US20140238258A1 - Colored Pyrotechnic Smoke-Producing Composition - Google Patents
Colored Pyrotechnic Smoke-Producing Composition Download PDFInfo
- Publication number
- US20140238258A1 US20140238258A1 US13/776,767 US201313776767A US2014238258A1 US 20140238258 A1 US20140238258 A1 US 20140238258A1 US 201313776767 A US201313776767 A US 201313776767A US 2014238258 A1 US2014238258 A1 US 2014238258A1
- Authority
- US
- United States
- Prior art keywords
- composition
- smoke
- dye
- fuel
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 157
- 239000000779 smoke Substances 0.000 claims abstract description 92
- 239000000446 fuel Substances 0.000 claims abstract description 31
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002826 coolant Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 16
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 15
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 15
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 14
- 229920001220 nitrocellulos Polymers 0.000 claims abstract description 14
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims abstract description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000007858 starting material Substances 0.000 claims abstract description 7
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 5
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims abstract description 5
- 229920002472 Starch Polymers 0.000 claims abstract description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 5
- 229930006000 Sucrose Natural products 0.000 claims abstract description 5
- 239000008121 dextrose Substances 0.000 claims abstract description 5
- 239000008101 lactose Substances 0.000 claims abstract description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 239000008107 starch Substances 0.000 claims abstract description 5
- 235000019698 starch Nutrition 0.000 claims abstract description 5
- 239000005720 sucrose Substances 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 50
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 239000008188 pellet Substances 0.000 claims description 11
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 claims description 5
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 5
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 claims description 5
- NLXFWUZKOOWWFD-UHFFFAOYSA-N 1-(2-hydroxyethylamino)-4-(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCO)=CC=C2NC NLXFWUZKOOWWFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004156 Azodicarbonamide Substances 0.000 claims description 4
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 4
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 4
- SVTDYSXXLJYUTM-UHFFFAOYSA-N disperse red 9 Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC SVTDYSXXLJYUTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 claims description 4
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- SSGALQHXKMAJTL-UHFFFAOYSA-N 1,4-diamino-2,3-dihydroanthraquinone Chemical compound C1=CC=C2C(=O)C3=C(N)CCC(N)=C3C(=O)C2=C1 SSGALQHXKMAJTL-UHFFFAOYSA-N 0.000 claims description 2
- VAIIGTVFJAYEKS-UHFFFAOYSA-N 2-(6-methylquinolin-2-yl)indene-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C1C1=NC2=CC=C(C)C=C2C=C1 VAIIGTVFJAYEKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- ALLOLPOYFRLCCX-VHEBQXMUSA-N amethoxybenzenazo-β-naphthol Chemical compound COC1=CC=CC=C1\N=N\C1=C(O)C=CC2=CC=CC=C12 ALLOLPOYFRLCCX-VHEBQXMUSA-N 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920001290 polyvinyl ester Polymers 0.000 claims description 2
- 229920001289 polyvinyl ether Polymers 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 4
- 238000007789 sealing Methods 0.000 claims 2
- 238000000227 grinding Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 38
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 19
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 20
- 238000002485 combustion reaction Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002893 slag Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- -1 carboxylate ion Chemical class 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000003550 marker Substances 0.000 description 5
- 230000009972 noncorrosive effect Effects 0.000 description 5
- 231100000252 nontoxic Toxicity 0.000 description 5
- 230000003000 nontoxic effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000013401 experimental design Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical group [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 231100000260 carcinogenicity Toxicity 0.000 description 2
- 230000007670 carcinogenicity Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- UFVDYITXJBCPMW-UHFFFAOYSA-N chembl1491913 Chemical compound C1=CC=C2C(O)=C(C(=N)CCC3=N)C3=C(O)C2=C1 UFVDYITXJBCPMW-UHFFFAOYSA-N 0.000 description 2
- ALLOLPOYFRLCCX-UHFFFAOYSA-N chembl1986529 Chemical compound COC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ALLOLPOYFRLCCX-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004200 deflagration Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- UIBAAMBCJDNDSQ-UHFFFAOYSA-N 4-[[2-chloro-4-[3-chloro-4-[[3-methyl-1-(4-methylphenyl)-5-oxo-4h-pyrazol-4-yl]diazenyl]phenyl]phenyl]diazenyl]-5-methyl-2-(4-methylphenyl)-4h-pyrazol-3-one Chemical compound CC1=NN(C=2C=CC(C)=CC=2)C(=O)C1N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C1=O)C(C)=NN1C1=CC=C(C)C=C1 UIBAAMBCJDNDSQ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000000981 bystander Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 210000000349 chromosome Anatomy 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001141 propulsive effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 230000000007 visual effect Effects 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
- C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal
- C06B29/16—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal with a nitrated organic compound
- C06B29/20—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal with a nitrated organic compound the compound being nitrocellulose
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B4/00—Fireworks, i.e. pyrotechnic devices for amusement, display, illumination or signal purposes
- F42B4/30—Manufacture
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D3/00—Generation of smoke or mist (chemical part)
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H9/00—Equipment for attack or defence by spreading flame, gas or smoke or leurres; Chemical warfare equipment
- F41H9/06—Apparatus for generating artificial fog or smoke screens
- F41H9/08—Smoke-pots without propulsive charge, i.e. stationary
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
- F42B12/02—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect
- F42B12/36—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information
- F42B12/46—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information for dispensing gases, vapours, powders or chemically-reactive substances
- F42B12/48—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information for dispensing gases, vapours, powders or chemically-reactive substances smoke-producing, e.g. infrared clouds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B4/00—Fireworks, i.e. pyrotechnic devices for amusement, display, illumination or signal purposes
Definitions
- the present invention relates to a smoke-producing pyrotechnic composition that is useful primarily in pyrotechnics for the production of colored smokes. More particularly, the present invention is related to generally cool-burning, non-toxic, and non-corrosive smoke producing compositions, which incorporate at least one affordable nitrogen-rich compound in addition to an oxidizer-fuel system, smoke-forming substance, and binder.
- Affordable nitrogen-rich compounds that are suitable for use with the current invention can include guanidine nitrate, guanidine carbonate, or dicyandiamide; azodicarbonamide, melamine, and oxamide.
- the ability to produce smoke at a particular location may provide the basis for a remote signaling system.
- a remote signaling system may have application in search and rescue operations and in military exercises.
- Smoke of a particular color and density may also be desirable for training purposes.
- individuals working in a fire-prone environment, such as on an aircraft or ship it would also be desirable to have the capability of simulating smoke produced by a fire in order to provide a realistic fire drill.
