EP2620422B1 - N2O-based, ionic monopropellants for space propulsion - Google Patents
N2O-based, ionic monopropellants for space propulsion Download PDFInfo
- Publication number
- EP2620422B1 EP2620422B1 EP13152595.8A EP13152595A EP2620422B1 EP 2620422 B1 EP2620422 B1 EP 2620422B1 EP 13152595 A EP13152595 A EP 13152595A EP 2620422 B1 EP2620422 B1 EP 2620422B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- triazolium
- nitrate
- dicyanamide
- fuel
- ammonium
- 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.)
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Links
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 75
- 150000003839 salts Chemical class 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 39
- 239000000446 fuel Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 37
- -1 hydrazinium ions Chemical class 0.000 claims description 35
- MJVUDZGNBKFOBF-UHFFFAOYSA-N n-nitronitramide Chemical compound [O-][N+](=O)N[N+]([O-])=O MJVUDZGNBKFOBF-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 28
- 239000001272 nitrous oxide Substances 0.000 claims description 25
- 238000002485 combustion reaction Methods 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 21
- 229910002651 NO3 Inorganic materials 0.000 claims description 21
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000007791 liquid phase Substances 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 18
- 150000001768 cations Chemical class 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 17
- 125000001425 triazolyl group Chemical group 0.000 claims description 15
- 150000001540 azides Chemical class 0.000 claims description 12
- SFLZICZHQSFYOR-UHFFFAOYSA-N 1-nitrotetrazole-5-carboxylic acid Chemical compound OC(=O)C1=NN=NN1[N+]([O-])=O SFLZICZHQSFYOR-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 10
- UAZDIGCOBKKMPU-UHFFFAOYSA-O azanium;azide Chemical compound [NH4+].[N-]=[N+]=[N-] UAZDIGCOBKKMPU-UHFFFAOYSA-O 0.000 claims description 10
- RBLWMQWAHONKNC-UHFFFAOYSA-N hydroxyazanium Chemical compound O[NH3+] RBLWMQWAHONKNC-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 9
- XYODKMYYACGWBN-UHFFFAOYSA-N aminoazanium;nitroformate Chemical compound [NH3+]N.[O-]C(=O)[N+]([O-])=O XYODKMYYACGWBN-UHFFFAOYSA-N 0.000 claims description 9
- CRJZNQFRBUFHTE-UHFFFAOYSA-N hydroxylammonium nitrate Chemical compound O[NH3+].[O-][N+]([O-])=O CRJZNQFRBUFHTE-UHFFFAOYSA-N 0.000 claims description 9
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 7
- BRUFJXUJQKYQHA-UHFFFAOYSA-O ammonium dinitramide Chemical compound [NH4+].[O-][N+](=O)[N-][N+]([O-])=O BRUFJXUJQKYQHA-UHFFFAOYSA-O 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- VMPIHZLTNJDKEN-UHFFFAOYSA-O triethanolammonium nitrate Chemical compound [O-][N+]([O-])=O.OCC[NH+](CCO)CCO VMPIHZLTNJDKEN-UHFFFAOYSA-O 0.000 claims description 7
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 claims description 6
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims description 6
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical class OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 5
- LJVQHXICFCZRJN-UHFFFAOYSA-N 1h-1,2,4-triazole-5-carboxylic acid Chemical compound OC(=O)C1=NC=NN1 LJVQHXICFCZRJN-UHFFFAOYSA-N 0.000 claims description 4
- 125000005235 azinium group Chemical group 0.000 claims description 4
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 claims description 4
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-O hydron;1,2-oxazole Chemical compound C=1C=[NH+]OC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-O 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical compound C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-O hydron;1h-pyrrole Chemical compound [NH2+]1C=CC=C1 KAESVJOAVNADME-UHFFFAOYSA-O 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 claims description 3
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 3
- CQDAMYNQINDRQC-UHFFFAOYSA-N oxatriazole Chemical compound C1=NN=NO1 CQDAMYNQINDRQC-UHFFFAOYSA-N 0.000 claims description 3
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 claims description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 3
- LAZVTKQYCZFNSZ-UHFFFAOYSA-N nitro formate Chemical compound [O-][N+](=O)OC=O LAZVTKQYCZFNSZ-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 24
- 239000003380 propellant Substances 0.000 description 20
- CCRNCEKMSVYFLU-UHFFFAOYSA-N 4,5-dinitro-1h-imidazole Chemical compound [O-][N+](=O)C=1N=CNC=1[N+]([O-])=O CCRNCEKMSVYFLU-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- IVRMZWNICZWHMI-UHFFFAOYSA-N Azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 230000001590 oxidative effect Effects 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- WVVQNTCHJACXPP-UHFFFAOYSA-O 4-methyltetrazol-4-ium-1,5-diamine Chemical compound C[N+]=1N=NN(N)C=1N WVVQNTCHJACXPP-UHFFFAOYSA-O 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-O hydrazinium(1+) Chemical compound [NH3+]N OAKJQQAXSVQMHS-UHFFFAOYSA-O 0.000 description 9
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 8
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 7
- MWZDIEIXRBWPLG-UHFFFAOYSA-O 2-methyl-1h-1,2,4-triazol-2-ium Chemical compound C[N+]1=CN=CN1 MWZDIEIXRBWPLG-UHFFFAOYSA-O 0.000 description 7
- OKHTZNLRYCWACF-UHFFFAOYSA-N 5-azido-1h-1,2,4-triazole Chemical compound [N-]=[N+]=NC1=NC=NN1 OKHTZNLRYCWACF-UHFFFAOYSA-N 0.000 description 7
- IGNDAXMAFOVNIC-UHFFFAOYSA-O 5-azido-2-methyl-1H-1,2,4-triazol-2-ium Chemical compound C[NH+]1C=NC(N=[N+]=[N-])=N1 IGNDAXMAFOVNIC-UHFFFAOYSA-O 0.000 description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 7
- UZXHZRFWCCZBDW-UHFFFAOYSA-O aminoazanium;azide Chemical compound [NH3+]N.[N-]=[N+]=[N-] UZXHZRFWCCZBDW-UHFFFAOYSA-O 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000002608 ionic liquid Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000006053 organic reaction Methods 0.000 description 6
- MXLZUALXSYVAIV-UHFFFAOYSA-N 1,2-dimethyl-3-propylimidazol-1-ium Chemical compound CCCN1C=C[N+](C)=C1C MXLZUALXSYVAIV-UHFFFAOYSA-N 0.000 description 5
- BSAYKWAKQFDCPG-UHFFFAOYSA-N 1-but-2-ynyl-3-methylimidazol-3-ium Chemical compound CC#CCN1C=C[N+](C)=C1 BSAYKWAKQFDCPG-UHFFFAOYSA-N 0.000 description 5
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 5
- ICIVTHOGIQHZRY-UHFFFAOYSA-N 1-butyl-3-methylimidazol-3-ium;cyanoiminomethylideneazanide Chemical compound [N-]=C=NC#N.CCCCN1C=C[N+](C)=C1 ICIVTHOGIQHZRY-UHFFFAOYSA-N 0.000 description 5
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000005649 metathesis reaction Methods 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 4
- UFDAQRCLFHCJEQ-UHFFFAOYSA-N 1,5-dimethyl-2H-tetrazol-3-amine Chemical compound CN1NN(N)N=C1C UFDAQRCLFHCJEQ-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IZBOAZUNIFCNBE-UHFFFAOYSA-N ethanol;1-methylimidazole Chemical compound CCO.CN1C=CN=C1 IZBOAZUNIFCNBE-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 241000894007 species Species 0.000 description 4
- OIEWJYPMDZYRBG-UHFFFAOYSA-N 1-azido-1h-triazol-1-ium;1-nitrotetrazole-5-carboxylate Chemical compound [N-]=[N+]=N[NH+]1C=CN=N1.[O-]C(=O)C1=NN=NN1[N+]([O-])=O OIEWJYPMDZYRBG-UHFFFAOYSA-N 0.000 description 3
- NIHOUJYFWMURBG-UHFFFAOYSA-N 1-ethyl-1-methylpyrrolidin-1-ium Chemical compound CC[N+]1(C)CCCC1 NIHOUJYFWMURBG-UHFFFAOYSA-N 0.000 description 3
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 3
- OGLIVJFAKNJZRE-UHFFFAOYSA-N 1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1 OGLIVJFAKNJZRE-UHFFFAOYSA-N 0.000 description 3
- YQFWGCSKGJMGHE-UHFFFAOYSA-N 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1 YQFWGCSKGJMGHE-UHFFFAOYSA-N 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 3
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 3
- MIFXNTWNZOVEFV-UHFFFAOYSA-N 3-azido-1h-1,2,4-triazol-1-ium;5-nitrotetrazole-5-carboxylate Chemical compound [N-]=[N+]=NC1=N[NH2+]C=N1.[O-]C(=O)C1([N+]([O-])=O)N=NN=N1 MIFXNTWNZOVEFV-UHFFFAOYSA-N 0.000 description 3
- WXMVWUBWIHZLMQ-UHFFFAOYSA-N 3-methyl-1-octylimidazolium Chemical compound CCCCCCCCN1C=C[N+](C)=C1 WXMVWUBWIHZLMQ-UHFFFAOYSA-N 0.000 description 3
- XAGXLODJENLEBR-UHFFFAOYSA-N 4,5-dimethyltetrazol-4-ium-1-amine Chemical compound CC=1N(N)N=N[N+]=1C XAGXLODJENLEBR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- GCMIVBDGXCCOEP-UHFFFAOYSA-N N#CNC#N.N Chemical compound N#CNC#N.N GCMIVBDGXCCOEP-UHFFFAOYSA-N 0.000 description 3
- GRWCKIFVULPUSU-UHFFFAOYSA-O N[N+]([O-])=O.N[N+]([O-])=O.CN1N=N[N+](N)=C1N Chemical compound N[N+]([O-])=O.N[N+]([O-])=O.CN1N=N[N+](N)=C1N GRWCKIFVULPUSU-UHFFFAOYSA-O 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005474 detonation Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000008040 ionic compounds Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 3
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-O propan-1-aminium Chemical compound CCC[NH3+] WGYKZJWCGVVSQN-UHFFFAOYSA-O 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 0 **1C(*)=*(*)C(*)=*1 Chemical compound **1C(*)=*(*)C(*)=*1 0.000 description 2
- AOCVWHNJJSAWLY-UHFFFAOYSA-O 1,5-dimethyl-1,2-dihydrotetrazol-1-ium-3-amine;nitrate Chemical compound [O-][N+]([O-])=O.CN1NN(N)[NH+]=C1C AOCVWHNJJSAWLY-UHFFFAOYSA-O 0.000 description 2
- FDWZAOGDOVQOLD-UHFFFAOYSA-N 1-methylpyrrolinium Chemical compound C[N+]1=CCCC1 FDWZAOGDOVQOLD-UHFFFAOYSA-N 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- UTYHRWFPLVSEEY-UHFFFAOYSA-N 3-azido-1-methyl-1h-1,2,4-triazol-1-ium;5-nitrotetrazole-5-carboxylate Chemical compound C[NH+]1C=NC(N=[N+]=[N-])=N1.[O-]C(=O)C1([N+]([O-])=O)N=NN=N1 UTYHRWFPLVSEEY-UHFFFAOYSA-N 0.000 description 2
- MIGFTZZNPSSSAV-UHFFFAOYSA-N 4,5-dimethyltetrazol-4-ium-1-amine;nitrate Chemical compound [O-][N+]([O-])=O.CC=1N(N)N=N[N+]=1C MIGFTZZNPSSSAV-UHFFFAOYSA-N 0.000 description 2
- FSGREQVUKVWGDV-UHFFFAOYSA-O 4-methyltetrazol-4-ium-1,5-diamine;nitrate Chemical compound [O-][N+]([O-])=O.C[N+]=1N=NN(N)C=1N FSGREQVUKVWGDV-UHFFFAOYSA-O 0.000 description 2
- HBVOEKFVEUNBRJ-UHFFFAOYSA-N 5-nitrotetrazole-5-carboxylate;1h-1,2,4-triazol-1-ium Chemical compound [NH2+]1C=NC=N1.[O-]C(=O)C1([N+]([O-])=O)N=NN=N1 HBVOEKFVEUNBRJ-UHFFFAOYSA-N 0.000 description 2
- HTJFMHFDZWNRLO-UHFFFAOYSA-N 5-nitrotetrazole-5-carboxylate;1h-1,2,4-triazol-4-ium-4-amine Chemical compound N[N+]=1C=NNC=1.[O-]C(=O)C1([N+]([O-])=O)N=NN=N1 HTJFMHFDZWNRLO-UHFFFAOYSA-N 0.000 description 2
- NKGQFSOOECRNTM-UHFFFAOYSA-N 5-nitrotetrazole-5-carboxylic acid Chemical compound OC(=O)C1([N+]([O-])=O)N=NN=N1 NKGQFSOOECRNTM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- AJPXOOXHHFMBQS-UHFFFAOYSA-N N[N+]([O-])=O.N[N+]([O-])=O.NO Chemical compound N[N+]([O-])=O.N[N+]([O-])=O.NO AJPXOOXHHFMBQS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FTPMPYVSRHETHX-UHFFFAOYSA-N [NH3+]O.[N-]=[N+]=[N-] Chemical compound [NH3+]O.[N-]=[N+]=[N-] FTPMPYVSRHETHX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RAESLDWEUUSRLO-UHFFFAOYSA-O aminoazanium;nitrate Chemical compound [NH3+]N.[O-][N+]([O-])=O RAESLDWEUUSRLO-UHFFFAOYSA-O 0.000 description 2
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IWMOUXZYHULGCL-UHFFFAOYSA-N nitro 2H-tetrazole-5-carboxylate Chemical compound [O-][N+](=O)OC(=O)C1=NN=NN1 IWMOUXZYHULGCL-UHFFFAOYSA-N 0.000 description 2
- 150000002829 nitrogen Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GMRIOAVKKGNMMV-UHFFFAOYSA-N tetrabutylazanium;azide Chemical compound [N-]=[N+]=[N-].CCCC[N+](CCCC)(CCCC)CCCC GMRIOAVKKGNMMV-UHFFFAOYSA-N 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- OEKLMVGIQXMHNW-UHFFFAOYSA-N tetrazole-2-carboxylic acid Chemical compound OC(=O)N1N=CN=N1 OEKLMVGIQXMHNW-UHFFFAOYSA-N 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PLFFHJWXOGYWPR-HEDMGYOXSA-N (4r)-4-[(3r,3as,5ar,5br,7as,11as,11br,13ar,13bs)-5a,5b,8,8,11a,13b-hexamethyl-1,2,3,3a,4,5,6,7,7a,9,10,11,11b,12,13,13a-hexadecahydrocyclopenta[a]chrysen-3-yl]pentan-1-ol Chemical compound C([C@]1(C)[C@H]2CC[C@H]34)CCC(C)(C)[C@@H]1CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@@H]1[C@@H](CCCO)C PLFFHJWXOGYWPR-HEDMGYOXSA-N 0.000 description 1
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 description 1
- YUQWYOKVPSTRNH-UHFFFAOYSA-L 1,3-dimethylimidazol-1-ium;methyl-dioxido-oxo-$l^{5}-phosphane Chemical compound CP([O-])([O-])=O.CN1C=C[N+](C)=C1.CN1C=C[N+](C)=C1 YUQWYOKVPSTRNH-UHFFFAOYSA-L 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- LGTRZSWLBHWTFT-UHFFFAOYSA-N 1-but-2-ynyl-3-methylimidazol-3-ium;azide Chemical compound [N-]=[N+]=[N-].CC#CCN1C=C[N+](C)=C1 LGTRZSWLBHWTFT-UHFFFAOYSA-N 0.000 description 1
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 1
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- MGLQVTQBBOYZKF-UHFFFAOYSA-N 1-methyl-1h-1,2,4-triazol-1-ium;5-nitrotetrazole-5-carboxylate Chemical compound C[NH+]1C=NC=N1.[O-]C(=O)C1([N+]([O-])=O)N=NN=N1 MGLQVTQBBOYZKF-UHFFFAOYSA-N 0.000 description 1
- UVAJCDOUVGWEFK-UHFFFAOYSA-N 1-methyl-2,3-dihydropyrrole Chemical compound CN1CCC=C1 UVAJCDOUVGWEFK-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- JODMJNWWSGYIJT-UHFFFAOYSA-O 4-methyltetrazol-4-ium-1,5-diamine;azide Chemical compound [N-]=[N+]=[N-].C[N+]=1N=NN(N)C=1N JODMJNWWSGYIJT-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000321453 Paranthias colonus Species 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- JJQIVFMEDDSMKS-UHFFFAOYSA-N [O-][N+](C(NC=N1)=C1[N+]([O-])=O)=O.C1=NC=NN1 Chemical compound [O-][N+](C(NC=N1)=C1[N+]([O-])=O)=O.C1=NC=NN1 JJQIVFMEDDSMKS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012223 aqueous fraction Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- MXTUDRWETHDXHP-UHFFFAOYSA-N cyanocyanamide 1H-imidazole Chemical compound C1=CNC=N1.N#CNC#N MXTUDRWETHDXHP-UHFFFAOYSA-N 0.000 description 1
- FMYCKRQZPVZFLW-UHFFFAOYSA-N cyanoiminomethylideneazanide tributyl(methyl)azanium Chemical compound [N-]=C=NC#N.CCCC[N+](C)(CCCC)CCCC FMYCKRQZPVZFLW-UHFFFAOYSA-N 0.000 description 1
- UBQLCZUQCFNAGM-UHFFFAOYSA-N cyanoiminomethylideneazanide;2-(3-methylimidazol-3-ium-1-yl)ethanol Chemical compound N#C[N-]C#N.CN1C=C[N+](CCO)=C1 UBQLCZUQCFNAGM-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-O hydron piperazine Chemical compound [H+].C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-O 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012073 inactive phase Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003853 pentazoles Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001141 propulsive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- JSFMCJBSPUHNHS-UHFFFAOYSA-N silver;cyanoiminomethylideneazanide Chemical compound [Ag+].N#C[N-]C#N JSFMCJBSPUHNHS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- IXBPPZBJIFNGJJ-UHFFFAOYSA-N sodium;cyanoiminomethylideneazanide Chemical compound [Na+].N#C[N-]C#N IXBPPZBJIFNGJJ-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000003039 volatile agent 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
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
-
- 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)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/08—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more liquids
Definitions
- the chemical propulsion of the satellites is generally ensured by the decomposition or the combustion of propellants thus producing gases with very high temperature and very high pressure.
