 15. The binder was added simultaneously with the oxidant. Water uptake was determined as described in Example 2. The data is summarized in Table 2.
表１からわかる様に、本発明の配合物は従来の黒色粉末及び従来の黒色火薬代替物組成物と等しいか又はそれらより優れた弾道性能を有した。硫黄を含まない態様のものでは、弾道性能は実施例１、３、５、７及び８において特に良好であり、これらの実施例においては全酸化剤濃度は６５〜８０重量％の範囲で存在し、そしてフェノールフタレインが１３〜２２重量％の範囲で存在する。実施例２は比較的おおきな７０ミクロンのフェノールフタレイン粒子を使用する。実施例６及び９は８０重量％より多い酸化剤を有する。こっらの因子は、実施例１、３〜５及び７と比較して弾道性能、特に平均スロープ測定値を下げる。 As can be seen from Table 1, the formulations of the present invention had ballistic performance equal to or better than conventional black powder and conventional black powder substitute compositions. For those embodiments that do not contain sulfur, ballistic performance is particularly good in Examples 1, 3, 5, 7, and 8, in which the total oxidant concentration is in the range of 65-80 wt%. And phenolphthalein is present in the range of 13-22% by weight. Example 2 uses relatively large 70 micron phenolphthalein particles. Examples 6 and 9 have greater than 80 wt% oxidizer. These factors reduce ballistic performance, especially the average slope measurement, compared to Examples 1, 3-5 and 7.
表２は、フェノールフタレインの結晶がもつ、その有機結晶質状態でのフェノールフタレインと比較して高い水分取り込みを示す。有機結晶質化合物の塩に対する比は水分取り込みと逆相関し、すなわち比が増すほど水分取り込みは減少する。 Table 2 shows the high water uptake of phenolphthalein crystals compared to phenolphthalein in its organic crystalline state. The ratio of organic crystalline compound to salt is inversely related to water uptake, ie, water uptake decreases as the ratio increases.
本発明の前述の詳細な説明は本発明の原理及びその実際上の用途を説明し、それによって本技術の当業者が本発明を種々の態様及び意図あれる実際上の用途に適した種々の修正を理解できるようにする目的のために与えらている。この説明は網羅的であることを意図するものでも、開示した正確な態様に本発明を限定することを意図するものではない。修正及び均等が本技術における当業者に明らかであり、そして特許請求の範囲の精神及び範囲内に含まれる。 The foregoing detailed description of the invention explains the principles of the invention and its practical application, so that those skilled in the art can make the invention suitable for various aspects and intended practical applications. It is given for the purpose of making the modifications understandable. This description is intended to be exhaustive and is not intended to limit the invention to the precise form disclosed. Modifications and equivalents will be apparent to those skilled in the art and are included within the spirit and scope of the claims.
Claims (61)
４０〜９０重量％の酸化剤粒子、酸化剤粒子は３０ミクロン以下の平均粒径を有し、かつアルカリ金属硝酸塩及び硝酸アンモニウムより成る群から選択される少なくとも１種、及びアルカリ金属過塩素酸塩及び過塩素酸アンモニウムより成る群から選択される少なくとも１種を含む、
有機結晶質粒子及び所望による少なくとも１種の有機結晶質粒子の塩、ここで有機結晶質粒子及び所望による少なくとも１種の有機結晶質粒子の塩が、固体火工品組成物の全重量の１０〜６０重量％を占める、ここで有機結晶質粒子が、フェノール化合物と無水フタル酸との反応から誘導される有機結晶質化合物及びフェノールフタレインより成る群から選択される少なくとも１種を含む有機結晶質化合物を含む；並びに
非吸湿性バインダー
から成る、前記の固形火工品組成物。A solid pyrotechnic composition,
40 to 90% by weight of oxidant particles, the oxidant particles having an average particle size of 30 microns or less and at least one selected from the group consisting of alkali metal nitrates and ammonium nitrates, and alkali metal perchlorates and Comprising at least one selected from the group consisting of ammonium perchlorate,
The organic crystalline particles and optionally a salt of at least one organic crystalline particle, wherein the organic crystalline particles and optionally a salt of at least one organic crystalline particle are 10 of the total weight of the solid pyrotechnic composition. Organic crystals comprising ˜60% by weight, wherein the organic crystalline particles comprise at least one selected from the group consisting of organic crystalline compounds derived from the reaction of phenolic compounds and phthalic anhydride and phenolphthalein A quality compound; and
Non-hygroscopic binder
Consisting of, said of solid pyrotechnic composition.