- Smoke can be used as a marker for various purposes.
- a smoke marker can be seen from substantial distances, both from the ground and from the air. Accordingly, a smoke marker would be useful in military operations, search and rescue, certain types of industrial projects, or in any other situation in which it is important to find and mark a particular location.
- smoke-producing devices and compositions In a military context, the need for smoke-producing devices and compositions is well appreciated. Not only can smoke be used as a marker for search and rescue, but smoke may also be used to mark a particular target. It can also be used as a marker to determine the position of specific personnel and equipment.
- Smoke can also be used to obscure vision.
- a smoke shield can be very helpful in conducting military operations in order to prevent adverse forces from obtaining a clear view of the operations. For example, it may be desirable to use a vision obscuring smoke in order to move troops and equipment under at least partial cover.
- Prior art colored smoke formulations have employed the use of mixtures containing a fuel, an oxidizer, and a dye.
- the principle behind the use of such formulations lies in the reaction between the fuel and oxidizer, and the accompanying release of a large amount of energy during the reaction.
- the exothermic reaction releases the energy contained in the bonds of the highly structured fuel molecule as heat.
- This causes the dye component of the formulation to undergo a series of phase transitions from a solid to a liquid and ultimately to a gas.
- the temperature of the fuel-oxidizer reaction is too high, the dye will degrade, and the quantity and color quality of smoke generated will be unsatisfactory.
- the dye exists as a solid crystal at standard temperature and pressure.
- heat generated by a fuel-oxidizer reaction is applied to the solid crystal, dislocations of the molecules occur within the crystalline lattice.
- molecules of the dye become detached from the central lattice, a liquid is formed.
- the individual molecules of the dye begin to move faster and faster.
- the molecules translate through space, rotating about the axes of the dye structure, and vibrate in many complex modes. This molecular activity is responsible for the transition of the dye molecules from the liquid phase to the gas phase.
- Another problem encountered in the search for a desirable smoke-generating composition is the production of a solid residue as conventional smoke-producing compositions burn.
- the solid residue reaction product contributes to the formation of waste products such as slag and solid clinkers.
- waste products such as slag and solid clinkers.
- solid materials accumulate in the core of a pyrotechnic smoke-producing munition, they prevent the gas phase dye molecules from escaping into the environment.
- deflagration can occur, which can cause injury to bystanders, or result in only a limited release of colored smoke.
- the formation of slag increases the decomposition of the dye vapor, which may lead to color deterioration.
- Another major drawback of using such mixtures is the hazard created by the creation of a flame front at the moment of ignition of the main filling composition.
- a smoke grenade has been observed to emit a flame front with a height of approximately 4-10 inches through the grenade's emission ports. The flame from was observed to last from 1-5 seconds while the smoke charge began burning. This behavior can create safety hazards to personnel and equipment, as well as potentially causing brush and grass fires in dry environments with significantly elevated fire danger conditions.
- the various embodiments of the present invention substantially fulfill at least some of these needs.
- the flameless igniting slurry composition according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in doing so provides a composition primarily developed for the purpose of providing a cool-burning, non-toxic, and non-corrosive smoke producing composition.
- the present invention provides an improved colored pyrotechnic smoke-producing composition, and overcomes the above-mentioned disadvantages and drawbacks of the prior art.
- the general purpose of the present invention which will be described subsequently in greater detail, is to provide an improved colored pyrotechnic smoke-producing composition that has all the advantages of the prior art mentioned above.
- the preferred embodiment of the present invention essentially comprises a composition of an oxidizer, a fuel, a flame retardant, a dye, a coolant, and a binder.
- the oxidizer may be potassium chlorate.
- the fuel may be starch, dextrose, lactose, and/or sucrose.
- the coolant may be sodium bicarbonate or magnesium carbonate.
- the binder may be nitrocellulose or a halogen-free thermoplastic.
- the flame retardant may be one or more nitrogen-rich compounds.
- the composition may be in pelletized form or in the form of a solid charge.
- the composition may consist of on a mass basis oxidizer 20-35%, fuel 15-25%, flame retardant 5-15%, dye 27-40%, coolant 8-18%, and binder 1-2%.
- the invention may be a device consisting of a body filled with the composition and a first fire starter composition, and an attached squib igniter.
- the body may be a grenade.
- a process for producing the composition is also disclosed.
- FIG. 1 is a flowchart of the manufacturing process for the current embodiment of the colored pyrotechnic smoke-producing composition constructed in accordance with the principles of the present invention.
- An embodiment of the process for manufacturing a colored pyrotechnic smoke-producing composition of the present invention is shown and generally designated by the reference numeral 10 .
- the invention relates to a smoke-producing pyrotechnic composition and more particularly, is related to generally cool-burning, non-toxic and non-corrosive smoke producing compositions, which incorporate:
- High-energy reactions are generally classified as “burning” (approximate reaction velocity in the range of mm or cm s ⁇ 1 ), “deflagration” (m s ⁇ 1 ), or “detonation” (km s ⁇ 1 ).
- An ideal dye material for this application transforms “sublimes” directly from the solid phase to the gas phase with little or no intermediate liquid phase.
- the direct transformation to a gas enhances the likelihood of the dye molecules escaping from the solid matrix made of fuel, oxidizer, and dye to the external environment without the dye molecules reaching an undesirably high temperature.
- dyes are sought for the composition that have the property of sublimation at increased temperatures and normal pressures.
- flame suppressant/flame retardant compounds act in one of two ways: either by preventing ignition of a product or by preventing the spread of a fire once a product is ignited.
- the ignition susceptibility of a product is lowered when the flame retardant increases the net heat capacity of the product.
- flame retardants can reduce the tendency of the fire to spread by reacting with the product and forming a less flammable char or noncombustible gaseous layer along the boundary of the fire.
- compositions that are generally non-toxic, non-corrosive, and that can be formulated to burn at lower temperatures and with a lower energy output while still producing effective smoke output.
- the combustion temperature is at least 400° C. (750° F.). At this temperature, the dye is nearly completely destroyed, making the composition ineffective at producing smoke.
- the combustion temperature of the smoke-generating composition of the present invention is reduced to a range from 100° to 250° C. (200 to 480° F.). At the lower end of this range, thermal degradation of the dye is largely prevented, resulting in the effective production of colored smoke.
- the combustion temperature drops to a range between 190° and 300° C. (375 to 575° F.). The temperature reduction is achieved by the guanidine nitrate catalyzing the decomposition of the chlorate, which makes it possible for the decomposition reaction to occur at a lower temperature than would be conventionally required.