- the propellants may be monergols or bergols.
- hydrazine and its methylated derivatives pose significant risks in terms of manufacturing, handling and operations because of their sensitivity to impurities and, to a lesser extent, to temperature and their extreme toxicity. . These constraints generate cumbersome operating procedures and high implementation costs.
- hydrazine is currently on the list of compounds listed by REACh (European Chemical Regulation), because of its dangerousness (carcinogenic substance, mutagenic or toxic, persistent, biaccumulable or toxic). In fact, a potential progressive ban on hydrazine and its derivatives is to be expected and its substitution may be necessary in the near future.
- the patent application WO0050363 discloses a formulation based on the dinitramide anion (N (NO 2 ) 2 - ) associated with an energetic cation - preferably ammonium (NH 4 + ), hydrazinium (N 2 H 5 + ) or hydroxylammonium (OHNH 3 + ), ammonium being preferred - the salt formed being dissolved in an aqueous reducing solution or not.
- the liquid reductant can thus serve as a solvent or be in equilibrium with a water fraction so as to form a liquid ionic energy solution.
- the reducing agent may in particular be chosen from alcohols, amines, aldehydes or ketones, a large polarity being sought in order to promote the solubility of the energetic salt.
- Patent applications WO01 / 51433 and WO2009 / 062183 teach as liquid monolols mixtures of nitrous oxide (N 2 O) as an oxidant and hydrocarbon fuel, such as propane (C 3 H 8 ) or ethane (C 2 H) 6 ), ethylene (C 2 H 4 ), acetylene (C 2 H 2 ).
- the choice of nitrous oxide as oxidant is motivated by its very good oxidizing power and by its volatile nature offering the possibility of a self-pressurization of the tank.
- the binary N 2 O / hydrocarbon formed mixture has a high saturation vapor pressure (38 bar at 10 ° C for the monergol NOFB34) and very sensitive to the temperature (48 bar at 20 ° C for the same monergol), which, on the one hand, requires qualified equipment for a higher operating pressure than those currently encountered and, on the other hand, makes its thermal control continuously delicate.
- the energy density of these mixtures remains to be improved in particular because of their density sometimes less than 700 kg.m -3 .
- the subject of the present invention is therefore a monergol based on nitrous oxide which does not have the disadvantages stated above, and in particular instability.
- the problem related to the sensitivity of the mixture has been solved by generating a monergol in which the fuel is, in its isolated form, an energetic salt. Its dissolution in the nitrous oxide generates an ionic liquid phase. Due to its reduced saturated vapor pressure, the fuel is fixed in the liquid phase, so that the vapor phase coexisting with the liquid contains only nitrous oxide.
- the density of monergols thus formed is high thanks to the contribution of salt, thus guaranteeing a high energy density.
- the salts used have enthalpies of formation and structures such that their association with nitrous oxide provides theoretical Isp between 300s and 350s depending on the candidates.
- Nitrous oxide N 2 O molar mass 44.013 kg mol -1
- N 2 O molar mass 44.013 kg mol -1
- Its saturation vapor pressure (the pressure at which the gas phase is in equilibrium with its liquid phase) varies in the range [0 +20] ° C between 31.3 bar and 50.6 bar. Over the same interval, the density of its liquid phase increases from 907.4 kg.m -3 to 786.6 kg.m -3 , while that of its gas phase increases from 84.9 kg.m -3 to 158.1 kg.m -3 .
- Nitrous oxide is therefore a highly volatile compound.
- N 2 O can exist in diphasic form (thermodynamic liquid / gas equilibrium) or monophasic beyond its critical point. Under normal temperature and pressure conditions, nitrous oxide is in liquid / gas equilibrium.
- the nitrous oxide is in liquid form. It can be partially in the form of gas.
- N 2 O in liquid form is particularly advantageous in that it solubilizes the fuel and thus act as a solvent.
- the nitrous oxide is then in solution with the liquid phase of fuel.
- the liquid phase of N 2 O is then mixed with the fuel.
- the oxidizing and combustible species are in the same phase.
- Pressurizing gas is a neutral gas - that is, not intended to participate in the chemical reaction - used in reservoirs to pressurize the monergols and allow them to flow back into the fluidic lines in the direction of flow. thrusters. The system associated with this mode of operation is then called “positive expulsion".
- Helium (He) and dinitrogen (N 2 ) are the most common pressurizing gases.
- the use of an additional gas induces certain disadvantages such as the loss of effective volume in the reservoir and the presence of traces of gas in the monergol by absorption.
- the fuel is an ionic compound introduced into the liquid phase of the monergol.
- An ionic solution is a liquid containing ions among the solvent.
- the salt is generally polar, is solid under standard temperature conditions, and is soluble in N 2 O.
- the salt is generally present as a pure liquid at room temperature (RTIL: Room Temperature Lonic Liquid), has a melting temperature below -20 ° C, and forms a binary mixture with N 2 O.
- RTIL Room Temperature Lonic Liquid
- the salt, solid in the standard state is dissolved in a solvent to form an ionic solution itself in admixture with N 2 O present in liquid form.
- the solvent is advantageously an energy solvent, such as methanol, for example.
- the liquid phase contains this part of N 2 O in solution.
- the fuel in liquid form makes it possible to guarantee an advanced stability of the monergol in the face of thermomechanical stimuli, in particular of detonation (shocks, adiabatic compression, etc.) and electrostatic stimuli.
- the fuel is such that it is compatible with N 2 O and of reduced volatility by its ionic nature.
- the fuel can be considered as non-volatile.
- the fuel must be an N 2 O reducing species but may optionally include certain oxidizing groups.
- the fuel is selected from the salts of the energetic compounds.
- Energetic compounds are molecules or combinations of molecules with high energy density and high material density. This results in a standard enthalpy of positive and high formation, which may reach several thousand kJ.kg -1 - typically 2000 to 3000 kJ.kg -1 - and a high density, generally greater than 1000 kg.m -3. . This is called HEDM (High Energy Density Materials). Some HEDMs demonstrate outstanding performance but have limitations of use because of their instability (uncontrolled release of energy) and are classified in the category of explosive materials. This is particularly the case of derivatives of pentazole. In addition, an additional feature specific to space propulsion concerns the molar mass of the products resulting from the combustion of these energetic compounds. The latter must be as low as possible - generally less than 30 gmol -1 - in order to guarantee a flame temperature to molar mass ratio. T ad M high, pledge of high specific impulse.
- the fuel also called “reducing agent”
- the fuel is any combination of a linear or heterocyclic cation and a linear or heterocyclic anion meeting the criteria presented above.
- the anion and / or the cation generally comprise one or more nitrogenous and / or unsaturated energetic groups such as amino, azido, cyano, propargyl, tripropargyl and guanidyl.
- the fuel is usually a nitrogen derivative, in the form of salt.
- the anion and / or the cation of said salt may contain one or more nitrogen atoms.
- Said cation may be chosen from nitrogen derivatives such as aliphatic, cyclic or aromatic, quaternary amines.
- said cation may be chosen from ammonium, imidazolium, triazolium and tetrazolium ions and their derivatives.
- ion derivatives refers to compounds having a nitrogen atom in the form of said ion.
- the analogues -inium and -idinium of the above unsaturated heterocyclic compounds refer to the corresponding partially saturated (-inium) and saturated (-idinium) analogues resulting from a partial or complete partial hydrogenation, such as, for example, pyrrolinium as an analogue. partially unsaturated and pyrrolidinium as a saturated analogue of pyrrolium.
- ammonium derivatives that may be mentioned are substituted ammonium compounds, such as ethylenediammonium, ethanolammonium, propylammonium, monopropargylammonium, tripropargylammonium, tetraethylammonium, N-tributyl-N-methylammonium, N-trimethylammonium, N-butylammonium, N-trimethyl-N-hexylammonium, N-trimethyl-N-propylammonium.
- substituted ammonium compounds such as ethylenediammonium, ethanolammonium, propylammonium, monopropargylammonium, tripropargylammonium, tetraethylammonium, N-tributyl-N-methylammonium, N-trimethylammonium, N-butylammonium, N-trimethyl-N-hexylammonium, N-trimethyl-N-propylammonium.
- pyrrolium derivatives that may be mentioned are substituted pyrroliums, in particular with an alkyl group, such as N-methylpyrrolium.
- imidazolium derivatives mention may be made of substituted imidazoliums, in particular with one or more alkyl groups, and / or hydroxyalkyls, such as 1-butyl-2,3-dimethylamidazolium or 1-butyl-3-methylimidazolium, 1,3-dimethylimidazolium, 1-ethanol-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, methylimidazolium, 1-octyl-3-methylimidazolium, 1-propyl-2 3-dimethylimidazolium, 1-propyl-2,3-dimethylimidazolium.
- 1-butyl-2,3-dimethylamidazolium or 1-butyl-3-methylimidazolium 1,3-dimethylimidazolium, 1-ethanol-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-hexyl
- pyrrolidinium derivatives By way of pyrrolidinium derivatives, mention may be made of substituted pyrrolidiniums, in particular with one or more alkyl groups, such as 1-butyl-1-methylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium and N-propyl-N-methylpyrrolidinium. .
- piperidinium derivatives mention may be made of piperidinium substituted with one or more alkyl groups, such as 1-methyl-1-propylpiperidinium.
- triazolium derivatives there may be mentioned 1-methyl-1,2,4-triazolium, 3-azido-1,2,4-triazolium, 1-methyl-3-azido-1,2,4 -triazolium, 4-amino-1,2,4-triazolium.
- tetrazolium As derivatives of tetrazolium, there may be mentioned 1-amino-4,5-dimethyltetrazolium, 2-amino-4,5-dimethyltetrazolium, 1,5-diamino-4-methyltetrazolium.
- alkyl group saturated hydrocarbon radicals, straight or branched chain, of 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms. Mention may in particular be made, when they are linear, the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl and octadecyl radicals.
- alkyl radicals When they are branched or substituted by one or more alkyl radicals, mention may be made especially of the isopropyl, tert-butyl, 2-ethylhexyl, 2-methylbutyl, 2-methylpentyl, 1-methylpentyl and 3-methylheptyl radicals.
- the counterion is especially chosen from azide, nitrate, dinitramide, dicyanamide, imidazolate and tetrazolate ions and their derivatives.
- the salts according to the invention can be obtained by application or adaptation of known methods, in particular according to the methods described by Keskin et al., J. of Supercritical Fluids 43 (2007) 150-180 , in particular by coupling of its constituents, by metathesis or by acid-base reaction.
- the desired salt can be prepared from the compound in neutral form by salification, for example by addition of the acid containing the desired anion; or from another ionic compound by ion exchange, for example on a column, or by transsalification in the presence of an acid containing the desired anion, or by metathesis.
- nitrate, dinitramide and azide salts can be advantageously prepared by metathesis in the presence of the silver salts of nitrate, dinitramide and azide from the corresponding halides.
- the monergols according to the invention are such that the ratio N 2 O / fuel (by mass), known as the mixing ratio and often noted O / F or OF (for Oxidizer / Fuel ratio) is generally between 0, 1 and 10, preferably between 1 and 6.