４０〜９０重量％の酸化剤粒子、酸化剤粒子は３０ミクロン以下の平均粒径を有し、かつアルカリ金属過塩素酸塩及び過塩素酸アンモニウムより成る群から選択される少なくとも１種、及び所望によってアルカリ金属硝酸塩及び硝酸アンモニウムより成る群から選択される少なくとも１種を含む；
有機結晶質粒子、及び所望による少なくとも１種の有機結晶質粒子の塩、ここで有機結晶質粒子及び所望による少なくとも１種の有機結晶質粒子の塩が、固体火工品組成物の全重量の１０〜６０重量％を構成し、ここで有機結晶質粒子が、フェノール化合物と無水フタル酸との反応から誘導される有機結晶質化合物及びフェノールフタレインより成る群から選択される少なくとも１種を含む結晶質有機化合物を含み；並びに
非吸湿性バインダーから成り、
固体火工品組成物の２０〜９０重量％が、アルカリ金属過塩素酸塩及び過塩素酸アンモニウムより成る群から選択される少なくとも１種から成る
前記の固形火工品組成物。A solid pyrotechnic composition,
40-90% by weight oxidant particles, the oxidant particles having an average particle size of 30 microns or less and at least one selected from the group consisting of alkali metal perchlorates and ammonium perchlorate, and desired Including at least one selected from the group consisting of alkali metal nitrates and ammonium nitrates ;
Organic crystalline particles, and salts of at least one organic crystalline particles that by the desired salt wherein the organic crystalline particles and at least one organic crystalline particles by desirable, solid pyrotechnic compositions all At least one selected from the group consisting of organic crystalline compounds derived from the reaction of phenolic compounds with phthalic anhydride and phenolphthalein, comprising 10-60% by weight of the organic crystalline particles A crystalline organic compound comprising:
Consisting of a non-hygroscopic binder,
The solid pyrotechnic composition as described above, wherein 20 to 90% by weight of the solid pyrotechnic composition comprises at least one selected from the group consisting of alkali metal perchlorates and ammonium perchlorate.
アルカリ金属ヒドロキシドと少なくとも１種の有機結晶質化合物とを組み合わせて、少なくとも１種の有機結晶質化合物の塩を含む溶液を生成すること、
該溶液と硝酸とを組み合わせてアルカリ金属硝酸塩を形成し、そして該塩を粒子態の少なくとも１種の有機結晶質化合物に転化してもどすこと、ここでアルカリ金属硝酸塩粒子及び粒子形態の少なくとも１種の有機結晶質化合物はそれぞれ３０ミクロン以下の平均粒径を有し、
アルカリ金属硝酸塩粒子及び粒子形態の少なくとも１種の有機結晶質化合物を、追加の酸化剤粒子と組み合わせて火工品組成物を形成すること、ここで追加の酸化剤粒子は３０ミクロン以下の平均粒径を有し、そしてアルカリ金属過塩素酸塩及び過塩素酸アンモニウムから成る群から選択される少なくとも１種を含み、そして追加の酸化剤粒子は所望によってアルカリ金属硝酸塩及び硝酸アンモニウムより成る群から選択される少なくとも１種をさらに含み、
所望によって火工品組成物を乾燥して固体火工品組成物を得ること
を含み、
該固体火工品組成物の全重量の４０〜９０重量％が、アルカリ金属硝酸塩粒子及び追加の酸化剤粒子から成る、
前記の方法。A method for producing a solid pyrotechnic composition comprising:
Combining an alkali metal hydroxide and at least one organic crystalline compound to produce a solution comprising a salt of at least one organic crystalline compound;
Combining the solution with nitric acid to form an alkali metal nitrate and converting the salt back into at least one organic crystalline compound in particulate form, wherein the alkali metal nitrate particles and at least one in particulate form Each of the organic crystalline compounds has an average particle size of 30 microns or less,
At least one organic crystalline compound of an alkali metal nitrate particles and particle morphology, forming a pyrotechnic composition in combination with an additional oxidizing agent particles, wherein additional oxidizer particles 30 microns or less in average particle And having at least one selected from the group consisting of alkali metal perchlorates and ammonium perchlorates, and the additional oxidant particles are optionally selected from the group consisting of alkali metal nitrates and ammonium nitrates. Further comprising at least one of
Optionally drying the pyrotechnic composition to obtain a solid pyrotechnic composition;
40-90% by weight of the total weight of the solid pyrotechnic composition consists of alkali metal nitrate particles and additional oxidant particles;
Said method.