- the nitrogen-rich compounds suitable for use in this invention have been found to be excellent additives for use in a smoke-producing composition containing a degradable dye.
- the cited additives have been found to be a very efficient coolant because they are nitrogen producing agents that act as flame retardants. Because the additives' decomposition process generates the liberation of gases (carbon dioxide and nitrogen), they assist sublimation of the organic dye and provide thermal protection from the fuel-oxidizer reaction.
- the additives also inhibit slag build-up and facilitate the production of uniformly porous slag. These slag characteristics enhance the production of color in the smoke generated.
- conventional pyrotechnic compositions pass the vaporized dye through significant amounts of hot slag of limited porosity before the dye escapes into the environment, which has a deleterious effect on the color of the vaporized dye.
- Nitrogen-rich compounds are not only remarkable energy-rich and oxygen-nitrogen-containing compounds that act exothermically to supply heat to the smoke-generating reaction.
- the nitrogen-rich compounds also simultaneously yield decomposition products that neutralize the acids generated by the smoke-producing composition of the present invention.
- the dyes which may be used in this invention corresponding to the color standard FED-STD-595C color chip, are listed by the Society of Dyers and Colorists in dye classification materials according to chemical structure, and include the following:
- compositions of the present invention also incorporate at least one binder to provide the desired consistency.
- a binding agent from the group of the halogen-free thermoplastics can be used for the physical stabilization of the mixture of the pyrotechnic smoke-producing composition.
- the binding agent can preferably be polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl ester, or polyvinyl ether.
- nitrocellulose is specifically desirable in that it results in a decreased solid residue within the burned grain. Nitrocellulose is used in solution (6 to 12% nitrocellulose dissolved in acetone).
- Binders of these types in addition to providing desirable binding characteristics, produce only a small energy output upon combustion. This is important in avoiding very high-energy outputs, high temperatures, and flames, which render smoke producing compositions dangerous and difficult to handle.
- composition of the present invention also includes one or more oxidizer compounds. It is found that potassium chlorate (KClO 3 ) is an efficient oxidizer and produces good results when coupled with the fuel and previously mentioned nitrogen-rich compounds.
- the present invention includes a fuel.
- the fuel is preferably a relatively low energy fuel similar to the binder. It is also preferred that the fuel produce gaseous reaction products capable of carrying the smoke producing agent into the environment.
- suitable fuels include starch, dextrose, and polyhydroxylic compounds such as lactose and sucrose.
- magnesium carbonate acts as a buffer, which prevents autocatalytic decomposition of the KClO 3 . Magnesium carbonate also functions as a coolant when the smoke-producing composition combusts.
- sodium bicarbonate can be used.
- Another useful additive in the present invention is aluminum. In some cases, atomized aluminum can provide additional thermal conductivity within the composition. This results in more uniform heat transfer and ignition of the fuel.
- ingredients of the composition may be within the ranges indicated in Table 2:
- the pyrotechnic smoke-producing compositions were produced as follows: The process starts ( 12 ) by individually weighing ( 14 ) a quantity of nitrogen-rich compound(s) 16 , a quantity of oxidizer 18 , a quantity of fuel 20 , a quantity of dye 22 , a quantity of magnesium carbonate 24 , and a quantity of nitrocellulose 26 . The weighed dry ingredients are then added to a mixing bowl ( 28 ) and undergo a first mixing step ( 30 ).
- the mixer utilized as a Hobart planetary gear-style mixer.
- acetone solvent 32 (0.2-0.3 L/kg of the dry mix resulting from step 30 ) is measured ( 34 ) and subsequently added to the mixing bowl ( 36 ).
- the resulting mixture undergoes a second mixing step ( 38 ).
- the mix is a very viscous wet slurry of the components.
- the acetone begins to evaporate, and the composition assumes the consistency of wet dough.
- Mixing continues, and as more acetone evaporates, the doughy composition breaks into increasingly smaller chunks. Mixing is further continued until all visible acetone has evaporated and relatively dry, well-mixed spherical chunks of agglomerated mix have been produced.
- the entire mixing process can be accomplished in approximately 25 minutes for each kilogram of finished mixture when a 5-quart mixing bowl is used.
- compositions ingredients can also be blended together as dry powders using standard pyrotechnic techniques.
- wet mixing technique using acetone is preferable because it is safer and produces a more homogeneous mixture.
- the smaller spherical chunks are poured ( 40 ) from the mixing bowl into drying trays.
- the mix is spread on the drying trays so the mix is flat at a uniform level in the trays.
- the trays are placed in an oven ( 42 ) maintained at 60 ⁇ 5° C. (140 ⁇ 10° F.), for 24 to 36 hours to evaporate any residual acetone.
- the material is ground ( 44 ) to achieve small grains of pyrotechnic mixture, which can be further loaded or preferably pelletized ( 46 ).
- Pelletizing can be achieved by harshly mixing the powdered ingredients and then using a pill press to produce pellets.
- the powdered mixture can be granulated and then formed into noodles by extruding the mixture through a screen.
- Pelletizing has been found advantageous because the mixed powder has some undesirable characteristics.
- the powder tends to separate, with the oxidizer at the bottom and the fuel at the top. As a result, when the powder burns, it burns with different characteristics depending upon the degree to which the powder mixture is homogeneous.
- the powder may be loosely packed or tightly packed, which also affects its combustion characteristics. These variations in homogeneity and packing can lead to inconsistent combustion results when using the composition in powder form. When using the composition in pellet form, the combustion results are more consistent.
- the pellets are hydraulically loaded ( 48 ) into grenade bodies 50 or pelletized to adjust the combustion characteristics of the composition so the devices have the required burning time.
- the load applied to the surface of the mix in the grenade body is about 5000 to 7000 pounds per square inch (psi).
- a MIL SPEC No. 508 first fire starter mixture or a flameless first fire starter mixture 52 is applied to the grenades, and tops 54 are sealed onto the bodies ( 56 ).
- a No. 565 squib igniter 58 can be used to ignite the grenade.
- the loaded and sealed grenades are the end result ( 60 ) of the process.
- the colored smokes produced by the pyrotechnic compositions of the present invention were compared to smoke produced by conventional formulations based on 1,4-benzendicarboxylic acid or aliphatic dicarboxylic acids.
- Each smoke color produced by the pyrotechnic compositions of the present invention was also compared to the corresponding color standard FED-STD-595C color chip. This was accomplished by making the various pyrotechnic mixtures and forming them into grenades in the manner previously described. The grenades were then burned adjacent to one another to enable side-by-side visual comparison.
