CN113840815A - Low smoke pyrotechnic composition - Google Patents
Low smoke pyrotechnic composition Download PDFInfo
- Publication number
- CN113840815A CN113840815A CN202080034977.9A CN202080034977A CN113840815A CN 113840815 A CN113840815 A CN 113840815A CN 202080034977 A CN202080034977 A CN 202080034977A CN 113840815 A CN113840815 A CN 113840815A
- Authority
- CN
- China
- Prior art keywords
- low smoke
- pyrotechnic composition
- weight percent
- smoke pyrotechnic
- oxidizer
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000000779 smoke Substances 0.000 title claims abstract description 74
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims abstract description 40
- 239000000446 fuel Substances 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 10
- 229920001220 nitrocellulos Polymers 0.000 claims abstract description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005751 Copper oxide Substances 0.000 claims abstract description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- -1 hydroxypropyl ethyl Chemical group 0.000 claims description 8
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002449 FKM Polymers 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 2
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 claims description 2
- IMFYAZJNDOZIFV-UHFFFAOYSA-N 3-methyl-1,1-diphenylurea Chemical compound C=1C=CC=CC=1N(C(=O)NC)C1=CC=CC=C1 IMFYAZJNDOZIFV-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004343 Calcium peroxide Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019402 calcium peroxide Nutrition 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims 1
- 235000004692 Eucalyptus globulus Nutrition 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 21
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/006—Stabilisers (e.g. thermal stabilisers)
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
- C06B25/20—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with a non-explosive or a non-explosive or a non-thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
Abstract
A low smoke pyrotechnic composition is provided. The composition may include cerium ammonium nitrate as an oxidizer, a fuel source, a stabilizer, and a binder. The use of cerium ammonium nitrate as an oxidizer in the composition may allow for a reduction in the amount of smoke generated during combustion of the composition, which may be beneficial for certain pyrotechnic applications. In certain configurations, the composition may include cerium ammonium nitrate as an oxidizer, nitrocellulose and titanium as a fuel source, cyanoguanidine as a stabilizer, copper oxide as a burn rate catalyst, and any suitable binder. The amount of cerium ammonium nitrate in the composition may range between 20-80%, 30-40%, or 30.0-37.5% by weight. In certain configurations, the amount of cerium ammonium nitrate may be about 36.7 wt%.
Description
Cross Reference to Related Applications
Priority is claimed in U.S. provisional patent application serial No.62/832,003 entitled "Low-Smoke Pyrotechnic Composition" filed 2019, month 4 and 10, by Lyle Salmi et al, the entire disclosure of which is incorporated herein by reference, which is currently under examination.
Technical Field
The present invention relates generally to ingredients or components used in fireworks and, more particularly, as a low smoke substitute for black powder used in fireworks.
Background
Black powder has been used in pyrotechnical devices for thousands of years. It is an intimate mixture of approximately 75% potassium nitrate, 15% charcoal and 10% sulphur. Although its initial development was aimed at using it as an explosive weapon, its use is rapidly expanding into the civil engineering and entertainment fields. The beginning of history should not be surprising because there are many positive properties that make black powder an attractive composition for use in fireworks. First, black powder is easily ignited due to the presence of sulfur and its low melting point. Secondly, black powder is made of readily available and relatively inexpensive components. Finally, black powder is not only able to effectively push or "lift" other pyrotechnic compositions, but also to form a large number of hot solid particles during combustion, which promotes ignition of the secondary pyrotechnic composition.
There is a high demand for black powder substitutes that provide acceptable burn rates upon combustion, generate large amounts of gas, and successfully initiate and drive the combustion of other pyrotechnic compositions. The black powder used in current pyrotechnic devices is undesirable for certain applications because it typically produces a large amount of solid byproducts from the combustion of the composition in the form of smoke and other solid particulate matter. Current black powder substitutes typically fail to reliably ignite the secondary pyrotechnic composition.
Accordingly, there is a need for gas generant compositions suitable for use in pyrotechnic applications that require similar gas generant and heat transfer properties while also reducing smoke output.