- the specific impulse represents the duration during which the engine provides a thrust equal to the weight of the consumed propellant. It is thus an indicator of the "sobriety" and therefore of the energy performance of an ergol.
- C *, g 0 , ⁇ , P e and P c respectively represent the characteristic velocity of the gases ejected by the nozzle, the gravity at the altitude considered, the average isentropic coefficient of the ejected gases, the ejection pressure and the pressure in the room.
- R, T ad and M are respectively the universal constant of the ideal gases, the adiabatic temperature within the chamber (so-called "flame" if presence of combustion) and the average molar mass of the ejected gases.
- the present invention also relates to the process for preparing the monergol according to the invention.
- said process comprises the step of mixing the fuel and N 2 O.
- This mixture can be carried out at room temperature, but in the case where a solid salt in the standard state is used, the maximum solubility should be considered at room temperature.
- the minimum storage temperature of the monergol orbit to overcome any risk of saturation and recrystallization in flight. It is therefore necessary, during the synthesis of the monergol, to respect this threshold.
- the minimum operating temperature of the monolgy in orbit is typically 0 ° C.
- the monolif according to the invention can be stored taking care not to exceed the maximum permissible storage temperature so as not to exceed a certain saturation vapor pressure level, the MEOP (Maximum Expected Operating Pressure, maximum pressure expected in operation) being between 10 and 50 bar, typically between 20 and 40 bar.
- the maximum storage temperature is generally between 0 ° and 50 ° C.
- the monoling stone must have sufficient stability to be stored in orbit for a period of several years - typically 5 years, but possibly up to 15 years. The stability must be reflected in particular by the absence of phase separation (demixing, settling, etc.).
- the present invention also relates to a method of spatial propulsion using the monergol according to the invention.
- Spatial propulsion is the propulsion of spacecraft such as launchers and satellites.
- the monergol according to the invention is suitable for combustion operation.
- Combustion makes it possible to dispense with a catalytic bed and consequently with a complex propellant structure.
- the life of the propellant may be extended insofar as the catalyst currently constitutes the limiting element due to phenomena such as catalyst deactivation by erosion, oxidation, sintering, etc.
- the method according to the invention therefore comprises the combustion of the monergol according to the invention.
- the combustion is generally carried out by controlled ignition. This can be done according to the usual technologies, in particular by means of a high energy candle.
- the spark plug is generally positioned in the injection head, at the arrival of the monergol in the combustion chamber, the gases burned and evacuated by a nozzle placed at the opposite end of the combustion chamber.
- the method according to the invention may also comprise the means for pressurizing the monergol in the tank.
- the present propellant systems known as "catalytic monergols" with hydrazine operate for pressures in the tank of the order of 20 bar at the beginning of life (initial pressure) and 5 bar at the end of life. This pressure decreases during the draining of the monergol due to the relaxation of the pressurizing gas in the volume released by the propellant.
- Some systems provide for tank pressure regulation to keep it constant over a certain part of the satellite's mission (performance optimization). This is the case on a telecommunication platform, but this introduces a complex and expensive equipment.
- the pressurization can be advantageously carried out by the N 2 O solution itself because of its volatile nature, so that the use of an additional inert gas is no longer necessary. This results in a gain on the filling rate of the reservoir as well as on the apparent density of the liquid-gas torque.
- the pressurizing means can be ensured only by filling the monergol in the tank.
- the return to equilibrium between the liquid and vapor phases by vaporization of a liquid N 2 O fraction is accompanied by a slight drop in temperature (endothermic phenomenon), so that a slight decrease in pressure will be observed.
- This phenomenon can be counterbalanced by the exercise of a reheating of the tank via a thermal control (thermistors).
- This phenomenon of self-pressurization "represents a major advantage since, similarly to pressure regulators on biliquid engines, it allows the thrusters to operate near their optimum performance.
- the tank then operates in a conventional "blow down" manner similar to an inert gas pressurization.
- the method according to the invention may also include the previous step of loading the monolgy into the tank of the spacecraft.
- 1-Butyl-3-methyl-imidazolium dicyanamide can be prepared using the methodology described by Asikkala et al (Application of Ionic Liquids and Microactivation in Selected Organic Reactions, Acta Univ Oul. A 502, 2008, p. 134) by transsalification from 1-butyl-3-methyl-imidazolium chloride in the presence of sodium dicyanamide, the chloride being prepared by reaction between 1-chlorobutane and 1-methylimidazole.
- the dicyanamide of 1-butyl-3-methyl-imidazolium can be prepared by metathesis as described in particular in US8,034,202 from 1-butyl-3-methylimidazolium bromide in the presence of silver dicyanamide.
- ⁇ Based on triazolium cation: Denomination Atomic composition T FUS T DECOMP ⁇ ⁇ H f ° VS NOT H O [° C] [° C] [Kg / m3] [KJ / kg] 1,2,4-triazolium 4,5-dinitroimidazolate 5 7 5 4 156 165 1730 1022.5 4,5-dinitroimidazolate of 1-methyl-1,2,4-triazolium 6 7 7 4 102 150 1660 831.1 3-azido-1,2,4-triazolium 4,5-dinitro-im idazoate 5 10 4 4 92 158 1700 2214.6 4,5-dinitroimidazolate of 1-methyl-3-azido-1,2,4-tri
- the above salts can be prepared according to Singh et al Structure Bond 2007, 125: 35-83.
- Example 1 the first case can be illustrated by the use of the azide of 1- (2-butynyl) -3-methyl-imidazolium, noted [ByMIM] [N 3 - ].
- This compound can be prepared from bromide of 1- (2-butynyl) -3-methyl-imidazolium on azide exchange resin according to Schneider et al Inorganic Chemistry 2008, 47 (9), 3617-3624 . It can be dissolved by direct dissolution in N 2 O. The following figure gives the structure of [ByMIM] [N 3 - ]:
- Example 2 the second case can be represented by the liquid-liquid binary mixture between 1-butyl-3-methyl-imidazolium dicyanamide, denoted [BMIM] [N (CN) 2 - ] (marketed by Solvionic), and the N 2 O.
- BMIM 1-butyl-3-methyl-imidazolium dicyanamide
- Example 3 the third case can be illustrated by the ternary equilibrium between 1,5-diamino-4-methyl-tetrazolium dinitramide, noted [DAMT] [N (NO 2 ) 2 ] synthesized according to Singh et al Structure Bond 2007, 125: 35-83 ,, pyrrolidine and N 2 O.
- the structure of [DAMT] [N (NO 2 ) 2 ] is as follows:
- the specific impulse generated by monergol combustion is closely dependent on the O / F mixture ratio between N 2 O and the fuel (dissolved "crystalline" salt or liquid salt).
- a curve can then be described by plotting the evolution of the Isp as a function of O / F , any other parameter being kept constant (chamber pressure, initial temperature, expansion ratio ⁇ ).
- a maximum of Isp can then be identified as well as the corresponding optimal O / F.
- the monergol must be synthesized respecting this mixing ratio in order to provide the best propulsive performance.
- the solubility of the salt in N 2 O or in the N 2 O combined solution limits the range of O / F available.
- the crystalline salts of interest must therefore either have a high solubility at the specified minimum temperature (typically S T min > 100 ⁇ boy Wut . k ⁇ boy Wut NOT 2 ⁇ O - 1 or to disassemble a high mixing ratio Isp optimum (typically 4 O O / F ⁇ 10).
- the use of energetic solvent makes it possible to enhance the optimal mixing ratio, to reduce the amount of salt required and thus to respect the solubility ceiling.
- an optimal mixing ratio of 3.4 is found, which makes it possible to lower the mass of salt necessary for 117 ⁇ boy Wut . k ⁇ boy Wut NOT 2 ⁇ O - 1 .
- this approach alters the maximum Isp (here, about -6s), which shows all the importance of the energy density of the solvent used.
- the filling of the satellite tank can then be carried out by placing the storage tank and the propulsion module tank in communication and withdrawing the liquid phase.
- the driving force for the transfer of monoling from the drum to the reservoir is directly ensured by the self-pressurization of the monergol.
- the use of an additional neutral gas may be considered to expel the monolgy from the storage drum.
- the monol ⁇ N 2 O + ionic fuel ⁇ stored in the pressurized tank is injected into the propellant via a usual fluid line including in particular a flow control valve called "motor valve".
- the monergol is withdrawn at the reservoir by its liquid phase insofar as only this phase comprises both the oxidant and the fuel.
- a bleeding technique well adapted to the present invention is the capillary network system (also known as the surface tension tank), well known to those skilled in the art.
- the expulsion of the monergol through the fluidic line supplying the thrusters is ensured by the pressure generated by the N 2 O gas in equilibrium with the liquid solution. Only the liquid phase is then expelled.
- the value of the mass flow rate of the monergol injected into the propellant (s) is dictated by the total pressure drop in the fluid lines of the reservoir to the engine (s), in particular by the singular pressure drop of the injector (dictated by its design). As long as the monergol has not crossed the injection head, it remains in liquid phase as long as it exists in this state in the tank.
- the monergol When the monergol goes through the injector located at the engine head (called “front end”), the latter undergoes a relaxation. It then enters the upstream part of the combustion chamber and is caused to undergo a phase change.
- the cause of the phase change differs according to the state of the combustion chamber, more precisely its pressure and temperature level. If it is an ignition, it can be assumed that the monergol enters a "fresh" environment and empty or near vacuum (so-called rarefied medium) to the extent that the room communicates with the vacuum space via the nozzle.
- the monolol will volatilize rapidly since its saturation vapor pressure will be significantly higher than the residual pressure within the combustion chamber. This phenomenon will be exacerbated if the monolayer or the walls of the thruster are at a higher temperature.
- the ignition phase consists in synchronizing the triggering of the spark plug with the arrival of the flow of the monergol in order to generate a "soft" ignition (contrary to the "hard start” involving a peak of transient pressure and violent damage to the system) .
- the assurance of a quality ignition can also be achieved by the realization of a train of triggers of the candle (bursts of electric arcs) with relatively constant frequency (period of the order of a few tens of milliseconds to hundreds of milliseconds).
- the arcing stream can also be fired in a slight phase advance over the injection to act as a local preheat.
- the optimization of the ignition thus relies on the conjunction of a geometric design and an optimized sequence of trips.
- the combustion is maintained after ignition as long as the monergol flow is maintained (open motor valve) and therefore does not require additional spark plugs.
- the energy released by the combustion of the monergol is sufficient to maintain the reaction of the fresh species injected.
- Combustion consists of a reaction between the main oxidant, namely N 2 O, and the ionic fuel optionally comprising oxidizing groups (eg nitramides).
- the reaction produces hot gases at high pressure.
- the combustion chamber is dimensioned such that the thermodynamic equilibrium is reached before ejection of the flue gas so as to achieve maximum efficiency.
- the gases are ejected through a nozzle provided with a convergent, sonic and divergent neck to initiate and accelerate the flow to generate an optimal thrust force.
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Description
La propulsion chimique des satellites est généralement assurée par la décomposition ou la combustion d'ergols produisant ainsi des gaz à très haute température et très forte pression. Les ergols peuvent être de type monergols ou biergols.The chemical propulsion of the satellites is generally ensured by the decomposition or the combustion of propellants thus producing gases with very high temperature and very high pressure. The propellants may be monergols or bergols.
La propulsion biergol est sans conteste l'une des deux technologies les plus utilisées de nos jours, en particulier sur satellites. Son grand volume d'utilisation s'explique notamment par son adoption sur satellites de télécommunication (marché important), de masses élevées, où les poussées mises en jeu sont de gamme supérieure (10N à 400N). Leurs hautes performances (impulsion spécifique (Isp)=320s pour une expansion ε de 330, réelle) sont de plus un paramètre de choix qui réduit la quantité d'ergol embarquée pour les longues manoeuvres de transfert en orbite géostationnaire. En revanche, les biergols nécessitent le stockage de deux composés chimiques (un oxydant et un combustible) dans des réservoirs séparés, et impliquent donc une architecture complexe. Le biergol peroxyde d'azote (NTO)/monométhylhydrazine (MMH) est actuellement la combinaison oxydant/réducteur de choix.Biergol propulsion is undoubtedly one of the two technologies most used today, especially on satellites. Its large volume of use is mainly due to its adoption on telecommunications satellites (large market), high masses, where the thrusts involved are higher range (10N to 400N). Their high performance (specific impulse (Isp) = 320s for an expansion ε of 330, real) are also a parameter of choice that reduces the amount of embedded propellant for long transfer operations in geostationary orbit. In contrast, biogas require the storage of two chemical compounds (an oxidant and a fuel) in separate tanks, and therefore involve a complex architecture. Biergol Nitrogen Peroxide (NTO) / Monomethylhydrazine (MMH) is currently the oxidant / reducer combination of choice.
La propulsion monergol constitue la seconde technologie la plus utilisée sur satellites. Sa forme la plus répandue consiste à utiliser un ergol métastable pouvant se décomposer au passage d'un lit catalytique de façon exothermique, ce qui a pour effet de convertir l'ergol en produits gazeux à haute température et faible masse molaire. La propulsion monergol dans sa généralité s'adresse aux petites poussées (1 N à 10N) et montre des performances assez moyennes. L'hydrazine (N2H4) est le monergol le plus courant et affiche une Isp de l'ordre de 210s à ε=80 (réelle). Son avantage majeur est de reposer sur une architecture assez simple en raison de la présence d'un unique ergol. Néanmoins, l'utilisation de l'hydrazine et de ses dérivés méthylés (MMH ou UDMH) présente des risques importants en termes de fabrication, manipulation et opérations du fait de leur sensibilité aux impuretés et, moindrement, à la température et de leur extrême toxicité. Ces contraintes sont génératrices de procédures opératoires lourdes et de coûts de mise en oeuvre élevés. De plus, l'hydrazine figure actuellement sur la liste des composés listés par REACh (Réglementation chimique européenne), en raison de sa dangerosité (substance cancérigène, mutagène ou toxique, persistante, biaccumulable ou toxique). De fait, une interdiction potentielle progressive de l'hydrazine puis de ses dérivés est à prévoir et sa substitution pourrait être nécessaire dans un futur proche.Monergol propulsion is the second most widely used satellite technology. Its most common form is to use a metastable propellant that can decompose in the passage of a catalytic bed exothermically, which has the effect of converting propellant into gaseous products at high temperature and low molar mass. Propulsion monergol in its generality is for small outbreaks (1 N to 10N) and shows fairly average performance. Hydrazine (N 2 H 4 ) is the most common monergol and displays an Isp of the order of 210s at ε = 80 (real). Its major advantage is to rely on a fairly simple architecture due to the presence of a unique propellant. However, the use of hydrazine and its methylated derivatives (MMH or UDMH) poses significant risks in terms of manufacturing, handling and operations because of their sensitivity to impurities and, to a lesser extent, to temperature and their extreme toxicity. . These constraints generate cumbersome operating procedures and high implementation costs. In addition, hydrazine is currently on the list of compounds listed by REACh (European Chemical Regulation), because of its dangerousness (carcinogenic substance, mutagenic or toxic, persistent, biaccumulable or toxic). In fact, a potential progressive ban on hydrazine and its derivatives is to be expected and its substitution may be necessary in the near future.