- the subjective evaluation of the color quality the smoke produced provided a reliable indication of the improved effectiveness and efficiency of the pyrotechnic composition of the present invention.
- compositions of the present invention were placed in standard military-style metal cans used for signal colored smoke grenade.
- the compositions were compacted as pressed pellets as a first experimental design, and as solid charges in a second experimental design (see the second column of Table 3 below).
- the weight of pyrotechnic filling was about 210 to 235 grams (7.5 to 8.2 oz.).
- the pressed or pelletized grains were ignited, and their burning characteristics, including ignition time and flame, burning time, burning temperature, can temperature and pressure were recorded. The results of these tests are summarized in Table 3.
- guanidine salts such as guanidine nitrate
- guanidine nitrate are conventionally employed in the an of ignition as an exothermic reactant in a smoke grenade (U.S. Pat. No. 4,238,254), or as an additional fuel for a flare igniter (U.S. Pat. No. 6,170,399). This makes their usage in the current invention for their flame retardant properties nonobvious.
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Abstract
Description
- The present invention relates to a smoke-producing pyrotechnic composition that is useful primarily in pyrotechnics for the production of colored smokes. More particularly, the present invention is related to generally cool-burning, non-toxic, and non-corrosive smoke producing compositions, which incorporate at least one affordable nitrogen-rich compound in addition to an oxidizer-fuel system, smoke-forming substance, and binder. Affordable nitrogen-rich compounds that are suitable for use with the current invention can include guanidine nitrate, guanidine carbonate, or dicyandiamide; azodicarbonamide, melamine, and oxamide.
- Effective and safe generation of colored smoke by the vaporization of an organic dye poses a challenging pyrotechnic problem. The military and the fireworks and entertainment industries rely on this technique for the generation of copious quantities of brilliantly colored smoke.
- The requirements for an effective colored-smoke composition include:
-
- The composition must produce sufficient heat to vaporize the dye, as well as produce a sufficient volume of gas to disperse the dye into the surrounding environment.
- The composition must ignite at a low temperature and continue to burn smoothly at a low temperature (well below 1000° C.). If the temperature is too high, the dye molecules will decompose, and the generated smoke's color quality and volume will deteriorate. The use of metal fuels should be avoided in colored smoke-generating compositions because of the high reaction temperatures they may produce.
- Although a low ignition temperature is required, the smoke-generating composition must be stable during manufacturing and storage over the expected range of ambient temperatures.
- The molecules creating the colored smoke must be of low toxicity (including low carcinogenicity). Further, they must readily sublime without decomposition at the temperature of the pyrotechnic reaction to yield a dense smoke of good color quality.
- In various contexts, it is desirable to have the capability to produce smoke suitable for a wide variety of applications. For example, the ability to produce smoke at a particular location may provide the basis for a remote signaling system. Such a system may have application in search and rescue operations and in military exercises. Smoke of a particular color and density may also be desirable for training purposes. For example, in order to train fire fighters, it would be advantageous to simulate specific types of smoke produced by various fire conditions. For individuals working in a fire-prone environment, such as on an aircraft or ship, it would also be desirable to have the capability of simulating smoke produced by a fire in order to provide a realistic fire drill.
- Smoke can be used as a marker for various purposes. A smoke marker can be seen from substantial distances, both from the ground and from the air. Accordingly, a smoke marker would be useful in military operations, search and rescue, certain types of industrial projects, or in any other situation in which it is important to find and mark a particular location.
- In a military context, the need for smoke-producing devices and compositions is well appreciated. Not only can smoke be used as a marker for search and rescue, but smoke may also be used to mark a particular target. It can also be used as a marker to determine the position of specific personnel and equipment.
- Smoke can also be used to obscure vision. A smoke shield can be very helpful in conducting military operations in order to prevent adverse forces from obtaining a clear view of the operations. For example, it may be desirable to use a vision obscuring smoke in order to move troops and equipment under at least partial cover.
- Various types of smoke-producing compositions and devices are presently known. It is known how to judiciously select the components of a smoke-producing composition that uses a sublimable organic coloring medium. By considering the kinetics of combustion and the desired yield of colored smoke, conventional smoke-producing compositions require a strongly exothermic composition, but struggle to limit the degradation of the coloring medium by combustion. A weakly exothermic composition is unsuitable because it permits only a minimal percentage of coloring medium and furnishes only a very mediocre smoke yield that is hardly visible, especially when there is a cloudy or dark sky. A weakly exothermic composition also is difficult to ignite to initiate smoke emission.
- It is also known that it is advantageous to adjust the combustion speed, because a too rapid combustion provokes the destruction of the coloring medium or liberates the smoke too briefly or in a non-workable manner. In contrast, a two slow combustion produces a smoke yield of minimal consequence and tends toward self-extinction of the combustion process. It is known to consider the effects of the reaction thermodynamics by making an appropriate choice of the components of the composition and by the conditions of compression of the composition.
- However, most existing smoke-producing compositions have severe limitations. One of the limitations is that of toxicity. Many smoke-producing compositions incorporate materials that are severely toxic or become irritants when subjected to the heat necessary to produce smoke.
- A variety of dyes have been used in colored smoke mixtures. Many of these dyes are presently under investigation for carcinogenicity and other potential health hazards.
- The materials that work best in colored smokes have several properties in common:
-
- Volatility: The dye must undergo a phase change to the gas state upon heating, without also undergoing substantial decomposition. Only low molecular weight dyes (less than 400 grams/mole) are usually used because volatility typically decreases as molecular weight increases. Salts do not work well: ionic species generally have low volatility because of their strong inter-ionic attractions within the crystalline lattice. Therefore, functional groups such as —COO— (carboxylate ion) and —NR3+ (a substituted ammonium salt) should be avoided.
- Chemical stability: Oxygen-rich functional groups (—NO2; —SO3H) should be avoided. At the typical reaction temperatures of smoke compositions, these groups are likely to release their oxygen, leading to oxidative decomposition of the dye molecules. Groups such as —NH2 and —NHR (amines) are used, but potentially dangerous oxidative coupling reactions can occur in an oxygen rich environment.
- Old-style dyes for military markers and grenades are polycyclic or aromatic amino, hydroxyl, azo and keto compounds, in which unsaturation conjugated with the aromatic structure. Such compounds are known to cause chromosome mutations, which may lead to cancer. Coloring agents for new munitions are chosen to minimize potential carcinogenicity, which increases their cost, but allows recycling of the dyes without high health risks.