Disclosure of Invention
The present invention relates to a low smoke pyrotechnic composition which may be suitable for use in applications where it is desirable to minimise the production of smoke or other solid particulate matter from the combustion of the composition.
The low smoke pyrotechnic composition of the invention includes Cerium Ammonium Nitrate (CAN) (formula: H)8N8CeO18) As an oxidizer to limit the production of solid by-products, including smoke generation, during combustion of the composition. The cerium ammonium nitrate in the low smoke pyrotechnic composition generates a significant amount of oxygen available for propagating combustion and nitrogen available for propulsion, while also providing significantly reduced smoke and particulate matter generation during combustion as compared to other common oxidizers.
According to one embodiment of the present invention, a low smoke pyrotechnic composition may include a fuel source, a stabilizer, a binder, and cerium ammonium nitrate as an oxidizer. In certain embodiments, the composition may include an additional oxidizing agent in addition to the cerium ammonium nitrate; however, ammonium cerium nitrate must be present in the compositions of the present invention. Low smoke pyrotechnic compositions in accordance with various embodiments of the invention may include: any suitable fuel source or sources, including but not limited to metallic and non-metallic fuel sources; a stabilizer or stabilizers of any suitable type; and any suitable type of adhesive or adhesives.
According to one embodiment of the present invention, a low smoke pyrotechnic composition may include 20-80 weight percent cerium ammonium nitrate, 5-60 weight percent fuel source(s), 1-20 weight percent stabilizer(s), and 0-15 weight percent binder(s).
According to one or more embodiments, the low smoke pyrotechnic composition may also include a burn rate catalyst. The burn rate catalyst may comprise any suitable type(s) of burn rate catalyst or heat generating compound. The particular burn rate catalyst or heat generating compound or combination thereof may be selected based at least in part on the desired effect and the particular pyrotechnic application.
According to one embodiment of the present invention, a low smoke pyrotechnic composition may include cerium ammonium nitrate as an oxidizer, nitrocellulose as a non-metallic fuel source, titanium as a metallic fuel source, cyanoguanidine as a stabilizer, copper oxide as a burn rate catalyst, and any suitable binder compound. In further embodiments, one or more fuel sources, stabilizers, burn rate catalysts, and/or oxidizers may be added to the low smoke pyrotechnic composition depending on the particular application.
According to one embodiment of the present invention, a low smoke pyrotechnic composition may include about 30-40% by weight cerium ammonium nitrate (oxidizer), about 45-55% by weight nitrocellulose (non-metallic fuel source), about 0.1-3.0% by weight cyanoguanidine (stabilizer), about 5-10% copper oxide (burn rate catalyst), and about 0-15% of a suitable binder material.
According to a particular embodiment, a low smoke pyrotechnic composition may include about 36.7 weight percent cerium ammonium nitrate (50 um), about 51.4 weight percent nitrocellulose, about 3.7 weight percent titanium (-325 mesh), about 0.9 weight percent cyanoguanidine, about 7.3 weight percent copper oxide, and about 0-15 weight percent binder material.
Other aspects and advantages of the present invention will become apparent from the following detailed description of the preferred embodiments.
Detailed Description
The following detailed description of the invention refers to specific embodiments in which the invention may be practiced. The embodiments are intended to describe aspects of the invention in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments may be utilized and changes may be made without departing from the scope of the present invention. The invention is defined by the following claims, and therefore the description is not to be taken in a limiting sense and is not intended to limit the scope of equivalents to which such claims are entitled.
The present invention relates to a low smoke pyrotechnic composition that may be used in pyrotechnic applications where it is desirable to minimize the amount of smoke or other solid particulate matter generated as a result of combustion of the composition. Depending on the desired application, the low smoke pyrotechnic composition of the invention may be used in connection with lighting pyrotechnic compositions and/or propellant compositions. For example, the low smoke pyrotechnic composition of the invention may be used to produce illumination light, a flash or flame, heat and/or sound associated with combustion of the composition, while limiting the overall production of smoke (total yield) associated with chemical reactions and combustion.