De nombreuses études sont actuellement menées pour identifier des alternatives qualifiées de « vertes » en raison de leur toxicité réduite comparée à celle de l'hydrazine. Les « ergols verts » recherchés, respectant la réglementation REACh, devront également obéir à des exigences spécifiques au domaine spatial, notamment en termes de stockage à long terme, de stabilités thermique et mécanique (vis-à-vis des chocs, détonation, compression adiabatique, etc.), de large compatibilité avec les matériaux des systèmes de propulsion (réservoirs, tuyauteries, vannes...), de compatibilité avec les contraintes spatiales (points de fusion/ébullition, pression de vapeur etc.), de maîtrise des impacts systèmes (encombrement/masse, assemblage, intégration et tests) tout en présentant des performances élevées (Isp, masse volumique).Many studies are currently being conducted to identify alternatives labeled "green" because of their reduced toxicity compared to that of hydrazine. The "green propellants" sought, complying with the REACh regulations, will also have to comply with specific requirements in the space field, particularly in terms of long-term storage, thermal and mechanical stability (with respect to shocks, detonation, adiabatic compression). , etc.), broad compatibility with propulsion system materials (tanks, pipes, valves, etc.), compatibility with spatial constraints (melting / boiling points, vapor pressure, etc.), impact control systems (bulk / mass, assembly, integration and tests) while presenting high performances (Isp, density).
Parmi les alternatives étudiées ont été envisagés des monergols basés sur l'ADN (dinitramide d'ammonium), le HAN (nitrate d'hydroxylammonium) ou encore HNF (nitroformate d'hydrazinium). Leur mise en oeuvre est identique à celle de l'hydrazine mais, contrairement à cette dernière, ces monergols ioniques ont la particularité d'entrer en combustion après leur décomposition catalytique en raison de la présence d'espèces oxydantes et réductrices propices à une oxydo-réduction. Ceci permet d'atteindre, sous l'effet de la température, des Isp légèrement supérieures à celle de l'hydrazine (Isp = 230s à ε=50, rélle). La demande de brevet
D'autres pistes ont été poursuivies en matière à la fois de monergols alternatifs « verts » et de mise en oeuvre de leur réaction. Les demandes de brevet
La présente invention a donc ainsi pour objet un monergol à base de protoxyde d'azote ne présentant pas les désavantages énoncés ci-avant, et notamment l'instabilité. En premier lieu, le problème lié à la sensibilité du mélange a été résolu en générant un monergol dans lequel le combustible est, sous sa forme isolée, un sel énergétique. Sa mise en solution dans le protoxyde d'azote génère une phase liquide ionique. De par sa pression de vapeur saturante réduite, le combustible est fixé en phase liquide, de sorte que la phase vapeur cohabitant avec le liquide contienne uniquement du protoxyde d'azote. En second lieu, la masse volumique des monergols ainsi formés est élevée grâce à l'apport du sel, garantissant ainsi une densité énergétique élevée. Les sels mis en oeuvre possèdent des enthalpies de formation et des structures telles que leur association au protoxyde d'azote fournit des Isp théoriques comprises entre 300s et 350s selon les candidats.The subject of the present invention is therefore a monergol based on nitrous oxide which does not have the disadvantages stated above, and in particular instability. In the first place, the problem related to the sensitivity of the mixture has been solved by generating a monergol in which the fuel is, in its isolated form, an energetic salt. Its dissolution in the nitrous oxide generates an ionic liquid phase. Due to its reduced saturated vapor pressure, the fuel is fixed in the liquid phase, so that the vapor phase coexisting with the liquid contains only nitrous oxide. Secondly, the density of monergols thus formed is high thanks to the contribution of salt, thus guaranteeing a high energy density. The salts used have enthalpies of formation and structures such that their association with nitrous oxide provides theoretical Isp between 300s and 350s depending on the candidates.
Selon un premier objet, la présente invention concerne donc un monergol formé par un mélange comprenant :
- du protoxyde d'azote (N2O) à titre d'oxydant au moins partiellement sous forme liquide, et
- un combustible sous forme de sel dans la phase liquide du N2O.
- nitrous oxide (N 2 O) as an oxidant at least partially in liquid form, and
- a fuel in the form of salt in the liquid phase of N 2 O.
Le protoxyde d'azote N2O, de masse molaire 44,013 kg.mol-1, est aussi appelé oxyde nitreux, monoxyde de diazote, oxyde d'azote, oxyde de diazote. Son point critique est à situé à Pc=72,51 bar et Tc=36,42°C. Sa pression de vapeur saturante (pression à laquelle la phase gazeuse est en équilibre avec sa phase liquide) varie dans l'intervalle [0 +20]°C entre 31,3 bar et 50,6 bar. Sur ce même intervalle, la masse volumique de sa phase liquide passe de 907,4 kg.m-3 à 786,6 kg.m-3, tandis que celle de sa phase gazeuse croît de 84,9 kg.m-3 à 158,1 kg.m-3. Le protoxyde d'azote est donc un composé fortement volatil. Selon les conditions de température et de pression, le N2O peut exister sous forme diphasique (équilibre thermodynamique liquide/gaz) ou monophasique au-delà de son point critique. Dans les conditions normales de température et de pression, le protoxyde d'azote est en équilibre liquide/gaz.Nitrous oxide N 2 O, molar mass 44.013 kg mol -1 , is also called nitrous oxide, nitrous oxide, nitrogen oxide, nitrous oxide. Its critical point is at P c = 72.51 bar and T c = 36.42 ° C. Its saturation vapor pressure (the pressure at which the gas phase is in equilibrium with its liquid phase) varies in the range [0 +20] ° C between 31.3 bar and 50.6 bar. Over the same interval, the density of its liquid phase increases from 907.4 kg.m -3 to 786.6 kg.m -3 , while that of its gas phase increases from 84.9 kg.m -3 to 158.1 kg.m -3 . Nitrous oxide is therefore a highly volatile compound. Depending on the temperature and pressure conditions, N 2 O can exist in diphasic form (thermodynamic liquid / gas equilibrium) or monophasic beyond its critical point. Under normal temperature and pressure conditions, nitrous oxide is in liquid / gas equilibrium.
Selon l'invention, le protoxyde d'azote est sous forme liquide. Il peut être partiellement sous forme de gaz.According to the invention, the nitrous oxide is in liquid form. It can be partially in the form of gas.
La présence de N2O sous forme liquide est particulièrement avantageuse en ce qu'elle permet de solubiliser le combustible et de jouer ainsi le rôle de solvant. Le protoxyde d'azote est alors en solution avec la phase liquide de combustible.The presence of N 2 O in liquid form is particularly advantageous in that it solubilizes the fuel and thus act as a solvent. The nitrous oxide is then in solution with the liquid phase of fuel.
La phase liquide du N2O est alors en mélange avec le combustible. De fait, les espèces oxydantes et combustibles sont dans une même phase.The liquid phase of N 2 O is then mixed with the fuel. In fact, the oxidizing and combustible species are in the same phase.
La présence d'une phase gazeuse constituée de N2O en équilibre dans le monergol est également intéressante en ce que le N2O gazeux joue le rôle de gaz de pressurisation.The presence of a gaseous phase consisting of N 2 O equilibrium in the monergol is also interesting in that the gaseous N 2 O plays the role of pressurizing gas.
On appelle « gaz de pressurisation » un gaz neutre - c'est-à-dire n'étant pas destiné à participer à la réaction chimique - utilisé dans les réservoirs pour mettre sous pression les monergols et permettre leur refoulement dans les lignes fluidiques en direction des propulseurs. Le système associé à ce mode de fonctionnement est alors dit « à expulsion positive ». L'hélium (He) et le diazote (N2) sont les gaz de pressurisation les plus courants. Le recours à un gaz additionnel induit certains inconvénients tels que la perte de volume efficace dans le réservoir et la présence de traces de gaz dans le monergol par absorption."Pressurizing gas" is a neutral gas - that is, not intended to participate in the chemical reaction - used in reservoirs to pressurize the monergols and allow them to flow back into the fluidic lines in the direction of flow. thrusters. The system associated with this mode of operation is then called "positive expulsion". Helium (He) and dinitrogen (N 2 ) are the most common pressurizing gases. The use of an additional gas induces certain disadvantages such as the loss of effective volume in the reservoir and the presence of traces of gas in the monergol by absorption.
Selon l'invention, le combustible est un composé ionique introduit dans la phase liquide du monergol.According to the invention, the fuel is an ionic compound introduced into the liquid phase of the monergol.
La phase liquide peut être constituée :
- 1) du combustible sous forme de sel solide lorsque isolé à température ambiante et solubilisé dans le N2O au moins partiellement présent sous forme liquide, ou
- 2) du sel fondu du combustible en mélange binaire avec le N2O au moins partiellement présent sous forme liquide, ou
- 3) d'une solution ionique du combustible dissous dans un solvant énergétique organique ou ionique, en mélange binaire avec le N2O au moins présent sous forme liquide. Si un solvant ionique est utilisé, il s'agit d'un sel fondu.
- 1) fuel in solid salt form when isolated at room temperature and solubilized in N 2 O at least partially present in liquid form, or
- 2) molten salt of the fuel in a binary mixture with N 2 O at least partially present in liquid form, or
- 3) an ionic solution of the fuel dissolved in an organic or ionic energy solvent, in a binary mixture with the N 2 O at least present in liquid form. If an ionic solvent is used, it is a molten salt.
On appelle solution ionique un liquide contenant des ions parmi le solvant.An ionic solution is a liquid containing ions among the solvent.
Selon le mode de réalisation 1), le sel est généralement polaire, est solide dans les conditions standard de température, et est soluble dans le N2O.According to embodiment 1), the salt is generally polar, is solid under standard temperature conditions, and is soluble in N 2 O.
A titre illustratif, on peut citer l'azoture de 1,5-diamino-4-méthyl-tétrazolium.By way of illustration, mention may be made of 1,5-diamino-4-methyl-tetrazolium azide.
Selon le mode de réalisation 2), le sel est généralement présent sous forme de liquide pur à température ambiante (RTIL : Room Température lonic Liquid), présente une température de fusion inférieure à -20°C, et formeun mélange binaire avec le N2O.According to Embodiment 2), the salt is generally present as a pure liquid at room temperature (RTIL: Room Temperature Lonic Liquid), has a melting temperature below -20 ° C, and forms a binary mixture with N 2 O.
A titre illustratif, on peut citer le 5-nitro-tétrazolate de 3-azido-1,2,4-triazolium.By way of illustration, mention may be made of 3-azido-1,2,4-triazolium-5-nitro-tetrazolate.
Selon le mode de réalisation 3), le sel, solide à l'état standard, est dissous dans un solvant pour former une solution ionique elle-même en mélange avec le N2O présent sous forme liquide. Le solvant est avantageusement un solvant énergétique, tel que le méthanol par exemple.According to Embodiment 3), the salt, solid in the standard state, is dissolved in a solvent to form an ionic solution itself in admixture with N 2 O present in liquid form. The solvent is advantageously an energy solvent, such as methanol, for example.
A titre illustratif, on peut citer le dinitramide de 1,5-diamino-4-méthyl-tétrazolium en mélange dans le méthanol.By way of illustration, mention may be made of 1,5-diamino-4-methyl-tetrazolium dinitramide mixed in methanol.
Lorsque le N2O est au moins partiellement présent sous forme liquide, la phase liquide contient cette part de N2O en solution.When the N 2 O is at least partially present in liquid form, the liquid phase contains this part of N 2 O in solution.
Le combustible sous forme liquide permet de garantir une stabilité avancée du monergol face aux stimuli thermo-mécaniques, notamment d'origine détonique (chocs, compression adiabatique, etc.) et électrostatiques.The fuel in liquid form makes it possible to guarantee an advanced stability of the monergol in the face of thermomechanical stimuli, in particular of detonation (shocks, adiabatic compression, etc.) and electrostatic stimuli.
Le combustible est tel qu'il est compatible avec N2O et de volatilité réduite de par sa nature ionique. En particulier, dans les conditions de stockage du monergol, le combustible peut être considéré comme non volatil.The fuel is such that it is compatible with N 2 O and of reduced volatility by its ionic nature. In particular, under the monergol storage conditions, the fuel can be considered as non-volatile.
Le terme « compatible » signifie ici que le combustible est, suivant sa phase dans les conditions standard :
- soluble ou miscible et apte à former des mélanges binaires solide-liquide ou liquide-liquide respectivement avec le N2O liquide ;
- donne lieu à un mélange thermodynamiquement stable avec le N2O liquide dans les conditions standard.
- soluble or miscible and capable of forming solid-liquid or liquid-liquid binary mixtures respectively with liquid N 2 O;
- gives rise to a thermodynamically stable mixture with liquid N 2 O under standard conditions.
Le combustible doit être une espèce réductrice de N2O mais peut éventuellement comporter certains groupes oxydants.The fuel must be an N 2 O reducing species but may optionally include certain oxidizing groups.
Pour répondre aux exigences de densité énergétique nécessaire à la propulsion spatiale, le combustible est choisi parmi les sels des composés énergétiques.To meet the energy density requirements necessary for space propulsion, the fuel is selected from the salts of the energetic compounds.
On appelle composés énergétiques les molécules ou associations de molécules présentant une densité d'énergie et une densité de matière élevées. Ceci se traduit par une enthalpie standard de formation positive et élevée, pouvant atteindre plusieurs milliers de kJ.kg-1 - typiquement 2000 à 3000 kJ.kg-1 - et par une masse volumique élevée, généralement supérieure à 1000 kg.m-3. On parle alors de HEDM (High Energy Density Materials). Certains HEDM démontrent des performances hors du commun mais présentent des limites d'utilisation en raison de leur instabilité (libération non contrôlée d'énergie) et sont classés dans la catégorie des matières explosives. C'est notamment le cas des dérivées du pentazole. En outre, une caractéristique supplémentaire propre à la propulsion spatiale concerne la masse molaire des produits issus de la combustion de ces composés énergétiques. Cette dernière doit être la plus faible possible - généralement inférieure à 30 g.mol-1 - afin de garantir un rapport température de flamme sur masse molaire
Selon l'invention, le combustible (aussi appelé « réducteur ») est toute association d'un cation linéaire ou hétérocyclique et d'un anion linéaire ou hétérocyclique répondant aux critères présentés ci-avant. L'anion et/ou le cation comprennent généralement un ou plusieurs groupes énergétiques azotés et/ou insaturés tels que amino, azido, cyano, propargyl, tripropargyl et guanidyl.According to the invention, the fuel (also called "reducing agent") is any combination of a linear or heterocyclic cation and a linear or heterocyclic anion meeting the criteria presented above. The anion and / or the cation generally comprise one or more nitrogenous and / or unsaturated energetic groups such as amino, azido, cyano, propargyl, tripropargyl and guanidyl.