- Prior art colored smoke formulations have employed the use of mixtures containing a fuel, an oxidizer, and a dye. The principle behind the use of such formulations lies in the reaction between the fuel and oxidizer, and the accompanying release of a large amount of energy during the reaction. The exothermic reaction releases the energy contained in the bonds of the highly structured fuel molecule as heat. This causes the dye component of the formulation to undergo a series of phase transitions from a solid to a liquid and ultimately to a gas. However, if the temperature of the fuel-oxidizer reaction is too high, the dye will degrade, and the quantity and color quality of smoke generated will be unsatisfactory.
- Conventionally, the dye exists as a solid crystal at standard temperature and pressure. When heat generated by a fuel-oxidizer reaction is applied to the solid crystal, dislocations of the molecules occur within the crystalline lattice. As molecules of the dye become detached from the central lattice, a liquid is formed. As more heat energy is applied, the individual molecules of the dye begin to move faster and faster. The molecules, as a result, translate through space, rotating about the axes of the dye structure, and vibrate in many complex modes. This molecular activity is responsible for the transition of the dye molecules from the liquid phase to the gas phase.
- Although heat is required for the dye to undergo the essential phase changes to produce colored smoke, individual molecules of the dye are subject to degradation at elevated temperatures. If the molecular structure of the dye is subject to forces and energies that are great enough to cleave the molecule's bonds, changes in smoke color or loss of color properties are likely to occur.
- Another problem encountered in the search for a desirable smoke-generating composition is the production of a solid residue as conventional smoke-producing compositions burn. The solid residue reaction product contributes to the formation of waste products such as slag and solid clinkers. When such solid materials accumulate in the core of a pyrotechnic smoke-producing munition, they prevent the gas phase dye molecules from escaping into the environment. As a result, deflagration can occur, which can cause injury to bystanders, or result in only a limited release of colored smoke. Furthermore, the formation of slag increases the decomposition of the dye vapor, which may lead to color deterioration. Only a few dye materials have been found suitable for use in prior art smoke-producing compositions that rely upon the vaporization of an organic dye because most dye materials generate excessive slag or clinkers. The importance of obtaining uniform and porous slag reaction products is already known, as well as the possibilities of selecting components of the smoke-producing composition that enable obtaining such slag. It is also known that the extent of porosity of the slag regulates the smoke yield and favors heat exchange between the components of the smoke-generating composition.
- Other known compositions have the drawback of burning at temperatures that are too high (600-800° C.) or leave too many carbonaceous residues, which are impermeable to the dye molecules in the gas phase. These conditions cause the destruction of the smoke-producing components and therefore demonstrate poor effectiveness in producing colored smokes. Another drawback may be the rapid ascent of the smoke because of the smoke's high temperature, which causes the smoke to dissipate too quickly for the desired effect to be achieved.
- Another major drawback of using such mixtures is the hazard created by the creation of a flame front at the moment of ignition of the main filling composition. For example, a smoke grenade has been observed to emit a flame front with a height of approximately 4-10 inches through the grenade's emission ports. The flame from was observed to last from 1-5 seconds while the smoke charge began burning. This behavior can create safety hazards to personnel and equipment, as well as potentially causing brush and grass fires in dry environments with significantly elevated fire danger conditions.
- In summary, there is a need for effective colored smoke-producing compositions. This need exists in both military and civilian operations. However, many smoke-producing compositions presently used are difficult to handle. Many such compositions are toxic and irritating, requiring special precautions during use. Many such compositions are also corrosive and damaging to both electronic and mechanical equipment. Finally, some compositions produce an excess of heat and flame, again limiting their usefulness and requiring that additional safety measures be taken. For these reasons, conventional smoke-producing compositions are found to be inadequate
- Therefore, a need exists for a new and improved colored pyrotechnic smoke-producing composition that provides is generally non-toxic and non-corrosive, does not incorporate toxic or irritating materials such as zinc, phosphorous, and aromatic organic compounds, which is simple to manufacture and use, and is still in effective smoke producer. In this regard, the various embodiments of the present invention substantially fulfill at least some of these needs. In this respect, the flameless igniting slurry composition according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in doing so provides a composition primarily developed for the purpose of providing a cool-burning, non-toxic, and non-corrosive smoke producing composition.
- The present invention provides an improved colored pyrotechnic smoke-producing composition, and overcomes the above-mentioned disadvantages and drawbacks of the prior art. As such, the general purpose of the present invention, which will be described subsequently in greater detail, is to provide an improved colored pyrotechnic smoke-producing composition that has all the advantages of the prior art mentioned above.
- To attain this, the preferred embodiment of the present invention essentially comprises a composition of an oxidizer, a fuel, a flame retardant, a dye, a coolant, and a binder. The oxidizer may be potassium chlorate. The fuel may be starch, dextrose, lactose, and/or sucrose. The coolant may be sodium bicarbonate or magnesium carbonate. The binder may be nitrocellulose or a halogen-free thermoplastic. The flame retardant may be one or more nitrogen-rich compounds. The composition may be in pelletized form or in the form of a solid charge. The composition may consist of on a mass basis oxidizer 20-35%, fuel 15-25%, flame retardant 5-15%, dye 27-40%, coolant 8-18%, and binder 1-2%. The invention may be a device consisting of a body filled with the composition and a first fire starter composition, and an attached squib igniter. The body may be a grenade. A process for producing the composition is also disclosed. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims attached.
- There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood and in order that the present contribution to the art may be better appreciated.
-
FIG. 1 is a flowchart of the manufacturing process for the current embodiment of the colored pyrotechnic smoke-producing composition constructed in accordance with the principles of the present invention. - The same reference numerals refer to the same parts throughout the FIGURE.
- An embodiment of the process for manufacturing a colored pyrotechnic smoke-producing composition of the present invention is shown and generally designated by the
reference numeral 10. - The invention relates to a smoke-producing pyrotechnic composition and more particularly, is related to generally cool-burning, non-toxic and non-corrosive smoke producing compositions, which incorporate:
-
- Oxidizer—a presently preferred oxidizer is Potassium Chlorate (KCLO3).
- Fuel—a low energy fuel is preferred in order to minimize heat and flame produced. Such fuels may include, for example, starch, dextrose, lactose or sucrose.
- Dye—a sublimable and/or evaporable organic coloring substance which produces a colored smoke as a result of the dye undergoing a phase change.
- Coolant—sodium bicarbonate or magnesium carbonate may be added to act as a buffer for the KCLO3 and as a further coolant; presently the preferred coolant is magnesium carbonate.