The most important component of the low smoke pyrotechnic composition of the present invention is cerium ammonium nitrate, which acts as an oxidizer. Ammonium cerium nitrate is an inorganic compound with the molecular formula of (NH)4)2Ce(NO3)6(chemical formula: H)8N8CeO18) And are often used as oxidants in organic synthesis. Ammonium cerium nitrate (CAN) may also be referred to as diammonium cerium hexanitrate, 2-diammonium hexanitroceric acid, and cerium ammonium nitrate (VAN). CAN is used as a primary oxidizer in low smoke pyrotechnic compositions and limits the production of solid by-products, including smoke generation, during combustion of the composition.
Ammonium cerium nitrate is necessary in the low smoke pyrotechnic composition of the present invention because it generates significant amounts of oxygen available for propagating combustion and nitrogen available for propulsion; it also ignites easily in the presence of organic fuels. CAN may have limited use in the pyrotechnic industry due to usability issues and the ability to readily oxidize various materials at room temperature when solvated.
Decomposition of one gram of cerium ammonium nitrate produced 0.53 grams of oxygen, 0.2 grams of nitrogen, and 0.1 grams of hydrogen. The mass of oxygen produced was comparable to other common oxidants such as potassium nitrate (0.40 grams of oxygen per gram), potassium chlorate (0.39 grams of oxygen per gram) and potassium perchlorate (0.46 grams of oxygen per gram). The combustion of CAN forms 0.31 grams of cerium (IV) oxide and 0.13 grams of water vapor. After subtracting the oxygen discharged as cerium (IV) oxide and water vapor, 0.35 grams of free oxygen remained to participate in the combustion process. Using this information, it was found that over 69% of the by-products of the decomposition of CAN were gaseous and that combustion of formulations using CAN as the oxidant had significantly reduced smoke generation.
Ammonium cerium nitrate is also advantageous in the low smoke pyrotechnic composition of the present invention because of its low melting point. The implementation of sulfur as a low melting point ignition charge in black powder has a disadvantage because its presence results in a large amount of solid sulfide by-product, which increases the smoke output of the composition. The low melting point of CAN and the high ignitability of organic fuels greatly reduce the amount of activation energy required for combustion and eliminate the need for sulfur. In addition, ammonium cerium nitrate and its by-products are environmentally benign.
As shown in table I below, according to one embodiment, the low smoke pyrotechnic composition of the present disclosure may include a fuel source, a stabilizer, a binder, and cerium ammonium nitrate as an oxidizer. In certain embodiments, additional oxidizing agents may be used with the cerium ammonium nitrate; however, ammonium cerium nitrate is the only specific component of the composition that is not removable or replaceable. Additional oxidizers that may be used in combination with the cerium ammonium nitrate may include, but are not limited to, nitrates, perchlorates, and metal oxides. In certain embodiments, the low smoke pyrotechnic compositions of the invention may include one or more of each type of component comprising the composition. In such embodiments, the low smoke pyrotechnic composition may include at least one fuel source agent, at least one stabilizer, at least one binder, and at least one oxidizer including at least cerium ammonium nitrate.
In certain embodiments, the fuel may be a metal or non-metal source and the composition may include multiple fuel sources. Non-limiting examples of suitable fuel sources that may be used in the low smoke pyrotechnic compositions of the present invention may include: nitrocellulose, hexamine, nitroguanidine, Red Gum (Red Gum), titanium, aluminum, magnesium, boron, charcoal, silicon, any transition metal, or other type of fuel source now known or later developed or commonly used in the art.
The stabilizer may be any suitable stabilizer, including but not limited to: cyanoguanidine, Dicyanodiamide (Dicyanodiamide), 2-cyanoguanidine, guanidine-1-carbonitrile, diphenylamine, nitrodiphenylamine, 3-Methyl-1, 1-diphenylurea (Akardite), Ethyl neutralizer (Ethyl center), Methyl neutralizer (Methyl center), carbonate, or other types of stabilizers now known or later developed in the art or commonly used.