Le combustible est généralement un dérivé azoté, sous forme de sel. Ainsi, l'anion et/ou le cation dudit sel peuvent contenir un ou plusieurs atomes d'azote.The fuel is usually a nitrogen derivative, in the form of salt. Thus, the anion and / or the cation of said salt may contain one or more nitrogen atoms.
Ledit cation peut être choisi parmi les dérivés azotés tels que les amines aliphatiques, cycliques, ou aromatiques, quaternaires.Said cation may be chosen from nitrogen derivatives such as aliphatic, cyclic or aromatic, quaternary amines.
Ledit cation peut notamment être choisi parmi :
- les cations linéaires, tels que les ions ammonium, hydroxylammonium, hydrazinium, et leurs dérivés ;
- les cations hétérocycliques saturés tels que pipéridinium, pipérazinium, et leurs dérivés ; et
- les cations hétérocycliques aromatiques ou non, tels que les azinium, azolium, diazolium, triazolium et tétrazolium, notamment pyridinium, pyrrolium, isoxazolium, pyrazolium, oxazolium, pyrazolium, imidazolium, oxadiazolium, triazolium, oxatriazolium, tétrazolium, pyrrolidium, triazinium, pyridazinium, pyrimidinium, pyrazinium, pipéridinium, 1,2,3-
1,2,4-triazolium, 1,4,5-ou 2,4,5- tétrazolium, ainsi que leurs analogues -inium et -idinium, et leurs dérivés.ou
- linear cations, such as ammonium, hydroxylammonium, hydrazinium, and their derivatives;
- saturated heterocyclic cations such as piperidinium, piperazinium, and their derivatives; and
- aromatic or non-aromatic heterocyclic cations, such as azinium, azolium, diazolium, triazolium and tetrazolium, in particular pyridinium, pyrrolium, isoxazolium, pyrazolium, oxazolium, pyrazolium, imidazolium, oxadiazolium, triazolium, oxatriazolium, tetrazolium, pyrrolidium, triazinium, pyridazinium, pyrimidinium , pyrazinium, piperidinium, 1,2,3- or 1,2,4-triazolium, 1,4,5- or 2,4,5-tetrazolium, as well as their analogues -inium and -idinium, and their derivatives.
Plus particulièrement, ledit cation peut être choisi parmi les ions ammonium, imidazolium, triazolium, tétrazolium et leurs dérivés.More particularly, said cation may be chosen from ammonium, imidazolium, triazolium and tetrazolium ions and their derivatives.
L'expression « dérivés d'ion » fait référence aux composés possédant un atome d'azote sous forme dudit ion.The term "ion derivatives" refers to compounds having a nitrogen atom in the form of said ion.
Les analogues -inium et -idinium des composés hétérocycliques insaturés ci-dessus font référence aux analogues partiellement saturés (-inium) et saturés (-idinium) correspondant résultant d'une hydrogénation partielle respectivement complète, comme par exemple le pyrrolinium à titre d'analogue partiellement insaturé et le pyrrolidinium à titre d'analogue saturé du pyrrolium.The analogues -inium and -idinium of the above unsaturated heterocyclic compounds refer to the corresponding partially saturated (-inium) and saturated (-idinium) analogues resulting from a partial or complete partial hydrogenation, such as, for example, pyrrolinium as an analogue. partially unsaturated and pyrrolidinium as a saturated analogue of pyrrolium.
A titre de dérivés ammonium, on peut notamment citer les ammonium substitués, tel que l'éthylènediammonium, l'éthanolammonium, le propylammonium, le monopropargylammonium, le tripropargylammonium, le tétraéthylammonium, le N-tributyl-N-méthylammonium, le N-triméthyl-N-butylammonium, le N-triméthyl-N-hexylammonium, le N-triméthyl-N-propylammonium.Examples of ammonium derivatives that may be mentioned are substituted ammonium compounds, such as ethylenediammonium, ethanolammonium, propylammonium, monopropargylammonium, tripropargylammonium, tetraethylammonium, N-tributyl-N-methylammonium, N-trimethylammonium, N-butylammonium, N-trimethyl-N-hexylammonium, N-trimethyl-N-propylammonium.
A titre de dérivés de pyrrolium, on peut par exemple citer les pyrrolium substitués, notamment par un groupe alkyle, tels que le N-méthylpyrrolium.Examples of pyrrolium derivatives that may be mentioned are substituted pyrroliums, in particular with an alkyl group, such as N-methylpyrrolium.
A titre de dérivés d'imidazolium, on peut citer les imidazolium substitués, notamment par un ou plusieurs groupes alkyles, et/ou hydroxyalkyles, tels que le 1-butyl-2,3-diméthylamidazolium, le 1-butyl-3-méthylimidazolium, le 1,3-diméthylimidazolium, le 1-éthanol-3-méthylimidazolium, le 1-éthyl-3méthylimidazolium, le 1-héxyl-3-méthylimidazolium, le méthylimidazolium, le 1-octyl-3-méthylimidazolium, le 1-propyl-2,3-diméthylimidazolium, le 1-propyl-2,3-diméthylimidazolium.As imidazolium derivatives, mention may be made of substituted imidazoliums, in particular with one or more alkyl groups, and / or hydroxyalkyls, such as 1-butyl-2,3-dimethylamidazolium or 1-butyl-3-methylimidazolium, 1,3-dimethylimidazolium, 1-ethanol-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, methylimidazolium, 1-octyl-3-methylimidazolium, 1-propyl-2 3-dimethylimidazolium, 1-propyl-2,3-dimethylimidazolium.
A titre de dérivés de pyrrolidinium, on peut citer les pyrrolidinium substitués, notamment par un ou plusieurs groupes alkyles, tels que le 1-butyl-1-méthylpyrrolidinium, le 1-éthyl-1-méthylpyrrolidinium, le N-propyl-N-méthylpyrrolidinium.By way of pyrrolidinium derivatives, mention may be made of substituted pyrrolidiniums, in particular with one or more alkyl groups, such as 1-butyl-1-methylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium and N-propyl-N-methylpyrrolidinium. .
A titre de dérivés de pipéridinium, on peut citer les pipéridinium substitués par un ou plusieurs groupes alkyles, tels que le 1-méthyl-1-propylpipéridinium.As piperidinium derivatives, mention may be made of piperidinium substituted with one or more alkyl groups, such as 1-methyl-1-propylpiperidinium.
A titre de dérivés de triazolium, on peut citer le 1-méthyl-1,2,4-triazolium, le 3-azido-1,2,4-triazolium, le 1-méthyl-3-azido-1,2,4-triazolium, le 4-amino-1,2,4-triazolium.As triazolium derivatives, there may be mentioned 1-methyl-1,2,4-triazolium, 3-azido-1,2,4-triazolium, 1-methyl-3-azido-1,2,4 -triazolium, 4-amino-1,2,4-triazolium.
A titre de dérivés de tétrazolium, on peut citer le 1-amino-4,5-diméthyltétrazolium, le 2-amino-4,5-diméthyltétrazolium, le 1,5-diamino-4-méthyltétrazolium.As derivatives of tetrazolium, there may be mentioned 1-amino-4,5-dimethyltetrazolium, 2-amino-4,5-dimethyltetrazolium, 1,5-diamino-4-methyltetrazolium.
A titre illustratif, on peut mentionner les familles de cations suivantes :
Le contre-ion (anion) du combustible peut être tout anion présentant une charge négative, azoté ou non. Il peut notamment être choisi parmi
- les anions linéaires tels que les ions azoture, nitrate, nitramide, nitroformiate, dinitramide, nitrite, acétate, cyanamide, dicyanamide, phosphate, méthylphosphonate, éthylphosphonate ; et
- les anions hétérocycliques insaturés tels que les azolates (tels que pyrrolate), diazolate (tel que pyrazolate, imidazolate), triazolate (1,2,3-
1,2,4-triazolate) et tétrazolate (tel que nitrotétrazolate),et
- linear anions such as azide, nitrate, nitramide, nitroformate, dinitramide, nitrite, acetate, cyanamide, dicyanamide, phosphate, methylphosphonate, ethylphosphonate; and
- unsaturated heterocyclic anions such as azolates (such as pyrrolate), diazolate (such as pyrazolate, imidazolate), triazolate (1,2,3- and 1,2,4-triazolate) and tetrazolate (such as nitrotetrazolate),
A titre illustratif, on peut citer les familles d'anions suivantes :
Par groupe alkyle, on entend les radicaux hydrocarbonés saturés, en chaîne droite ou ramifiée, de 1 à 20 atomes de carbone, de préférence de 1 à 5 atomes de carbone. On peut notamment citer, lorsqu'ils sont linéaires, les radicaux méthyle, éthyle, propyle, butyle, pentyle, hexyle, octyle, nonyle, décyle, dodécyle, hexadécyle, et octadécyle. On peut notamment citer, lorsqu'ils sont ramifiés ou substitués par un ou plusieurs radicaux alkyle, les radicaux isopropyle, tert-butyl, 2-éthylhexyle, 2-méthylbutyle, 2-méthylpentyle, 1-méthylpentyle et 3-méthylheptyle.By alkyl group is meant saturated hydrocarbon radicals, straight or branched chain, of 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms. Mention may in particular be made, when they are linear, the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl and octadecyl radicals. When they are branched or substituted by one or more alkyl radicals, mention may be made especially of the isopropyl, tert-butyl, 2-ethylhexyl, 2-methylbutyl, 2-methylpentyl, 1-methylpentyl and 3-methylheptyl radicals.
Le contre-ion (anion) est notamment choisi parmi les ions azoture, nitrate, dinitramide, dicyanamide, imidazolate et tétrazolate et leurs dérivés.The counterion (anion) is especially chosen from azide, nitrate, dinitramide, dicyanamide, imidazolate and tetrazolate ions and their derivatives.
Plus particulièrement, on peut notamment citer à titre de combustible les composés suivants :
- l'azoture d'ammonium (AA),
- l'azoture de tétrabutylammonium,
- le nitrotétrazolate de triazolium,
- le nitrotétrazolate d'azidotriazolium,
- le dinitramide d'ammonium (ADN),
- l'azoture d'hydroxylammonium (HAA),
- l'azoture d'hydrazinium (HA),
- le nitrate d'hydroxylammonium (HAN),
- le dinitramide d'ammonium (ADN),
- le nitroformiate d'hydrazinium (HNF),
- le nitrate d'ammonium (AN),
- le nitrate d'hydrazinium (HN),
- le nitrate de triéthanolammonium (TEAN),
- le dinitramide d'hydroxylammonium (HADN),
- les sels d'azoture, d'acétate, de nitrate, de dinitramide, de dicyanamide, de méthylphosphonate, de 4,5-dinitroimidazolate, de 5-nitro-tétrazolate et d'éthylphosphonate
- ammonium azide (AA),
- tetrabutylammonium azide,
- triazolium nitrotetrazolate,
- azidotriazolium nitrotetrazolate,
- ammonium dinitramide (DNA),
- hydroxylammonium azide (HAA),
- hydrazinium azide (HA),
- hydroxylammonium nitrate (HAN),
- ammonium dinitramide (DNA),
- hydrazinium nitroformate (HNF),
- ammonium nitrate (AN),
- hydrazinium nitrate (HN),
- triethanolammonium nitrate (TEAN),
- hydroxylammonium dinitramide (HADN),
- the salts of azide, acetate, nitrate, dinitramide, dicyanamide, methylphosphonate, 4,5-dinitroimidazolate, 5-nitro-tetrazolate and ethylphosphonate
A titre illustratif, on peut ainsi citer :
- l'azoture d'ammonium (AA),
- l'azoture de tétrabutylammonium,
- le nitrotétrazolate de triazolium,
- le nitrotétrazolate d'azidotriazolium,
- le dinitramide d'ammonium (ADN),
- l'azoture d'hydroxylammonium (HAA),
- l'azoture d'hydrazinium (HA),
- l'azoture de 1-(2-butynyl)-3-méthyl-imidazolium
- le nitrate d'hydroxylammonium (HAN),
- le dinitramide d'ammonium (ADN),
- le nitroformiate d'hydrazinium (HNF),
- le nitrate d'ammonium (AN),
- le nitrate d'hydrazinium (HN),
- le nitrate de triéthanolammonium (TEAN),
- le dinitramide d'hydroxylammonium (HADN),
- le dicyanamide d'ammonium,
- le dicyanamide d'imidazolium,
- le dicyanamide de 1-butyl-3-méthylimidazolium,
- l'acétate de 1-butyl-2,3-diméthylamidazolium,
- l'acétate, le dicyanamide, de 1-butyl-1-méthylpyrrolidinium,
- le méthylphosphonate de 1,3-diméthylimidazolium,
- le dicyanamide de 1-éthanol-3-méthylimidazolium,
- l'éthylphosphonate, le méthylphosphonate, de 1-éthyl-3-méthylimidazolium,
- le dicyanamide de N-tributyl-N-méthylammonium,
- le dicyanamide d'ammonium,
- l'azoture d'ammonium,
- le dicyanamide de 1-butyl-3-méthyl-imidazolium,
- 4,5-dinitro imidazolate de 1,2,4-triazolium
- 4,5-dinitro imidazolate de 1-méthyl-1,2,4-triazolium,
- 4,5-dinitro imidazolate de 3-azido-1,2,4-triazolium,
- 4,5-dinitro imidazolate de 1-méthyl-3-azido-1,2,4-triazolium,
- 4,5-dinitro imidazolate de 4-amino-1,2,4-triazolium,
- 5-
1,2,4-triazolium,nitro tétrazolate de - 5-nitro tétrazolate de 1-méthyl-1,2,4-triazolium,
- 5-nitro tétrazolate de 3-azido-1,2,4-triazolium,
- 5-nitro tétrazolate de 1-méthyl-3-azido-1,2,4-triazolium,
- 5-nitro tétrazolate de 4-amino-1,2,4-triazolium,
- Nitrate de 1-amino-4,5-diméthyltétrazolium
- Nitrate de 2-amino-4,5-diméthyltétrazolium
Nitrate de 1,5-diamino-4-méthyltétrazoliumDinitramide de 1,5-diamino-4-méthyltétrazoliumAzoture de 1,5-diamino-4-méthyltétrazolium- le dinitramide de 1,5-diamino-4-méthyl-tétrazolium.