- Binder—may be any one of a number of binders such as nitrocellulose or a polymer binder.
- Additives—at least one affordable nitrogen-rich compound selected from the group consisting of guanidine nitrate, guanidine carbonate or dicyandiamide, azodicarbonamide, melamine, and oxamide.
- It is clear from a vast array of studies that traditional pyrotechnics are a severe source of pollution. Environmentally friendly or “green” formulations are therefore based on nitrogen-rich compounds to avoid the use of heavy metals and perchlorates. High-nitrogen compounds gain their energetic character not by oxidation of carbon, but from their high heats of formation. They offer not only environmentally compatible combustion products, but in many cases even better color quality and intensity than older formulations.
- Nitrogen-rich materials combine several advantages:
-
- only or mostly gaseous products (smokeless combustion)
- high heats of formation
- high propulsive powder
- high specific impulse
- high flame temperatures
- Compounds for use in pyrotechnics should be cheap, easy to produce, and non-hygroscopic. High nitrogen content is desirable for reduction of smoke and particulate matter resulting from combustion. The reaction rate must therefore be adjusted for that purpose. High-energy reactions are generally classified as “burning” (approximate reaction velocity in the range of mm or cm s−1), “deflagration” (m s−1), or “detonation” (km s−1).
- An ideal dye material for this application transforms “sublimes” directly from the solid phase to the gas phase with little or no intermediate liquid phase. The direct transformation to a gas enhances the likelihood of the dye molecules escaping from the solid matrix made of fuel, oxidizer, and dye to the external environment without the dye molecules reaching an undesirably high temperature. Thus, dyes are sought for the composition that have the property of sublimation at increased temperatures and normal pressures.
- In general, flame suppressant/flame retardant compounds act in one of two ways: either by preventing ignition of a product or by preventing the spread of a fire once a product is ignited. First, the ignition susceptibility of a product is lowered when the flame retardant increases the net heat capacity of the product. Second, once a fire has already begun, flame retardants can reduce the tendency of the fire to spread by reacting with the product and forming a less flammable char or noncombustible gaseous layer along the boundary of the fire. Within these two general flame-retardant mechanisms, Kirk-Othmer's Encyclopedia of Chemical Technology (Kirk-Othmer, 2001) provides a more detailed summary of five specific mechanisms by which flame retardancy may occur: physical dilution, chemical interaction, inert gas dilution, thermal quenching, and protective coatings.
- The use of nitrogen-rich compounds as both nitrogen producing agents and flame retardants overcomes many of the severe problems encountered in the existing art. In particular, the present invention provides compositions that are generally non-toxic, non-corrosive, and that can be formulated to burn at lower temperatures and with a lower energy output while still producing effective smoke output.
- If potassium chlorate is used without the addition of a nitrogen-rich material to the smoke-producing composition, the combustion temperature is at least 400° C. (750° F.). At this temperature, the dye is nearly completely destroyed, making the composition ineffective at producing smoke. However, because the present invention adds a nitrogen-rich material to the smoke-producing composition, the combustion temperature of the smoke-generating composition of the present invention is reduced to a range from 100° to 250° C. (200 to 480° F.). At the lower end of this range, thermal degradation of the dye is largely prevented, resulting in the effective production of colored smoke. As an example, by using guanidine nitrate in combination with the potassium chlorate, the combustion temperature drops to a range between 190° and 300° C. (375 to 575° F.). The temperature reduction is achieved by the guanidine nitrate catalyzing the decomposition of the chlorate, which makes it possible for the decomposition reaction to occur at a lower temperature than would be conventionally required.
- The nitrogen-rich compounds suitable for use in this invention have been found to be excellent additives for use in a smoke-producing composition containing a degradable dye. The cited additives have been found to be a very efficient coolant because they are nitrogen producing agents that act as flame retardants. Because the additives' decomposition process generates the liberation of gases (carbon dioxide and nitrogen), they assist sublimation of the organic dye and provide thermal protection from the fuel-oxidizer reaction. The additives also inhibit slag build-up and facilitate the production of uniformly porous slag. These slag characteristics enhance the production of color in the smoke generated. In contrast, conventional pyrotechnic compositions pass the vaporized dye through significant amounts of hot slag of limited porosity before the dye escapes into the environment, which has a deleterious effect on the color of the vaporized dye.
- Nitrogen-rich compounds are not only remarkable energy-rich and oxygen-nitrogen-containing compounds that act exothermically to supply heat to the smoke-generating reaction. The nitrogen-rich compounds also simultaneously yield decomposition products that neutralize the acids generated by the smoke-producing composition of the present invention.
- The dyes, which may be used in this invention corresponding to the color standard FED-STD-595C color chip, are listed by the Society of Dyers and Colorists in dye classification materials according to chemical structure, and include the following:
-
TABLE 1 Chemical compositions of some of the dyes suitable for use in in colored smoke-producing compounds of the present invention CI Name CAS# Trade Name Chemical Name Solvent Red 1 1229-55-6 Anasol Red SG amethoxybenzenazo-β-naphthol Disperse Red 9 82-38-2 Anasperse Red SG 1-methylaminoanthraquinone Solvent Orange 7 3118-97-6 Anasol Orange SG 1-((2,4-Dimethylphenyl) azo)-2-naphthalenol Solvent Orange 86 81-64-1 Anasol Orange HF SG 1,4-dihydroxyanthraquinone Disperse Blue 3 2475-46-9 Anasperse Blue SG 1-methylamino-4-ethanolaminoanthraquinone Solvent Violet 47 81-63-0 Anasol Violet SG 1,4-diamino-2,3-dihydroanthraquinone Solvent Yellow 33 8003-22-3 Anasol Yellow SG Mixture of 2-(2-quinolinyl)-1,3-indandione and 2-(6-methyl-2-quinolinyl)-1,3-indandione Solvent Green 3 128-80-3 Anasol Green SG 1,4-di-p-toluidinoanthraquinone N/A 84-54-8 Anasol White SG 2-methylanthraquinone - The compositions of the present invention also incorporate at least one binder to provide the desired consistency. A binding agent from the group of the halogen-free thermoplastics can be used for the physical stabilization of the mixture of the pyrotechnic smoke-producing composition. The binding agent can preferably be polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl ester, or polyvinyl ether. In the present invention, nitrocellulose is specifically desirable in that it results in a decreased solid residue within the burned grain. Nitrocellulose is used in solution (6 to 12% nitrocellulose dissolved in acetone).