The binder may be a suitable compound or substance that may bind/bond with other components of the low smoke pyrotechnic composition. Non-limiting examples of suitable binders that may be used in the low smoke gas generating composition of the present invention may include: ethyl cellulose, methyl cellulose, hydroxypropyl ethyl cellulose polyvinyl alcohol, Viton rubber (Viton), Parlon (Parlon), polyvinyl pyrrolidone, polyethylene glycol-polyvinyl alcohol copolymers, epoxy resins, and suitable crosslinking compounds thereof, or other binders now known or later developed or commonly used in the art.
TABLE I
Basic formulation of the Low Smoke pyrotechnic composition:
as shown in Table II below, the low smoke gas generating composition of the present invention may also include at least one burn rate catalyst or a heat generating compound or compounds, depending on the desired effect and the particular pyrotechnic application. According to one embodiment, the low smoke pyrotechnic composition of the invention may include copper oxide as a burn rate catalyst. Other potentially suitable catalysts may include, but are not limited to, ferric oxide, titanium dioxide, dibismouth trioxide, molybdenum trioxide, barium peroxide, strontium peroxide, calcium peroxide, chromium oxide, silicon dioxide, manganese (II) oxide, boron oxide, or other desired compounds commonly used in the art.
TABLE II
Basic formulation of the Low Smoke pyrotechnic composition:
as shown in table III below, in accordance with a preferred embodiment of the present invention, a low smoke pyrotechnic composition includes cerium ammonium nitrate as an oxidizer, nitrocellulose as a non-metallic fuel source, titanium as a metallic fuel source, cyanoguanidine as a stabilizer, copper oxide as a burn rate catalyst, and any suitable binder compound. The following table illustrates this preferred formulation for a low smoke pyrotechnic composition. As shown, the cerium ammonium nitrate may have a suitable range of 20-80 wt% of the entire formulation. Furthermore, the other components of the composition may vary significantly in weight percent and may be replaced with other suitable compounds depending on the particular application.
TABLE III
Selecting a formulation of a low smoke pyrotechnic composition:
in accordance with a preferred embodiment of the present invention, a low smoke pyrotechnic composition includes about 36.7 weight percent cerium ammonium nitrate (-50 um), about 51.4 weight percent nitrocellulose, about 3.7 weight percent titanium (-325 mesh), about 0.9 weight percent cyanoguanidine, about 7.3 weight percent copper oxide, and about 0-15 weight percent binder material. The specific weight% may vary depending on the particular or desired application and or the amount of binder material utilized. For example, according to certain embodiments, the specific weight amount of cerium ammonium nitrate as the oxidizing agent may range between 36.0-37.5%, or in other embodiments may range between 30-40%. Table IV below illustrates one specific embodiment of the low smoke pyrotechnic composition and the potential ranges (in weight percent) for each ingredient or compound included in the composition.
TABLE IV
The specific formula of the low-smoke pyrotechnic composition is as follows:
as described herein, the low smoke pyrotechnic compositions of the present invention produce minimal solid particulates and smoke byproducts during combustion of the compositions while still providing desirable combustion temperatures, burn rates, and other desirable effects for various pyrotechnic applications. Ammonium cerium nitrate is a key ingredient in the compositions of the present invention, which produces performance characteristics comparable to black powder, while reducing or eliminating its negative attributes. In particular, the inclusion of cerium ammonium nitrate in the low smoke pyrotechnic composition of the invention according to the weight percentage ranges as described herein has the effect of producing limited smoke generation during combustion of the composition when compared to conventional pyrotechnic compositions.
For safety and lifetime reasons, the composition must be stabilized by using hydrophobic binders, such as epoxy resins, vinylon rubber or polyvinyl butyral. Depending on the particular embodiment, any number of suitable manufacturing and production methods may be used in the preparation of the low smoke pyrotechnic compositions of the invention, including, but not limited to, manufacturing and production methods currently used in the pyrotechnic industry or later developed or any other methods or techniques used in the production of chemical compositions. The low smoke pyrotechnic compositions of the present invention have several potential benefits, including, but not limited to, tunable performance aspects with minimal formulation changes, and the generation of predominantly gaseous by-products that enhance performance while reducing smoke output.