アルカリ金属ヒドロキシドと少なくとも１種の有機結晶質化合物とを組み合わせて、少なくとも１種の有機結晶質化合物の塩を含む溶液を生成すること、
該溶液と過塩素酸とを組み合わせてアルカリ金属過塩素酸塩を形成し、そして有機結晶質化合物の該塩を粒子形態の少なくとも１種の有機結晶質粒子に転化してもどすこと、ここでアルカリ金属過塩素酸塩粒子及び少なくとも１種の粒子形態の有機結晶質化合物はそれぞれ３０ミクロン以下の平均粒径を有し、
アルカリ金属過塩素酸塩粒子及び粒子形態の少なくとも１種の有機結晶質化合物を、追加の酸化剤粒子と組み合わせて火工品組成物を形成するこ、ここで追加の酸化剤粒子は３０ミクロン以下の平均粒径を有し、そして
アルカリ金属硝酸塩及び硝酸アンモニウムから成る群から選択される少なくとも１種と、
アルカリ金属過塩素酸塩及び過塩素酸アンモニウムより成る群から選択される少なくとも１種
のうちの少なくとも１種を含み、そして
所望によって火工品組成物を乾燥して固体火工品組成物を得ること
を含み、
該固体火工品組成物の全重量の４０〜９０重量％が、アルカリ金属過塩素酸粒子及び追加の酸化剤粒子から成る、
前記の方法。A method for producing a solid pyrotechnic composition comprising:
Combining an alkali metal hydroxide and at least one organic crystalline compound to produce a solution comprising a salt of at least one organic crystalline compound;
Combining the solution with perchloric acid to form an alkali metal perchlorate and converting the salt of the organic crystalline compound into at least one organic crystalline particle in particulate form, wherein an alkali The metal perchlorate particles and the organic crystalline compound in at least one particle form each have an average particle size of 30 microns or less;
Alkali metal perchlorate particles and at least one organic crystalline compound in particle form are combined with additional oxidant particles to form a pyrotechnic composition, wherein the additional oxidant particles are 30 microns or less And at least one selected from the group consisting of alkali metal nitrates and ammonium nitrates,
Comprises at least one at least one of selected from the group consisting of ammonium alkali metal perchlorate and perchloric acid, and obtaining a solid pyrotechnic composition by drying the pyrotechnic composition by the desired Including
40-90% by weight of the total weight of the solid pyrotechnic composition consists of alkali metal perchloric acid particles and additional oxidant particles;
Said method.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26111101P | 2001-01-12 | 2001-01-12 | |
| PCT/US2002/021566 WO2003022783A2 (en) | 2001-01-12 | 2002-01-11 | Low humidity uptake solid pyrotechnic compositions, and methods for making the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005506945A JP2005506945A (en) | 2005-03-10 |
| JP3981356B2 true JP3981356B2 (en) | 2007-09-26 |
Family
ID=22991995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003526862A Expired - Lifetime JP3981356B2 (en) | 2001-01-12 | 2002-01-11 | Solid pyrotechnic composition with low moisture uptake and method for producing the same |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US20020148541A1 (en) |
| EP (1) | EP1427683A2 (en) |
| JP (1) | JP3981356B2 (en) |
| AU (1) | AU2002353766A1 (en) |
| CA (1) | CA2434730A1 (en) |
| WO (1) | WO2003022783A2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1029465C2 (en) * | 2005-07-06 | 2007-01-09 | Tno | A pyrotechnic composition. |
| CN103880570A (en) * | 2014-03-15 | 2014-06-25 | 南京理工大学 | Pyrotechnic composition oxidant |
| CN106588522B (en) * | 2016-11-29 | 2018-05-29 | 湖北航天化学技术研究所 | Low melting point thermoplastic propellant and preparation method thereof |
| CN113354493A (en) * | 2021-07-16 | 2021-09-07 | 关秀琼 | Pyrotechnic propellant and preparation method thereof |
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| US2441248A (en) * | 1941-08-07 | 1948-05-11 | Ici Ltd | Fast burning delay fuze |
| GB630981A (en) * | 1946-11-22 | 1949-10-25 | Percy Alfred Harry Goldsmith | Improvements in and relating to compositions for ignition of combustible gas producing charges or heating mixtures |
| US3026674A (en) * | 1958-02-24 | 1962-03-27 | Phillips Petroleum Co | Solid propellant rocket motor |
| US3293056A (en) * | 1958-03-11 | 1966-12-20 | Walter S Baker | Composition for a combustible cartridge case |
| US3770524A (en) * | 1958-10-22 | 1973-11-06 | Rohm & Haas | Composite propellants containing polymers of trinitratopentaerythrityl acrylate |
| US3388554A (en) * | 1959-11-02 | 1968-06-18 | Solid Fuels Corp | Organic fusible solid fuel binders and stabilizers and method of extruding and burning |