- Binders of these types, in addition to providing desirable binding characteristics, produce only a small energy output upon combustion. This is important in avoiding very high-energy outputs, high temperatures, and flames, which render smoke producing compositions dangerous and difficult to handle.
- The composition of the present invention also includes one or more oxidizer compounds. It is found that potassium chlorate (KClO3) is an efficient oxidizer and produces good results when coupled with the fuel and previously mentioned nitrogen-rich compounds.
- The present invention includes a fuel. The fuel is preferably a relatively low energy fuel similar to the binder. It is also preferred that the fuel produce gaseous reaction products capable of carrying the smoke producing agent into the environment. Some suitable fuels include starch, dextrose, and polyhydroxylic compounds such as lactose and sucrose.
- Certain other materials may also be added to produce specific desirable results. One suitable material is magnesium carbonate. Magnesium carbonate acts as a buffer, which prevents autocatalytic decomposition of the KClO3. Magnesium carbonate also functions as a coolant when the smoke-producing composition combusts. Alternatively, sodium bicarbonate can be used. Another useful additive in the present invention is aluminum. In some cases, atomized aluminum can provide additional thermal conductivity within the composition. This results in more uniform heat transfer and ignition of the fuel.
- In general, the ingredients of the composition may be within the ranges indicated in Table 2:
-
TABLE 2 Ingredient ranges of the improved pyrotechnic smoke- producing composition of the present invention Percent by Weight Materials (in dry state), % Nitrogen-Rich Compounds 5 to 15 Potassium Chlorate 20 to 35 Sugar (Fuel) 15 to 25 Dye 27 to 40 Magnesium Carbonate 8 to 18 Nitrocellulose 1 to 2 - The following examples illustrate various embodiments of the invention, but it will be obvious that various changes and modifications may be made therein without departing from the scope of the invention.
- More specifically, excellent results are obtained with the formulation set forth in the following examples:
-
-
Percent by Weight Materials (in dry state), % Guanidine Nitrate 3.8 Guanidine Carbonate 3.8 Potassium Chlorate 24.9 Sugar 17.1 Solvent Orange 7 32.9 Magnesium Carbonate 15.8 Nitrocellulose 1.7 -
-
Percent by Weight Materials (in dry state), % Guanidine Nitrate 3.8 Guanidine Carbonate 3.8 Potassium Chlorate 27.7 Sugar 18.7 Solvent Red 9 31.0 Magnesium Carbonate 13.3 Nitrocellulose 1.7 -
-
Percent by Weight Materials (in dry state), % Dicyandiamide 9.0 Potassium Chlorate 23.5 Sugar 16.0 Solvent Orange 86 32.9 Magnesium Carbonate 16.8 Nitrocellulose 1.8 -
-
Percent by Weight Materials (in dry state), % Dicyandiamide 9.0 Potassium Chlorate 24.8 Sugar 17.0 Solvent Red 9 32.0 Magnesium Carbonate 15.4 Nitrocellulose 1.8 -
-
Percent by Weight Materials (in dry state), % Azodicarbonamide 10.0 Potassium Chlorate 25.0 Sugar 17.0 Solvent Red 9 32.5 Magnesium Carbonate 13.5 Nitrocellulose 2.0 - Referring now to
FIG. 1 , the pyrotechnic smoke-producing compositions were produced as follows: The process starts (12) by individually weighing (14) a quantity of nitrogen-rich compound(s) 16, a quantity ofoxidizer 18, a quantity offuel 20, a quantity ofdye 22, a quantity ofmagnesium carbonate 24, and a quantity ofnitrocellulose 26. The weighed dry ingredients are then added to a mixing bowl (28) and undergo a first mixing step (30). In the preferred embodiment, the mixer utilized as a Hobart planetary gear-style mixer. Then, a quantity of acetone solvent 32 (0.2-0.3 L/kg of the dry mix resulting from step 30) is measured (34) and subsequently added to the mixing bowl (36). The resulting mixture undergoes a second mixing step (38). Initially, the mix is a very viscous wet slurry of the components. As mixing proceeds, the acetone begins to evaporate, and the composition assumes the consistency of wet dough. Mixing continues, and as more acetone evaporates, the doughy composition breaks into increasingly smaller chunks. Mixing is further continued until all visible acetone has evaporated and relatively dry, well-mixed spherical chunks of agglomerated mix have been produced. The entire mixing process can be accomplished in approximately 25 minutes for each kilogram of finished mixture when a 5-quart mixing bowl is used. - The composition's ingredients can also be blended together as dry powders using standard pyrotechnic techniques. However, the wet mixing technique using acetone is preferable because it is safer and produces a more homogeneous mixture.
- The smaller spherical chunks are poured (40) from the mixing bowl into drying trays. The mix is spread on the drying trays so the mix is flat at a uniform level in the trays. The trays are placed in an oven (42) maintained at 60±5° C. (140±10° F.), for 24 to 36 hours to evaporate any residual acetone. After drying, the material is ground (44) to achieve small grains of pyrotechnic mixture, which can be further loaded or preferably pelletized (46).
- It has been found useful to pelletize the pyrotechnic composition of this invention, rather than to use the composition in powder form, to achieve predictable combustion performance of the composition. Pelletizing can be achieved by harshly mixing the powdered ingredients and then using a pill press to produce pellets. Alternatively, the powdered mixture can be granulated and then formed into noodles by extruding the mixture through a screen. Pelletizing has been found advantageous because the mixed powder has some undesirable characteristics. First, the powder tends to separate, with the oxidizer at the bottom and the fuel at the top. As a result, when the powder burns, it burns with different characteristics depending upon the degree to which the powder mixture is homogeneous. Second, the powder may be loosely packed or tightly packed, which also affects its combustion characteristics. These variations in homogeneity and packing can lead to inconsistent combustion results when using the composition in powder form. When using the composition in pellet form, the combustion results are more consistent.
- After drying, the pellets are hydraulically loaded (48) into
grenade bodies 50 or pelletized to adjust the combustion characteristics of the composition so the devices have the required burning time. The load applied to the surface of the mix in the grenade body is about 5000 to 7000 pounds per square inch (psi). A MIL SPEC No. 508 first fire starter mixture or a flameless firstfire starter mixture 52 is applied to the grenades, and tops 54 are sealed onto the bodies (56). A No. 565squib igniter 58 can be used to ignite the grenade. The loaded and sealed grenades are the end result (60) of the process. - The colored smokes produced by the pyrotechnic compositions of the present invention were compared to smoke produced by conventional formulations based on 1,4-benzendicarboxylic acid or aliphatic dicarboxylic acids. Each smoke color produced by the pyrotechnic compositions of the present invention was also compared to the corresponding color standard FED-STD-595C color chip. This was accomplished by making the various pyrotechnic mixtures and forming them into grenades in the manner previously described. The grenades were then burned adjacent to one another to enable side-by-side visual comparison. The subjective evaluation of the color quality the smoke produced provided a reliable indication of the improved effectiveness and efficiency of the pyrotechnic composition of the present invention.