From the foregoing it will be seen that this invention is one well adapted to attain all the ends and objects set forth above, together with other advantages which are obvious and which are inherent to the structure. It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims.
The above-described configurations are presented by way of example only and are not intended to limit the concepts and principles of the invention. Thus, several embodiments of the novel invention have been shown and described. It will be apparent from the foregoing that certain aspects of the invention are not limited by the specific details of the examples set forth herein, and it is therefore contemplated that other modifications and applications, or equivalents thereof, will occur to those skilled in the art. The terms "having" and "including" and similar terms as used in the foregoing specification are used in the sense of "optionally" or "may include" and not as "required. However, many alterations, modifications, variations and other uses and applications of the present construction will become apparent to those skilled in the art after considering the specification. All such changes, modifications, variations and other uses and applications which do not depart from the spirit and scope of the invention are deemed to be covered by the invention which is limited only by the claims which follow.
Claims (17)
1. A low smoke pyrotechnic composition comprising:
an oxidizer comprising cerium ammonium nitrate;
a fuel source;
a stabilizer; and
and (3) an adhesive.
2. A low smoke pyrotechnic composition as claimed in claim 1 wherein said fuel source comprises at least one of nitrocellulose, hexamine, cellulose nitrate, nitroguanidine, eucalyptus globulus gum, titanium, aluminium, magnesium, boron, charcoal, silicon and transition metals.
3. The low smoke pyrotechnic composition of claim 1 wherein the stabilizer comprises at least one of cyanoguanidine, dicyanodiamide, 2-cyanoguanidine, guanidine-1-carbonitrile, diphenylamine, nitrodiphenylamine, 3-methyl-1, 1-diphenylurea, ethyl neutralizer, methyl neutralizer, and carbonate.
4. The low smoke pyrotechnic composition of claim 1 wherein said binder comprises at least one of ethyl cellulose, methyl cellulose, hydroxypropyl ethyl cellulose polyvinyl alcohol, Viton rubber, Paron, polyvinylpyrrolidone, polyethylene glycol, and polyethylene glycol-polyvinyl alcohol copolymer.
5. The low smoke pyrotechnic composition of claim 1 further comprising a burn rate catalyst.
6. The low smoke pyrotechnic composition of claim 5 wherein the burn rate catalyst comprises at least one of copper oxide, ferric oxide, titanium dioxide, dibismuth trioxide, molybdenum trioxide, barium peroxide, strontium peroxide, calcium peroxide, chromium oxide, silicon dioxide, manganese (II) oxide, and boron oxide.
7. The low smoke pyrotechnic composition of claim 1 further comprising a second oxidizer comprising at least one of a nitrate, a perchlorate, and a metal oxide.
8. A low smoke pyrotechnic composition as claimed in claim 1 comprising from 20% to 80% by weight of said cerium ammonium nitrate.
9. A low smoke pyrotechnic composition as claimed in claim 1 comprising 30% to 40% by weight of said cerium ammonium nitrate.
10. The low smoke pyrotechnic composition of claim 1 comprising about 36.0% to 37.5% by weight of said cerium ammonium nitrate.
11. A low smoke pyrotechnic composition as claimed in claim 1 comprising 20 to 80 weight percent of said cerium ammonium nitrate, 0 to 60 weight percent of said fuel source, 1 to 20 weight percent of said stabilizer, and 0 to 15 weight percent of said binder.
12. A low smoke pyrotechnic composition comprising:
an oxidizer comprising cerium ammonium nitrate;
a non-metallic fuel source comprising nitrocellulose;
a metal fuel source comprising titanium;
a stabilizer comprising cyanoguanidine;
a burn rate catalyst comprising copper oxide; and
and (3) an adhesive.