| US3728173A (en) * | 1969-10-17 | 1973-04-17 | Intermountain Res & Eng Co Inc | Dense explosive slurry compositions of high energy containing a gum mixture |
| US3862866A (en) * | 1971-08-02 | 1975-01-28 | Specialty Products Dev Corp | Gas generator composition and method |
| US3902934A (en) * | 1972-06-08 | 1975-09-02 | Specialty Products Dev Corp | Gas generating compositions |
| US4047987A (en) * | 1973-02-27 | 1977-09-13 | Director-General Of The Agency Of Industrial Science And Technology | Underwater blasting explosives |
| US4128443A (en) * | 1975-07-24 | 1978-12-05 | Pawlak Daniel E | Deflagrating propellant compositions |
| GB1601392A (en) * | 1978-04-12 | 1981-10-28 | Pyrodex Corp | Gas generating compositions |
| US4238253A (en) * | 1978-05-15 | 1980-12-09 | Allied Chemical Corporation | Starch as fuel in gas generating compositions |
| USH72H (en) * | 1984-01-23 | 1986-06-03 | The United States Of America As Represented By The Secretary Of The Army | Organic substitutes for charcoal in black powder |
| US4570540A (en) * | 1984-08-09 | 1986-02-18 | Morton Thiokol, Inc. | LOVA Type black powder propellant surrogate |
| US4915755A (en) * | 1987-10-02 | 1990-04-10 | Kim Chung S | Filler reinforcement of polyurethane binder using a neutral polymeric bonding agent |
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| US5449423A (en) * | 1992-10-13 | 1995-09-12 | Cioffe; Anthony | Propellant and explosive composition |
| US5320691A (en) * | 1993-07-08 | 1994-06-14 | The United States Of America As Represented By The Secretary Of The Army | Charcoal-free black powder type granules and method of production |
| US5531845A (en) * | 1994-01-10 | 1996-07-02 | Thiokol Corporation | Methods of preparing gas generant formulations |
| US5725699A (en) * | 1994-01-19 | 1998-03-10 | Thiokol Corporation | Metal complexes for use as gas generants |
| EP0740645B1 (en) * | 1994-01-19 | 2012-08-22 | Alliant Techsystems Inc. | Metal complexes for use as gas generants |
| US5756929A (en) * | 1996-02-14 | 1998-05-26 | Automotive Systems Laboratory Inc. | Nonazide gas generating compositions |
| US5726378A (en) * | 1996-04-01 | 1998-03-10 | Hodgdon Powder Company, Inc. | Unitary propellant charge for muzzle loading firearms |
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| US5670098A (en) * | 1996-08-20 | 1997-09-23 | Thiokol Corporation | Black powder processing on twin-screw extruder |
| WO1998042640A1 (en) * | 1997-03-21 | 1998-10-01 | Cordant Technologies, Inc. | Method for manufacture of black powder and black powder substitute |
| US5917146A (en) * | 1997-05-29 | 1999-06-29 | The Regents Of The University Of California | High-nitrogen energetic material based pyrotechnic compositions |
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| DE19840993B4 (en) * | 1998-09-08 | 2006-03-09 | Trw Airbag Systems Gmbh & Co. Kg | Use of a gas-generating mixture as ignition mixture in a gas generator |
| US6045638A (en) * | 1998-10-09 | 2000-04-04 | Atlantic Research Corporation | Monopropellant and propellant compositions including mono and polyaminoguanidine dinitrate |
| US6214139B1 (en) * | 1999-04-20 | 2001-04-10 | The Regents Of The University Of California | Low-smoke pyrotechnic compositions |
-
2002
- 2002-01-11 EP EP02789146A patent/EP1427683A2/en not_active Withdrawn
- 2002-01-11 JP JP2003526862A patent/JP3981356B2/en not_active Expired - Lifetime
- 2002-01-11 WO PCT/US2002/021566 patent/WO2003022783A2/en active Search and Examination
- 2002-01-11 US US10/046,008 patent/US20020148541A1/en not_active Abandoned
- 2002-01-11 AU AU2002353766A patent/AU2002353766A1/en not_active Abandoned
- 2002-01-11 CA CA002434730A patent/CA2434730A1/en not_active Abandoned
-
2005
- 2005-08-26 US US11/213,416 patent/US20060042731A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP1427683A2 (en) | 2004-06-16 |
| CA2434730A1 (en) | 2003-03-20 |
| US20060042731A1 (en) | 2006-03-02 |
| WO2003022783A3 (en) | 2004-04-01 |
| WO2003022783A2 (en) | 2003-03-20 |
| JP2005506945A (en) | 2005-03-10 |
| AU2002353766A1 (en) | 2003-03-24 |
| US20020148541A1 (en) | 2002-10-17 |
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