- Another indication of the greater efficiency of smoke munitions that include the pyrotechnic compositions of the present invention was the length of flaming time recorded during the burn. It was found that flaming of the compositions of the present invention was reduced in comparison to the more frequent flaming of the standard mixtures based on 1,4-benzendicarboxylic acid or aliphatic dicarboxylic acids. The improved effectiveness and efficiency of the composition of the present invention was shown throughout the comparison.
- Various smoke-producing pyrotechnic compositions of the present invention, previously detailed above as Examples 1 to 5, were placed in standard military-style metal cans used for signal colored smoke grenade. The compositions were compacted as pressed pellets as a first experimental design, and as solid charges in a second experimental design (see the second column of Table 3 below). In both experimental designs, the weight of pyrotechnic filling was about 210 to 235 grams (7.5 to 8.2 oz.). The pressed or pelletized grains were ignited, and their burning characteristics, including ignition time and flame, burning time, burning temperature, can temperature and pressure were recorded. The results of these tests are summarized in Table 3.
-
TABLE 3 Test results. Burning Can Ignition Burning Temperature Temperature Flame, Time Time Range*** Range*** Experimental Range Range*** (° C.) (° C.) Composition Design Type (sec) (sec) (° F.) (° F.) Remarks Example1 Pressed Pellets 2-5* 40-60 120-150 100-150 ** No top flame 250-300 200-300 Solid Charge 2-5* 90-110 120-150 100-150 ** No top flame 250-300 200-300 Example2 Pressed Pellets 2-5* 50-70 100-140 150-190 ** No top flame 200-275 300-375 Solid Charge 2-5* 100-120 100-140 150-190 ** No top flame 200-275 300-375 Example3 Pressed Pellets 2-5* 50-70 100-150 120-175 ** No top flame 200-300 250-350 Solid Charge 2-5* 100-120 100-150 120-175 ** No top flame 200-300 250-350 Example4 Pressed Pellets 2-5* 50-70 120-175 150-200 ** No top flame 250-350 300-400 Solid Charge 2-5* 100-120 120-175 150-200 ** No top flame 250-350 300-400 Example5 Pressed Pellets 2-5* 60-80 100-150 150-200 ** No top flame 200-300 300-400 Solid Charge 2-5* 110-150 100-150 150-200 ** No top flame 200-300 300-400 *Includes 1.5 seconds to account for fuse delay. **qualitative evaluation determined visually, which indicated good smoke yield, no burnt color, and good combustion pressure range. ***temperatures were registered using a dual input thermometer data logger model EXTECH EasyView 15 compatible with 7 types of thermocouples. - The use of a flame retardant and a coolant within the colored pyrotechnic smoke-producing composition of the current invention is counterintuitive for two reasons. First, the goal of a colored pyrotechnic smoke-producing composition is to burn with sufficient intensity to vaporize the dye component of the composition, so the use of ingredients that impede burning is contraindicated. Second, guanidine salts, such as guanidine nitrate, are conventionally employed in the an of ignition as an exothermic reactant in a smoke grenade (U.S. Pat. No. 4,238,254), or as an additional fuel for a flare igniter (U.S. Pat. No. 6,170,399). This makes their usage in the current invention for their flame retardant properties nonobvious.
- While current embodiments of a colored pyrotechnic smoke-producing composition and methods of preparation have been described in detail, it should be apparent that modifications and variations thereto are possible, all of which fall within the true spirit and scope of the invention.
- With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention.
- Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
Claims (22)
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US20140283706A1 (en) * | 2013-03-21 | 2014-09-25 | Kms Consulting, Llc | Training ammunition cartridge with a gaseous plume signature |
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US20180141880A1 (en) * | 2016-11-23 | 2018-05-24 | John L. Lombardi | Nontoxic and Non-incendiary Obscurant Compositions and Method of Using Same |
WO2018183523A1 (en) * | 2017-03-28 | 2018-10-04 | Lombardi John L | Obscurant compositions |
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WO2019205996A1 (en) * | 2018-04-25 | 2019-10-31 | 微山宏瑞电力科技有限公司 | Contamination residue-free easily-degradable environmentally-friendly firecracker and manufacturing method therefor |
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US10663272B1 (en) * | 2018-11-06 | 2020-05-26 | The United States Of America As Represented By The Secretary Of The Army | Low toxicity, environmentally friendly violet smoke generating compositions and methods of making the same |
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US10905115B2 (en) | 2018-08-23 | 2021-02-02 | Arjesil Inc. | Smoke producing tablet and methof of use |
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US20140283706A1 (en) * | 2013-03-21 | 2014-09-25 | Kms Consulting, Llc | Training ammunition cartridge with a gaseous plume signature |
US20180141880A1 (en) * | 2016-11-23 | 2018-05-24 | John L. Lombardi | Nontoxic and Non-incendiary Obscurant Compositions and Method of Using Same |
CN106831275A (en) * | 2017-01-13 | 2017-06-13 | 长沙跃奇节能电气设备有限公司 | Pyrotechnic composition production system |
WO2018183523A1 (en) * | 2017-03-28 | 2018-10-04 | Lombardi John L | Obscurant compositions |
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US10905115B2 (en) | 2018-08-23 | 2021-02-02 | Arjesil Inc. | Smoke producing tablet and methof of use |
US10663272B1 (en) * | 2018-11-06 | 2020-05-26 | The United States Of America As Represented By The Secretary Of The Army | Low toxicity, environmentally friendly violet smoke generating compositions and methods of making the same |
CN109956843A (en) * | 2019-03-08 | 2019-07-02 | 醴陵恒达烟花有限公司 | A kind of smokeless propellant and preparation method thereof |
CN110963870A (en) * | 2019-12-03 | 2020-04-07 | 北京理工大学 | Smokeless and sulfur-free firework delay powder and preparation method thereof |
CN111410593A (en) * | 2020-03-14 | 2020-07-14 | 中北大学 | Environment-friendly firework and preparation method and assembly method thereof |
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CN116964024A (en) * | 2020-12-04 | 2023-10-27 | 埃杰拉夸烟花股份有限公司 | Fuming composition |
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