13. A low smoke pyrotechnic composition as claimed in claim 12 comprising from 20 to 80% by weight of said oxidizer.
14. A low smoke pyrotechnic composition as claimed in claim 12 comprising 30 to 40% by weight of said oxidizer.
15. The low smoke pyrotechnic composition of claim 12 comprising about 36.0-37.5 weight percent of said oxidizer.
16. A low smoke pyrotechnic composition as claimed in claim 12 comprising 20 to 80 weight percent of said oxidizer, 0 to 60 weight percent of said non-metallic fuel source, 5 to 20 weight percent of said metallic fuel source, 1 to 5 weight percent of said stabilizer, 0.5 to 20 weight percent of said burn rate catalyst and 0 to 15 weight percent of said binder.
17. The low smoke pyrotechnic composition of claim 12 comprising about 36.7 weight percent of said oxidizer, about 51.4 weight percent of said non-metallic fuel source, about 3.7 weight percent of said metallic fuel source, about 0.9 weight percent of said stabilizer, and about 7.3 weight percent of said burn rate catalyst.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201962832003P | 2019-04-10 | 2019-04-10 | |
| US62/832,003 | 2019-04-10 | ||
| PCT/US2020/027216 WO2020210318A1 (en) | 2019-04-10 | 2020-04-08 | Low-smoke pyrotechnic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113840815A true CN113840815A (en) | 2021-12-24 |
Family
ID=72748864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080034977.9A Pending CN113840815A (en) | 2019-04-10 | 2020-04-08 | Low smoke pyrotechnic composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20200325083A1 (en) |
| EP (1) | EP3953319A4 (en) |
| CN (1) | CN113840815A (en) |
| AU (1) | AU2020272752A1 (en) |
| CA (1) | CA3132944A1 (en) |
| MX (1) | MX2021012451A (en) |
| WO (1) | WO2020210318A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582793A (en) * | 2021-08-27 | 2021-11-02 | 陈昊彬 | Carbon nano tube micro-pyrotechnic composition and production method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247525A (en) * | 1996-07-25 | 2000-03-15 | 科丹特技术公司 | Metal complexes for use as gas generants |
| US20020148540A1 (en) * | 2001-04-12 | 2002-10-17 | Hiskey Michael A. | Low-smoke nitroguanidine and nitrocellulose based pyrotechnic compositions |
| US20030015266A1 (en) * | 2001-05-07 | 2003-01-23 | Wheatley Brian K. | Gas generant compositions exhibiting low autoignition temperatures and methods of generating gases therefrom |
| US6749702B1 (en) * | 1996-05-14 | 2004-06-15 | Talley Defense Systems, Inc. | Low temperature autoignition composition |
| US20070068610A1 (en) * | 2005-02-15 | 2007-03-29 | Nickel Russell R | Microcrystalline Nitrocellulose Pyrotechnic Compositions |
| US20110168307A1 (en) * | 2005-06-06 | 2011-07-14 | D Arche Steven P | Smokeless flash powder |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3399089A (en) * | 1967-06-29 | 1968-08-27 | Trojan Powder Co | Gelatinized dinitrotoluenenitrostarch explosives |
| AU465635B2 (en) * | 1972-09-07 | 1975-10-02 | Ici Australia Limited | Processes and products |
| US6235132B1 (en) * | 1995-03-10 | 2001-05-22 | Talley Defense Systems, Inc. | Gas generating compositions |
| US5780768A (en) * | 1995-03-10 | 1998-07-14 | Talley Defense Systems, Inc. | Gas generating compositions |
| US6605233B2 (en) * | 2001-03-02 | 2003-08-12 | Talley Defense Systems, Inc. | Gas generant composition with coolant |
| US6699379B1 (en) * | 2002-11-25 | 2004-03-02 | Industrial Technology Research Institute | Method for reducing stress in nickel-based alloy plating |
| US8641842B2 (en) * | 2011-08-31 | 2014-02-04 | Alliant Techsystems Inc. | Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same |
-
2020
- 2020-04-08 WO PCT/US2020/027216 patent/WO2020210318A1/en active Search and Examination