- ammonium azide (AA),
- tetrabutylammonium azide,
- triazolium nitrotetrazolate,
- azidotriazolium nitrotetrazolate,
- ammonium dinitramide (DNA),
- hydroxylammonium azide (HAA),
- hydrazinium azide (HA),
- 1- (2-butynyl) -3-methyl-imidazolium azide
- hydroxylammonium nitrate (HAN),
- ammonium dinitramide (DNA),
- hydrazinium nitroformate (HNF),
- ammonium nitrate (AN),
- hydrazinium nitrate (HN),
- triethanolammonium nitrate (TEAN),
- hydroxylammonium dinitramide (HADN),
- ammonium dicyanamide,
- imidazolium dicyanamide,
- 1-butyl-3-methylimidazolium dicyanamide,
- 1-butyl-2,3-dimethylamidazolium acetate,
- acetate, dicyanamide, 1-butyl-1-methylpyrrolidinium,
- 1,3-dimethylimidazolium methylphosphonate,
- 1-ethanol-3-methylimidazolium dicyanamide,
- ethylphosphonate, methylphosphonate, 1-ethyl-3-methylimidazolium,
- N-tributyl-N-methylammonium dicyanamide,
- ammonium dicyanamide,
- ammonium azide,
- 1-butyl-3-methylimidazolium dicyanamide,
- 4,5-dinitro-1,2,4-triazolium imidazolate
- 4,5-dinitro imidazolate of 1-methyl-1,2,4-triazolium,
- 4,5-dinitro imidazolate of 3-azido-1,2,4-triazolium,
- 4,5-dinitro imidazolate of 1-methyl-3-azido-1,2,4-triazolium,
- 4,5-dinitroimidazolate of 4-amino-1,2,4-triazolium,
- 1,2,4-triazolium 5-nitro tetrazolate,
- 1-methyl-1,2,4-triazolium 5-nitro tetrazolate,
- 3-azido-1,2,4-triazolium 5-nitro tetrazolate,
- 1-methyl-3-azido-1,2,4-triazolium 5-nitro tetrazolate,
- 4-amino-1,2,4-triazolium 5-nitro tetrazolate,
- 1-amino-4,5-dimethyltetrazolium nitrate
- 2-amino-4,5-dimethyltetrazolium nitrate
- 1,5-Diamino-4-methyltetrazolium nitrate
- Dinitramide of 1,5-diamino-4-methyltetrazolium
- Azide of 1,5-diamino-4-methyltetrazolium
- 1,5-diamino-4-methyl-tetrazolium dinitramide.
Ces sels sont généralement disponibles commercialement. Ainsi, l'AA, le HAA, le HA, le nitrotétrazolate de triazolium, le nitrotétrazolate d'azidotriazolium et le dinitramide d'ammonium (ADN) sont notamment commercialisés par EURENCO Bofors (Suède).These salts are usually commercially available. Thus, AA, HAA, HA, triazolium nitrotetrazolate, azidotriazolium nitrotetrazolate and ammonium dinitramide (DNA) are sold in particular by EURENCO Bofors (Sweden).
Les autres sels listés ci-dessus peuvent par exemple être commercialisés par Solvionic.The other salts listed above may for example be marketed by Solvionic.
Les sels selon l'invention, s'ils ne sont pas disponibles commercialement peuvent être obtenus par application ou adaptation de méthodes connues, notamment selon les méthodes décrites par
On peut ainsi citer les méthodes décrites dans
Il est entendu que d'autres sels peuvent être utilisés. Ainsi, en fonction des anions et cations disponibles commercialement et de l'optimisation de ceux-ci (en fonction des performances énergétiques, et/ou propriétés de compatibilité avec N2O, stabilité, toxicité etc., désirées), il peut être intéressant de faire varier leur structure. Différents contre-ions peuvent être obtenus à cation ou anion donné.It is understood that other salts can be used. Thus, depending on the commercially available anions and cations and the optimization thereof (depending on the energy performances, and / or compatibility properties with N 2 O, stability, toxicity, etc., desired), it may be advantageous to vary their structure. Different counter ions can be obtained with a given cation or anion.
Les monergols selon l'invention sont tels que le rapport N2O/combustible (en masse), connu sous le nom de rapport de mélange et souvent noté O / F ou OF (pour Oxidizer/Fuel ratio) est généralement compris entre 0,1 et 10, préférentiellement entre 1 et 6.The monergols according to the invention are such that the ratio N 2 O / fuel (by mass), known as the mixing ratio and often noted O / F or OF (for Oxidizer / Fuel ratio) is generally between 0, 1 and 10, preferably between 1 and 6.
Un moyen de quantifier les performances d'un ergol est constitué par l'impulsion spécifique, souvent notée Isp. L'impulsion spécifique représente la durée pendant laquelle le moteur fournit une poussée égale au poids de l'ergol consommé. Il s'agit ainsi d'un indicateur de la « sobriété » et donc de la performance énergétique d'un ergol. L'Isp être exprimée de la manière suivante :
La vitesse caractéristique des gaz éjectés est liée à la célérité du son selon :
où R , Tad et M sont respectivement la constante universelle des gaz parfaits, la température adiabatique au sein de la chambre (dite « de flamme » si présence de combustion) et la masse molaire moyenne des gaz éjectés.The characteristic speed of ejected gases is related to the speed of sound according to:
where R, T ad and M are respectively the universal constant of the ideal gases, the adiabatic temperature within the chamber (so-called "flame" if presence of combustion) and the average molar mass of the ejected gases.
Le rapport des pressions d'éjection et de chambre intervenant dans l'expression de l'Isp dépend de la nature des gaz éjectés mais également des caractéristiques géométriques de la tuyère :
avec ε le rapport d'expansion tuyère égal au rapport entre les sections d'éjection (Ae ) et du col sonique (Acol ).The ratio of the ejection and chamber pressures involved in the expression of the Isp depends on the nature of the ejected gases but also on the geometrical characteristics of the nozzle:
with ε the nozzle expansion ratio equal to the ratio between the ejection sections ( A e ) and the sonic neck ( A neck ).
Les monergols selon l'invention présentent généralement une Isp théorique comprise entre 300s et 350s lorsque calculée dans les conditions suivantes: pression dans la chambre de combustion de 10 bar, rapport d'expansion de tuyère de ε=100 et détente à l'équilibre dans la tuyère.The monergols according to the invention generally have a theoretical Isp of between 300s and 350s when calculated under the following conditions: pressure in the combustion chamber of 10 bar, nozzle expansion ratio of ε = 100 and expansion at equilibrium in the nozzle.
Selon un autre objet, la présente invention concerne également le procédé de préparation du monergol selon l'invention. Ainsi, ledit procédé comprend l'étape de mélange du combustible et de N2O. Ce mélange peut être réalisé à température ambiante, mais dans le cas où un sel solide à l'état standard est utilisé, la solubilité maximale doit être considérée à la température minimale de stockage du monergol en orbite afin de s'affranchir de tout risque de saturation et de recristallisation en vol. Il convient donc, lors de la synthèse du monergol, de respecter ce seuil. La température minimale d'utilisation du monergol en orbite est typiquement de 0°C.According to another object, the present invention also relates to the process for preparing the monergol according to the invention. Thus, said process comprises the step of mixing the fuel and N 2 O. This mixture can be carried out at room temperature, but in the case where a solid salt in the standard state is used, the maximum solubility should be considered at room temperature. the minimum storage temperature of the monergol orbit to overcome any risk of saturation and recrystallization in flight. It is therefore necessary, during the synthesis of the monergol, to respect this threshold. The minimum operating temperature of the monolgy in orbit is typically 0 ° C.
Le monergol selon l'invention peut être stocké en veillant à ne pas dépasser la température maximale de stockage autorisée afin de ne pas dépasser un certain niveau de pression de vapeur saturante, la MEOP (Maximal Expected Operating Pressure, pression maximale attendue en opération) étant comprise entre 10 et 50 bar, typiquement entre 20 et 40 bar. La température maximale de stockage est généralement comprise entre 0° et 50°C. Le monergol doit posséder une stabilité suffisante pour être stocké en orbite pour une durée de plusieurs années - typiquement 5 ans, mais jusqu'à 15 ans éventuellement. La stabilité doit se traduire notamment par l'absence de séparation de phase (démixtion, décantation, etc.).The monolif according to the invention can be stored taking care not to exceed the maximum permissible storage temperature so as not to exceed a certain saturation vapor pressure level, the MEOP (Maximum Expected Operating Pressure, maximum pressure expected in operation) being between 10 and 50 bar, typically between 20 and 40 bar. The maximum storage temperature is generally between 0 ° and 50 ° C. The monoling stone must have sufficient stability to be stored in orbit for a period of several years - typically 5 years, but possibly up to 15 years. The stability must be reflected in particular by the absence of phase separation (demixing, settling, etc.).
Selon un autre objet, la présente invention concerne également un procédé de propulsion spatiale au moyen du monergol selon l'invention. On entend par propulsion spatiale la propulsion d'engins spatiaux tels que lanceurs et satellites.According to another object, the present invention also relates to a method of spatial propulsion using the monergol according to the invention. Spatial propulsion is the propulsion of spacecraft such as launchers and satellites.
Avantageusement, le monergol selon l'invention convient à un fonctionnement par combustion. La combustion permet de s'affranchir d'un lit catalytique et par conséquent d'une structure de propulseur complexe. En outre, la durée de vie du propulseur pourra être étendue dans le mesure où le catalyseur constitue actuellement l'élément limitant en raison de phénomènes tels que désactivation du catalyseur par érosion, oxydation, frittage, etc.Advantageously, the monergol according to the invention is suitable for combustion operation. Combustion makes it possible to dispense with a catalytic bed and consequently with a complex propellant structure. In addition, the life of the propellant may be extended insofar as the catalyst currently constitutes the limiting element due to phenomena such as catalyst deactivation by erosion, oxidation, sintering, etc.
Le procédé selon l'invention comprend donc la combustion du monergol selon l'invention.The method according to the invention therefore comprises the combustion of the monergol according to the invention.
La combustion est généralement réalisée par allumage commandé. Ceci peut être effectué selon les technologies habituelles, notamment au moyen d'une bougie haute énergie. La bougie est généralement positionnée dans la tête d'injection, à l'arrivée du monergol dans la chambre de combustion, les gaz ainsi brûlés s'évacuant par une tuyère placée à l'extrémité opposée de la chambre de combustion.The combustion is generally carried out by controlled ignition. This can be done according to the usual technologies, in particular by means of a high energy candle. The spark plug is generally positioned in the injection head, at the arrival of the monergol in the combustion chamber, the gases burned and evacuated by a nozzle placed at the opposite end of the combustion chamber.
Le procédé selon l'invention peut également comprendre le moyen de pressurisation du monergol dans le réservoir. Généralement, les systèmes propulsifs actuels dits « monergols catalytiques » à hydrazine fonctionnent pour des pressions dans le réservoir de l'ordre de 20 bar en début de vie (pression initiale) et 5 bar en fin de vie. Cette pression diminue au cours de la vidange du monergol en raison de la détente du gaz de pressurisation dans le volume libéré par l'ergol. Certains systèmes prévoient une régulation de la pression réservoir afin de la maintenir constante sur une certaine partie de la mission du satellite (optimisation des performances). Tel est le cas sur plateforme de télécommunication, mais ceci introduit un équipement complexe et coûteux.The method according to the invention may also comprise the means for pressurizing the monergol in the tank. Generally, the present propellant systems known as "catalytic monergols" with hydrazine operate for pressures in the tank of the order of 20 bar at the beginning of life (initial pressure) and 5 bar at the end of life. This pressure decreases during the draining of the monergol due to the relaxation of the pressurizing gas in the volume released by the propellant. Some systems provide for tank pressure regulation to keep it constant over a certain part of the satellite's mission (performance optimization). This is the case on a telecommunication platform, but this introduces a complex and expensive equipment.
Dans le cas de la présente invention, il peut être envisagé de fonctionner à une pression réservoir supérieure - typiquement comprise entre 25 et 40 bar en début de vie - afin de tenir compte de la pression de vapeur saturante du mélange à base de N2O. La pressurisation peut être avantageusement réalisée par la solution de N2O elle-même étant donné son caractère volatil, si bien que le recours à un gaz inerte additionnel n'est plus nécessaire. Il en découle un gain sur le taux de remplissage du réservoir ainsi que sur la masse volumique apparente du couple liquide-gaz.In the case of the present invention, it can be envisaged to operate at an upper reservoir pressure - typically between 25 and 40 bar at the beginning of life - in order to take into account the saturation vapor pressure of the N 2 O-based mixture. The pressurization can be advantageously carried out by the N 2 O solution itself because of its volatile nature, so that the use of an additional inert gas is no longer necessary. This results in a gain on the filling rate of the reservoir as well as on the apparent density of the liquid-gas torque.
Tant que les phases liquide et vapeur coexistent (équilibre entre phases), la pression demeure constante (à température constante imposée) en raison de la vaporisation du liquide dont l'effet est de générer un volume de gaz compensant la vidange du réservoir. Dans ce cas, le moyen de pressurisation peut être assuré uniquement par le remplissage du monergol dans le réservoir. En réalité, la remise à l'équilibre entre les phases liquide et vapeur par vaporisation d'une fraction de N2O liquide s'accompagne d'une légère baisse de température (phénomène endothermique), si bien qu'une légère diminution de pression sera observée. Ce phénomène peut être contrebalancé par l'exercice d'un réchauffage du réservoir via un contrôle thermique (thermistances). Ce phénomène d'auto-pressurisation » représente un avantage majeur puisque, de manière analogue aux régulateurs de pression sur moteurs biliquides, il permet aux propulseurs de fonctionner près de leur optimum de performances.As long as the liquid and vapor phases coexist (equilibrium between phases), the pressure remains constant (at constant temperature imposed) due to the vaporization of the liquid whose effect is to generate a volume of gas compensating the emptying of the reservoir. In this case, the pressurizing means can be ensured only by filling the monergol in the tank. In reality, the return to equilibrium between the liquid and vapor phases by vaporization of a liquid N 2 O fraction is accompanied by a slight drop in temperature (endothermic phenomenon), so that a slight decrease in pressure will be observed. This phenomenon can be counterbalanced by the exercise of a reheating of the tank via a thermal control (thermistors). This phenomenon of self-pressurization "represents a major advantage since, similarly to pressure regulators on biliquid engines, it allows the thrusters to operate near their optimum performance.
Dès appauvrissement de la phase liquide, l'équilibre entre phase n'est désormais plus réalisable. Le réservoir fonctionne alors classiquement en « blow down » de manière analogue à une pressurisation par gaz inerte.As soon as the liquid phase is depleted, the phase balance is no longer feasible. The tank then operates in a conventional "blow down" manner similar to an inert gas pressurization.
Le procédé selon l'invention peut également comprendre l'étape antérieure de chargement du monergol dans le réservoir de l'engin spatial.The method according to the invention may also include the previous step of loading the monolgy into the tank of the spacecraft.
-
Les
figures 1-3 représentent l'impulsion spécifique (Isp) en fonction du rapport de mélange pour deux rapports d'expansion (ε = 80 et ε = 330) pour chacun des monergols des exemples 1, 2 et 3 respectivement.Thefigures 1-3 represent the specific impulse (Isp) as a function of the mixing ratio for two expansion ratios ( ε = 80 and ε = 330) for each of the monergols of Examples 1, 2 and 3 respectively. -
La
figure 4 illustre la contrainte de solubilité vis-à-vis des performances optimales dans le cas d'un monergol faisant intervenir un sel solide à l'état standard (exemple 1 ou 3).Thefigure 4 illustrates the solubility stress with respect to optimal performance in the case of a monergol involving a solid salt in the standard state (Example 1 or 3).
Les exemples suivants sont donnés à titre illustratif et non limitatif de la présente invention.The following examples are given by way of non-limiting illustration of the present invention.
Les tableaux ci-après donnent quelques exemples de sels énergétiques parmi les cations ammonium, diazolium, triazolium et tétrazolium, certains étant pourvus de groupes substitutifs de type alkyle, azido ou amino. Les anions associés sont pris parmi les dicyanamide, azoture, imidazolate, tétrazolate, nitrate ou encore dinitramide, substitués ou non par le groupe nitro. La composition atomique et quelques-unes de leurs propriétés y sont précisées (point de fusion, seuil de décomposition thermique, masse volumique du sel à l'état standard, enthalpie standard de formation).
■ A base de cation ammonium :
■ A base de cation diazolium (imidazolium) :
■ Based on ammonium cation:
■ Based on cation diazolium (imidazolium):
Le dicyanamide de 1-butyl-3-méthyl-imidazolium peut être préparé par application de la méthodologie décrite par Asikkala et al (Application of ionic liquids and microwave activation in selected organic reaction, Acta Univ Oul. A 502, 2008, page 134) par transsalification à partir de chlorure de 1-butyl-3-méthyl-imidazolium en présence de dicyanamide de sodium, le chlorure étant préparé par réaction entre le 1-chlorobutane et le 1-méthylimidazole.1-Butyl-3-methyl-imidazolium dicyanamide can be prepared using the methodology described by Asikkala et al (Application of Ionic Liquids and Microactivation in Selected Organic Reactions, Acta Univ Oul. A 502, 2008, p. 134) by transsalification from 1-butyl-3-methyl-imidazolium chloride in the presence of sodium dicyanamide, the chloride being prepared by reaction between 1-chlorobutane and 1-methylimidazole.
Alternativement, le dicyanamide de 1-butyl-3-méthyl-imidazolium peut être préparé par métathèse telle que décrite notamment dans
■ A base de cation triazolium :
■ A base de cation tétrazolium
■ Based on triazolium cation:
■ Based on tetrazolium cation
Les sels ci-dessus peuvent être préparés selon Singh et al Structure bond 2007, 125 :35-83 .The above salts can be prepared according to Singh et al Structure Bond 2007, 125: 35-83.
On donne ici les performances théoriques de certains couples cations/anions en mélange avec le N2O sur la base des enthalpies de formation trouvées dans la littérature. Les tableaux et figures ci-dessous précisent l'évolution de l'impulsion spécifique (Isp) dans le vide du monergol en fonction du rapport de mélange ( O / F ). Les calculs sont effectués pour une pression dans la chambre de combustion de 10 bar, un rapport d'expansion de tuyère de ε=100 et une détente à l'équilibre dans la tuyère. Les tableaux et courbes sont donnés pour des valeurs autour du maximum d'Isp et du rapport de mélange optimal correspondant. Les exemples donnés ci-après font intervenir des sels énergétiques mis en solution selon chacune des trois méthodes décrites plus tôt, à savoir :
- Exemple 1 : monergol formé par un sel « cristal » dissous dans le N2O liquide ;
- Exemple 2 : sel liquide en mélange binaire avec le N2O liquide ;
- Exemple 3 : solution formée d'un sel « cristal » dissous dans un solvant énergétique organique ou ionique, elle-même en équilibre binaire avec le N2O liquide :
- Example 1: monergol formed by a "crystal" salt dissolved in liquid N 2 O;
- Example 2: liquid salt in a binary mixture with liquid N 2 O;
- Example 3: solution formed of a "crystal" salt dissolved in an organic or ionic energy solvent, itself in binary equilibrium with liquid N 2 O:
Exemple 1 : le premier cas peut être illustré par l'utilisation de l'azoture de 1-(2-butynyl)-3-méthyl-imidazolium, noté [ByMIM][N3 -]. Ce composé peut être préparé à partir du bromure de 1-(2-butynyl)-3-méthyl-imidazolium sur résine d'échange d'azoture selon
Le tableau ci-après et la
Exemple 2 : le deuxième cas peut être représenté par le mélange binaire liquide-liquide entre le dicyanamide de 1-butyl-3-méthyl-imidazolium, noté [BMIM][N(CN)2 -] (commercialisé par Solvionic), et le N2O. La figure suivante donne la structure du [BMIM][N(CN)2 -]:
La variation de l'Isp avec le rapport de mélange est décrite dans le tableau ci-après et la
Exemple 3 : le troisième cas peut être illustré par l'équilibre ternaire entre le dinitramide de 1,5-diamino-4-méthyl-tétrazolium, noté [DAMT][N(NO2)2] synthétisé selon
S'agissant d'un mélange ternaire, la notion de rapport de mélange O / F n'est plus utilisée ici. On étudie plutôt le diagramme ternaire d'Isp où sont balayées les fractions massiques des trois composés. Le tableau ci-après et la
Les sels selon l'invention peuvent être péparés notamment :
- par quaternarisation par alkylation selon
Singh et al., Structure bond 2007, 125 :35-83 US 8,034,202 Asikkala et al. (Application of ionic liquids and microwave activation in selected organic reaction, Acta Univ. Oul. A 502, 2008 - par métathèse en présence des sels d'argent de nitrate, dinitramide, azoture à partir des halogénures correspondants selon
Singh et al Structure bond 2007, 125 :35-83 US 8,034,202 - à partir d'un autre composé ionique par échange d'ions selon
Asikkala et al (Application of ionic liquids and microwave activation in selected organic reaction, Acta Univ Oul. A 502, 2008 Schneider et al Inorganic Chemistry 2008, 47(9), 3617-3624
- by quaternization by alkylation according to
Singh et al., Structure Bond 2007, 125: 35-83 US8,034,202 Asikkala et al. (Application of ionic liquids and micron activation in the organic reaction, Acta Univ., A 502, 2008 - by metathesis in the presence of the silver salts of nitrate, dinitramide, azide from the corresponding halides according to
Singh et al Structure Bond 2007, 125: 35-83 US8,034,202 - from another ionic compound by ion exchange according to
Asikkala et al (Application of ionic liquids and micron activation in selected organic reactions, Acta Univ Oul. A 502, 2008 Schneider et al Inorganic Chemistry 2008, 47 (9), 3617-3624
L'impulsion spécifique générée par la combustion du monergol dépend étroitement du rapport de mélange O / F entre le N2O et le combustible (sel « cristallin » dissous ou sel liquide). Une courbe peut alors être décrite en traçant l'évolution de l'Isp en fonction de O / F , tout autre paramètre étant maintenu constant (pression chambre, température initiale, rapport de détente ε). Un maximum d'Isp peut alors être identifié ainsi que le O / F optimal correspondant. Idéalement, le monergol doit être synthétisé en respectant ce rapport de mélange afin de founir les meilleures performances propulsives.The specific impulse generated by monergol combustion is closely dependent on the O / F mixture ratio between N 2 O and the fuel (dissolved "crystalline" salt or liquid salt). A curve can then be described by plotting the evolution of the Isp as a function of O / F , any other parameter being kept constant (chamber pressure, initial temperature, expansion ratio ε ). A maximum of Isp can then be identified as well as the corresponding optimal O / F. Ideally, the monergol must be synthesized respecting this mixing ratio in order to provide the best propulsive performance.
Toutefois, dans le cas d'un sel cristallin (i.e. solide dans les conditions standard), la solubilité du sel dans le N2O ou dans la solution combinée au N2O limite l'intervalle de O / F accessible. En effet, le rapport de mélange doit être supérieur à une valeur seuil dictée par la solubilité du sel à la température minimale d'utilisation (typiquement Tmin = 0°C). Il apparaît clairement qu'à monergol donné, I est préfarable que le rapport de mélange optimal se trouve dans une zone de solubilité réalisable de manière à pouvoir atteindre le maximum d'Isp :
Ceci est illustré sur la
Les sels cristallins d'intêret doivent donc soit posséder une grande solubilité à la température minimale spécifiée (typiquement
L'exemple 3 donné ci-avant illustre bien cette problématique : sans recours au solvant, le maximum d'Isp est trouvé pour ( O / F ) opt =0.5, ce qui correspond à une dissolution de
Le respect de la condition sur le rapport de mélange minimum ( O / F )min doit être valable quel que soit l'avancement de la vidange du réservoir. Or, le changement de phase du N2O au cours de la vidange, dû au suivi de la courbe de saturation du mélange, va induire une augmentation de la teneur de la phase liquide en sel. Le rapport de mélange va progressivement diminuer au cours du soutirage de la phase liquide. Il convient de s'assurer que l'augmentation de la concentration en sel ne conduit pas à un dépassement de la solubilité, au risque de recristalliser ce dernier. Le choix du rapport de mélange initial du monergol doit alors tenir compte de son état en fin de vidange. C'est pourquoi dans certains cas, en particulier si ( O / F ) opt est très proche de ( O /F)min, il est nécessaire de se placer à un rapport de mélange initial supérieur à l'optimum. Dans un cas défavorable, l'Isp maximale est dans une zone au-delà de la saturation. L'Isp accessible sera inférieure à la valeur maximale et choisie dans une zone allant jusqu'au maximum de solubilité.The respect of the condition on the minimum mixing ratio ( O / F ) min must be valid regardless of the progress of the emptying of the tank. However, the phase change of the N 2 O during the emptying, due to the monitoring of the saturation curve of the mixture, will induce an increase in the content of the liquid phase salt. The mixing ratio will gradually decrease during the withdrawal of the liquid phase. It must be ensured that the increase in salt concentration does not lead to the solubility being exceeded, at the risk of recrystallizing the solubility. The choice of the initial mixture ratio of the monergol must then take into account its state at the end of emptying. This is why in some cases, especially if ( O / F ) opt is very close to ( O / F ) min , it is necessary to move to an initial mixing ratio higher than the optimum. In an adverse case, the maximum Isp is in an area beyond saturation. The accessible Isp will be less than the maximum value and chosen in an area up to the maximum of solubility.
La nature volatile du protoxyde d'azote implique un mode de préparation spécifique du monergol, au cours de laquelle le mélange sel et/ou solvant et N2O ne peut être réalisé à l'air libre, mais au contraire dans une enceinte fermée. Une procédure illustrative est la suivante, partant d'une enceinte propre et décontaminée :
- 1) Introduction dans l'enceinte du sel sous forme cristalline ou liquide, selon une masse respectant le critère d'optimisation présenté ci-avant ;
- 2) Le cas échéant, injection du solvant énergétique dans les proportions requises ;
- 3) Mise sous vide de l'enceinte (pression résiduelle typiquement de 103 Pa);
- 4) Injection dans l'enceinte du protoxyde d'azote avec contrôle de la masse introduite par pesée continue de l'enceinte d'arrivée ou pesée continue du contenant de départ du N2O;
- 5) Agitation du mélange ;
- 6) Stockage avec contrôle des conditions pression-température de l'enceinte - ou « fût de stockage » - afin de respecter l'intervalle de température spécifié.
- 1) Introduction into the chamber of the salt in crystalline or liquid form, according to a mass respecting the optimization criterion presented above;
- 2) If necessary, injection of the energy solvent in the required proportions;
- 3) evacuation of the chamber (residual pressure typically 10 3 Pa);
- 4) Injection into the nitrogen oxide enclosure with control of the mass introduced by continuous weighing of the inlet enclosure or continuous weighing of the N 2 O starting container;
- 5) Agitation of the mixture;
- 6) Storage with pressure-temperature control of the enclosure - or "storage drum" - to maintain the specified temperature range.
Le remplissage du réservoir sur satellite peut ensuite être effectué par mise en communication du fût de stockage et du réservoir du module de propulsion et soutirage de la phase liquide. La force motrice permettant le transfert du monergol du fût vers le réservoir est directement assuré par l'auto-pressurisation du monergol. L'utilisation d'un gaz neutre additionnel peut être envisagée pour expulser le monergol du fût de stockage.The filling of the satellite tank can then be carried out by placing the storage tank and the propulsion module tank in communication and withdrawing the liquid phase. The driving force for the transfer of monoling from the drum to the reservoir is directly ensured by the self-pressurization of the monergol. The use of an additional neutral gas may be considered to expel the monolgy from the storage drum.
Le monergol {N2O + combustible ionique} stocké dans le réservoir pressurisé est injecté dans le propulseur via une ligne fluidique habituelle comprenant notamment une vanne de contrôle du flux dite « vanne-moteur ». Le monergol est soutiré au niveau du réservoir par sa phase liquide dans la mesure où seule cette phase comporte à la fois l'oxydant et le combustible. Une technique de soutirage bien adaptée à la présente innovation est le système de réseau capillaire (connu aussi sous le terme de réservoir à tension de surface), bien connue de l'homme du métier. L'expulsion du monergol à travers la ligne fluidique alimentant les propulseurs est assurée par la pression générée par le N2O gazeux en équilibre avec la solution liquide. Seule la phase liquide est alors expulsée.The monol {N 2 O + ionic fuel} stored in the pressurized tank is injected into the propellant via a usual fluid line including in particular a flow control valve called "motor valve". The monergol is withdrawn at the reservoir by its liquid phase insofar as only this phase comprises both the oxidant and the fuel. A bleeding technique well adapted to the present invention is the capillary network system (also known as the surface tension tank), well known to those skilled in the art. The expulsion of the monergol through the fluidic line supplying the thrusters is ensured by the pressure generated by the N 2 O gas in equilibrium with the liquid solution. Only the liquid phase is then expelled.
La valeur du débit-masse du monergol injecté dans le(s) propulseur(s) est dictée par la perte de charge totale dans les lignes fluidiques du réservoir au(x) moteur(s), en particulier par la perte de charge singulière de l'injecteur (dictée par sa conception). Tant que le monergol n'a pas franchi la tête d'injection, il demeure sous phase liquide tant qu'il existe dans cet état dans le réservoir.The value of the mass flow rate of the monergol injected into the propellant (s) is dictated by the total pressure drop in the fluid lines of the reservoir to the engine (s), in particular by the singular pressure drop of the injector (dictated by its design). As long as the monergol has not crossed the injection head, it remains in liquid phase as long as it exists in this state in the tank.