- 2020-04-08 EP EP20788436.2A patent/EP3953319A4/en not_active Withdrawn
- 2020-04-08 US US16/843,291 patent/US20200325083A1/en not_active Abandoned
- 2020-04-08 CN CN202080034977.9A patent/CN113840815A/en active Pending
- 2020-04-08 MX MX2021012451A patent/MX2021012451A/en unknown
- 2020-04-08 AU AU2020272752A patent/AU2020272752A1/en not_active Abandoned
- 2020-04-08 CA CA3132944A patent/CA3132944A1/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6749702B1 (en) * | 1996-05-14 | 2004-06-15 | Talley Defense Systems, Inc. | Low temperature autoignition composition |
| CN1247525A (en) * | 1996-07-25 | 2000-03-15 | 科丹特技术公司 | Metal complexes for use as gas generants |
| US20020148540A1 (en) * | 2001-04-12 | 2002-10-17 | Hiskey Michael A. | Low-smoke nitroguanidine and nitrocellulose based pyrotechnic compositions |
| US20030015266A1 (en) * | 2001-05-07 | 2003-01-23 | Wheatley Brian K. | Gas generant compositions exhibiting low autoignition temperatures and methods of generating gases therefrom |
| US20070068610A1 (en) * | 2005-02-15 | 2007-03-29 | Nickel Russell R | Microcrystalline Nitrocellulose Pyrotechnic Compositions |
| US20110168307A1 (en) * | 2005-06-06 | 2011-07-14 | D Arche Steven P | Smokeless flash powder |
Non-Patent Citations (1)
| Title |
|---|
| 任慧: "《微纳米含能材料》", 30 April 2015, 北京理工大学出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020210318A1 (en) | 2020-10-15 |
| AU2020272752A1 (en) | 2021-11-11 |
| MX2021012451A (en) | 2021-12-15 |
| EP3953319A4 (en) | 2022-12-28 |
| US20200325083A1 (en) | 2020-10-15 |
| EP3953319A1 (en) | 2022-02-16 |
| CA3132944A1 (en) | 2020-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6599379B2 (en) | Low-smoke nitroguanidine and nitrocellulose based pyrotechnic compositions | |
| AU679301B2 (en) | Lead-free priming mixture for percussion primer | |
| US3912561A (en) | Pyrotechnic compositions for gas generation | |
| KR100318338B1 (en) | Ignition Composition for Expansion Gas Generators | |
| EP1195366B1 (en) | Non-toxic primer mix | |
| US5388519A (en) | Low toxicity primer composition | |
| US8282749B1 (en) | Green light emitting pyrotechnic compositions | |
| US5936195A (en) | Gas generating composition with exploded aluminum powder | |
| US4000022A (en) | Fast-burning compositions of fluorinated polymers and metal powders | |
| WO1997011926A1 (en) | Lead-free primer mix | |
| US5587552A (en) | Infrared illuminating composition | |
| US20070181236A1 (en) | Gas-generating pyrotechnical compositions and pyrotechnical compounds for automotive safety | |
| CN113840815A (en) | Low smoke pyrotechnic composition | |
| TW460433B (en) | Pyrotechnic composition having output that is substantially infrared radiation on combustion | |
| CA2743063C (en) | Ignition sets with improved ignition performance | |
| CZ70797A3 (en) | Igniting elements and finely graded ignition mixtures | |
| IL227588A (en) | Active composition for a decoy which radiates spectrally on burnup of the active composition | |
| US8002914B1 (en) | Smokeless flash powder | |
| EP4317122A3 (en) | Cool burning hydrate fuels in gas generant formulations for automotive airbag applications | |
| US6964715B2 (en) | High impetus, high burn rate gas generant propellant and seatbelt pretensioner incorporating same | |
| RU2202528C1 (en) | Thermostable ignition compound | |
| AU2021266255A1 (en) | Active composition for a pyrotechnic decoy target that burns at high wind speed | |
| US9193637B1 (en) | Magnesium/alkyl polysulfide white star illuminants | |
| KR20210080952A (en) | Explosives delay composition and method for producing explosives retardant using the same | |
| JPH01249684A (en) | Solid propellant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20211224 |
|
| WD01 | Invention patent application deemed withdrawn after publication |