Lorsque le monergol passe par l'injecteur situé à la tête du moteur (dit « fond avant »), ce dernier subit une détente. Il pénètre alors dans la partie amont de la chambre de combustion et est amené à subir un changement de phase. La cause du changement de phase diffère selon l'état de la chambre de combustion, plus précisément son niveau de pression et de température. S'il s'agit d'un allumage, il peut être supposé que le monergol pénètre dans un milieu « frais » et vide ou proche du vide (on parle alors de milieu raréfié) dans la mesure où la chambre communique avec le vide spatial via la tuyère. Le monergol se volatilisera rapidement puisque sa pression de vapeur saturante sera nettement supérieure à la pression résiduelle au sein de la chambre de combustion. Ce phénomène sera exacerbé si le monergol ou les parois du propulseur sont à une température supérieure.When the monergol goes through the injector located at the engine head (called "front end"), the latter undergoes a relaxation. It then enters the upstream part of the combustion chamber and is caused to undergo a phase change. The cause of the phase change differs according to the state of the combustion chamber, more precisely its pressure and temperature level. If it is an ignition, it can be assumed that the monergol enters a "fresh" environment and empty or near vacuum (so-called rarefied medium) to the extent that the room communicates with the vacuum space via the nozzle. The monolol will volatilize rapidly since its saturation vapor pressure will be significantly higher than the residual pressure within the combustion chamber. This phenomenon will be exacerbated if the monolayer or the walls of the thruster are at a higher temperature.
La phase d'allumage consiste à synchroniser le déclenchement de la bougie avec l'arrivée du flux du monergol afin de générer un allumage « doux » (contraire du « hard start » faisant intervenir un pic de pression transitoire et violent dommageable pour le système). L'assurance d'un allumage de qualité peut également être atteinte par la réalisation d'un train de déclenchements de la bougie (salves d'arcs électriques) à fréquence relativement soutenue (période de l'ordre de quelques dizaines de millisecondes à centaines de millisecondes). Le train d'arcs peut également être déclenché en légère avance de phase sur l'injection pour jouer le rôle de préchauffage local. L'optimisation de l'allumage repose ainsi sur la conjonction d'une conception géométrique et d'une séquence de déclenchements optimisées.The ignition phase consists in synchronizing the triggering of the spark plug with the arrival of the flow of the monergol in order to generate a "soft" ignition (contrary to the "hard start" involving a peak of transient pressure and violent damage to the system) . The assurance of a quality ignition can also be achieved by the realization of a train of triggers of the candle (bursts of electric arcs) with relatively constant frequency (period of the order of a few tens of milliseconds to hundreds of milliseconds). The arcing stream can also be fired in a slight phase advance over the injection to act as a local preheat. The optimization of the ignition thus relies on the conjunction of a geometric design and an optimized sequence of trips.
Dans le cas où le monergol pénètre dans une chambre « chaude », ce qui correspond par exemple à plusieurs mises à feu successives entrecoupées de phases inactives relativement rapprochées (cycles courts), l'allumage est facilité car le monergol reçoit un apport d'énergie supplémentaire avant les stimuli de la bougie. Ces problématiques sont bien connues de l'homme du métier, notamment en matière d'allumage des turboréacteurs en haute altitude ou des propulseurs biliquides cryotechniques.In the case where the monergol penetrates into a "hot" chamber, which corresponds for example to several successive firing interspersed with relatively close inactive phases (short cycles), the ignition is facilitated because the monergol receives a supply of energy extra before the stimuli of the candle. These problems are well known to those skilled in the art, especially in the field of ignition of turbojet engines at high altitude or cryocyclic liquid propellants.
Avantageusement, la combustion s'entretient après allumage tant que le flux du monergol est maintenu (vanne-moteur ouverte) et ne nécessite donc pas de déclenchements de bougie supplémentaires. L'énergie dégagée par la combustion du monergol est suffisante pour entretenir la réaction des espèces fraîches injectées. La combustion consiste en une réaction entre l'oxydant principal, à savoir le N2O, et le combustible ionique comprenant éventuellement des groupements oxydants (ex. nitramides). La réaction produit des gaz chauds à haute pression. La chambre de combustion est dimensionnée de telle façon que l'équilibre thermodynamique est atteint avant éjection des gaz brûlés de manière à atteindre un rendement maximal. Les gaz sont éjectés à travers une tuyère pourvue d'un convergent, d'un col sonique et d'un divergent de façon à amorcer et accélérer l'écoulement pour générer une force de poussée optimale.Advantageously, the combustion is maintained after ignition as long as the monergol flow is maintained (open motor valve) and therefore does not require additional spark plugs. The energy released by the combustion of the monergol is sufficient to maintain the reaction of the fresh species injected. Combustion consists of a reaction between the main oxidant, namely N 2 O, and the ionic fuel optionally comprising oxidizing groups (eg nitramides). The reaction produces hot gases at high pressure. The combustion chamber is dimensioned such that the thermodynamic equilibrium is reached before ejection of the flue gas so as to achieve maximum efficiency. The gases are ejected through a nozzle provided with a convergent, sonic and divergent neck to initiate and accelerate the flow to generate an optimal thrust force.
Claims (14)
- A monopropellant comprising a mixture comprising:- nitrous oxide (N2O) as an oxidizer, at least partly in liquid form, and- a fuel in the form of a salt in the liquid N2O phase.
- The monopropellant according to claim 1, such that said nitrous oxide is partly in the form of a gas.
- The monopropellant according to anyone of the preceding claims, such that its liquid phase is constituted by:(i) fuel in the form of a solid salt when it is isolated at room temperature and solubilized in said N2O at least partly present in liquid form, or(ii) a molten salt of the fuel in a binary mixture with said N2O at least partly present in liquid form, or(iii) an ionic solution of the fuel dissolved in an organic or ionic energetic solvent, in a binary mixture with said N2O at least present in liquid form.
- The monopropellant according to anyone of the preceding claims, such that the fuel is a salt of an energetic organic compound.
- The monopropellant according anyone of the preceding claims, such that the fuel is a salt of a nitrogen-containing derivative.
- The monopropellant according to anyone of the preceding claims, such that the cation of said salt is selected from:- linear cations, such as ammonium, hydroxyl ammonium, hydrazinium ions and their derivatives;- saturated heterocyclic cations such as piperidinium, piperazinium cations and their derivatives; and- heterocyclic cations, either aromatic or not, such as azinium, azolium, diazolium, triazolium and tetrazolium, notably pyridinium, pyrrolium, isoxazolium, pyrazolium, oxazolium, pyrazolium, imidazolium, oxadiazolium, triazolium, oxatriazolium, tetrazolium, pyrrolidium, triazinium, pyridazinium, pyrimidinium, pyrazinium, piperidinium, 1,2,3- or 1,2,4- triazolium, 1,4,5- or 2,4,5-tetrazolium, as well as their -inium and -idinium analogues, and their derivatives.
- The monopropellant according to claim 6 such that the cation is selected from ammonium, imidazolium, triazolium, tetrazolium ions and their derivatives.
- The monopropellant according to anyone of the preceding claims such that the anion of said salt is selected from:- linear anions such as azide, nitrate, nitramide, dinitramide, nitroformate, nitrite, acetate, cyanamide, dicyanamide ions; and- unsaturated heterocyclic anions such as azolates such as pyrrolate, diazolate such as pyrazolate, imidazolate, triazolate such as 1,2,3- and 1,2,4-triazolate and tetrazolate such as nitrotetrazolate, and their derivatives.
- The monopropellant according to claim 8, such that the counter-ion (anion) is selected from azide, nitrate, dinitramide, dicyanamide, imidazolate and tetrazolate ions and their derivatives.
- The monopropellant according to claim 1 such that the fuel is selected from:- ammonium azide (AA),- tetrabutylammonium azide,- triazolium nitrotetrazolate,- azidotriazolium nitrotetrazolate,- ammonium dinitramide (ADN),- hydroxylammonium azide (HAA),- hydrazinium azide(HA),- 1-(2-butynyl)-3-methyl-imidazolium azide- hydroxylammonium nitrate (HAN),- hydrazinium nitroformate (HNF),- ammonium nitrate (AN),- hydrazinium nitrate (HN),- triethanolammonium nitrate (TEAN),- hydroxylammonium dinitramide (HADN),- ammonium dicyanamide,- imidazolium dicyanamide,- 1-butyl-3-methylimidazolium dicyanamide,- 1-butyl-2,3-dimethylamidazolium acetate,- 1-butyl-1-methylpyrrolidinium acetate, dicyanamide,- 1-ethanol-3-methylimidazolium dicyanamide,- N-tributyl-N-methylammonium dicyanamide,- 1-butyl-3-methyl-imidazolium dicyanamide,- 1,2,4-triazolium 4,5-dinitro-imidazolate- 1-methyl-1,2,4-triazolium 4,5-dinitro-imidazolate,- 3-azido-1,2,4-triazolium 4,5-dinitro-imidazolate ,- 1-methyl-3-azido-1,2,4-triazolium 4,5-dinitro-imidazolate,- 4-amino-1,2,4-triazolium 4,5-dinitro-imidazolate,- 1,2,4-triazolium 5-nitro-tetrazolate,- 1-methyl-1,2,4-triazolium 5-nitro-tetrazolate,- 3-azido-1,2,4-triazolium 5-nitro-tetrazolate,- 1-methyl-3-azido-1,2,4-triazolium 5-nitro-tetrazolate,- 4-amino-1,2,4-triazolium 5-nitro-tetrazolate,- 1-amino-4,5-dimethyltetrazolium nitrate- 2-amino-4,5-dimethyltetrazolium nitrate- 1,5-diamino-4-methyltetrazolium nitrate- 1,5-diamino-4-methyltetrazolium dinitramide- 1,5-diamino-4-methyltetrazolium azide- 1,5-diamino-4-methyi-tetrazolium dinitramide.
- The method for preparing a monopropellant according to anyone of the preceding claims comprising the step of mixing the fuel and N2O in a closed enclosure.
- A space propulsion method using a monopropellant according to anyone of the preceding claims.
- The propulsion method according to claim 12, comprising the combustion of the monopropellant by controlled ignition.
- The method according to claim 12 or 13, comprising the means for pressurizing the monopropellant in the tank.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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FR1250794A FR2986229B1 (en) | 2012-01-27 | 2012-01-27 | NEW IONIC MONERGOLS BASED ON N2O FOR SPACE PROPULSION |
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EP2620422A1 EP2620422A1 (en) | 2013-07-31 |
EP2620422B1 true EP2620422B1 (en) | 2014-04-23 |
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EP13152595.8A Active EP2620422B1 (en) | 2012-01-27 | 2013-01-24 | N2O-based, ionic monopropellants for space propulsion |
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US (1) | US20130305685A1 (en) |
EP (1) | EP2620422B1 (en) |
JP (1) | JP6154142B2 (en) |
FR (1) | FR2986229B1 (en) |
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WO2014189450A1 (en) | 2013-05-20 | 2014-11-27 | Ecaps Ab | Oxidizer-rich liquid monopropellants for a dual mode chemical rocket engine |
US10253136B2 (en) | 2014-02-06 | 2019-04-09 | Adeka Corporation | Compound and epoxy resin composition containing same |
JP6240940B2 (en) * | 2014-02-06 | 2017-12-06 | 株式会社Adeka | Epoxy resin composition |
CN106370301A (en) * | 2016-08-24 | 2017-02-01 | 中国科学院合肥物质科学研究院 | Moisture-proof and anti-pollution diversion nitrogen purging protection system for space-borne atmospheric environment detector |
CN108981162A (en) * | 2018-06-06 | 2018-12-11 | 朱焕旺 | A kind of fused salt circular flow technique |
CN111925262B (en) * | 2020-08-19 | 2021-08-27 | 中国工程物理研究院化工材料研究所 | Preparation method of multi-component low-eutectic liquid based on metal chloride |
DE102020122337A1 (en) * | 2020-08-26 | 2022-03-03 | LabOrbital GmbH | Hot gas generating device with monergolic ionic fuel and low voltage ignition |
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US8006A (en) * | 1851-04-01 | Horseshoe-nail machine | ||
DE4303169C1 (en) * | 1993-02-04 | 1994-04-28 | Dynamit Nobel Ag | Gas evolving material contg. di:nitrogen mon:oxide and a fuel - useful as a gas generator for air bags in motor vehicles |
US6045638A (en) * | 1998-10-09 | 2000-04-04 | Atlantic Research Corporation | Monopropellant and propellant compositions including mono and polyaminoguanidine dinitrate |
SE513930C2 (en) | 1999-02-26 | 2000-11-27 | Svenska Rymdaktiebolaget | Liquid fuel |
AU5695001A (en) * | 1999-11-11 | 2001-07-24 | Kelly Space & Technology, Inc. | Nitrous oxide/fuel monopropellants |
US7771549B1 (en) * | 2002-10-07 | 2010-08-10 | United States Of America As Represented By The Secretary Of The Air Force | Energetic ionic liquids |
JP4333943B2 (en) * | 2003-05-01 | 2009-09-16 | 株式会社Ihi | High-temperature gas generation method using HAN / HN-based monopropellant |
US6931832B2 (en) * | 2003-05-13 | 2005-08-23 | United Technologies Corporation | Monopropellant combustion system |
US7745635B1 (en) * | 2003-06-16 | 2010-06-29 | Drake Greg W | Energetic ionic salts |
US20050269001A1 (en) * | 2004-04-22 | 2005-12-08 | Liotta Charles L | Ionic liquid energetic materials |
US20090031700A1 (en) * | 2006-11-13 | 2009-02-05 | Space Propulsion Group, Inc. | Mixtures of oxides of nitrogen and oxygen as oxidizers for propulsion, gas generation and power generation applications |
US8034202B1 (en) * | 2007-10-04 | 2011-10-11 | The United States Of America As Represented By The Secretary Of The Air Force | Hypergolic fuels |
CN101855325A (en) * | 2007-11-09 | 2010-10-06 | 火星工程有限公司 | Nitrous oxide fuel blend monopropellants |
US20120304620A1 (en) * | 2011-06-01 | 2012-12-06 | Aerojet-General Corporation | Catalyst, gas generator, and thruster with improved thermal capability and corrosion resistance |
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2012
- 2012-01-27 FR FR1250794A patent/FR2986229B1/en not_active Expired - Fee Related
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2013
- 2013-01-24 EP EP13152595.8A patent/EP2620422B1/en active Active
- 2013-01-25 JP JP2013012051A patent/JP6154142B2/en active Active
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FR2986229B1 (en) | 2014-03-21 |
US20130305685A1 (en) | 2013-11-21 |
JP6154142B2 (en) | 2017-06-28 |
FR2986229A1 (en) | 2013-08-02 |
JP2013155105A (en) | 2013-08-15 |
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