US3028272A - Self-igniting rocket propellants containing organic silanes - Google Patents
Self-igniting rocket propellants containing organic silanes Download PDFInfo
- Publication number
- US3028272A US3028272A US60618A US6061848A US3028272A US 3028272 A US3028272 A US 3028272A US 60618 A US60618 A US 60618A US 6061848 A US6061848 A US 6061848A US 3028272 A US3028272 A US 3028272A
- Authority
- US
- United States
- Prior art keywords
- silane
- nitric acid
- hydrogen
- nitrogen
- silanes
- 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.)
- Expired - Lifetime
Links
- 150000004756 silanes Chemical class 0.000 title description 19
- 239000003380 propellant Substances 0.000 title description 3
- 239000000446 fuel Substances 0.000 claims description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000011368 organic material Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000002429 hydrazines Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical class C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- -1 alkynyl silanes Chemical class 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- AKRQMTFHUVDMIL-UHFFFAOYSA-N tetrakis(prop-2-enyl)silane Chemical compound C=CC[Si](CC=C)(CC=C)CC=C AKRQMTFHUVDMIL-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HKILWKSIMZSWQX-UHFFFAOYSA-N tris(prop-2-enyl)silane Chemical compound C=CC[SiH](CC=C)CC=C HKILWKSIMZSWQX-UHFFFAOYSA-N 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000015842 Hesperis Nutrition 0.000 description 2
- 235000012633 Iberis amara Nutrition 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PMSZNCMIJVNSPB-UHFFFAOYSA-N bis(ethenyl)silicon Chemical compound C=C[Si]C=C PMSZNCMIJVNSPB-UHFFFAOYSA-N 0.000 description 1
- ZDWYFWIBTZJGOR-UHFFFAOYSA-N bis(trimethylsilyl)acetylene Chemical group C[Si](C)(C)C#C[Si](C)(C)C ZDWYFWIBTZJGOR-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 230000008021 deposition Effects 0.000 description 1
- ZDSFBVVBFMKMRF-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)silane Chemical compound C=CC[Si](C)(C)CC=C ZDSFBVVBFMKMRF-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- LFXRQWIAJWOJNE-UHFFFAOYSA-N prop-1-en-2-ylsilane Chemical class CC([SiH3])=C LFXRQWIAJWOJNE-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- BNCOGDMUGQWFQE-UHFFFAOYSA-N tris(ethenyl)silicon Chemical compound C=C[Si](C=C)C=C BNCOGDMUGQWFQE-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
- C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
Definitions
- Such fuels e.g., gasoline-nitric acid mixtures
- these fuels require ignition either by an electrical or mechanical device or by chemical means.
- This invention also relates to a new method of causing spontaneous ignition and to a new method of spontaneously igniting hydrocarbon fuels, particularly in rocket propulsion.
- the blend of the combustible organic material and the unsaturated silane (preferably from 0.1 to 50% by Weight based on the organic fuel) is admixed in the combustion chamber of the engine with an appro priate oxidizing agent and ignition occurs instantaneously thereby initiating combustion of the fuel.
- an appro priate oxidizing agent preferably at least of the unsaturated silane based on the hydrocarbon is employed.
- the amount employed should be sufficient to efiect ignition. The amount required for ignition will depend upon the particular unsaturated silane used and can be readily determined by those skilled in the art in the light of this specification.
- the unsaturated silanes which are operable in this invention include both alkenyl and alkynyl silanes and the former are preferred.
- R* is usually hydrogen or lower alkyl particularly methyl.
- Exemplary of such compounds are diallyl silane, tetra (Z-methallyl) silane, triallyl silane, tetraallyl silane, diallyl dimethyl silane, di(2-methylaliyl) dimethyl silane, allyl trimethyl silane and diallyl ethyl propyl silane. Tetraallyl silane and triallyl silane are especially preferred.
- These allylic-type silanes can be prepared by methods well-known to those skilled in the art, e.g., by the reaction of an allylic magnesium halide with a silicon halide.
- the corresponding vinyl and isopropenyl silanes e.g., divinyl silane, trivinyl silane and trivinylethyl silane are likewise operable but suffer the disadvantage of higher preparative costs.
- other unsaturated silanes include bis (trimethylsilyl) acetylene.
- Suitable combustible organic materials include those well-known to the art of jet-propulsion fuels such as hydrocarbons (e.g., propane, butane, butene, pentane, pentene-l, isopentane, cyclopentane, methylcyclopentane, hexane, isohexane, cyclohexane, heptane, octane, isooctane, mixtures thereof such as gasoline and kerosene, benzene, toluene and xylene), alcohols (e.g., methanol, ethanol, propanol, isopropanol, ethylene glycol, butanol and butanediol), ethers (e.g., dimethyl ether and dimethyl acetal), aldehydes
- hydrocarbons e.g., propane, butane, butene, pentane, pentene-l
- inorganic oxidizing agents those derived from nitrogen oxides e.g., concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid with sulfuric acid have proven satisfactory.
- EXAMPLE 1 The ignition ensuing from the reaction of the unsaturated silanes with various oxidizing agents derived from nitrogen oxides can be illustrated by adding 0.1 g. of the silane to 0.5 g. of the oxidizing agent. A number of these reactions are tabulated below (Table I) wherein the abbreviation Ig. signifies that ignition occurs while No Ig. means that no ignition is detected at the above concentrations.
- dispersion is used to denote g: the mixture of the unsaturated hydrocarbon silane and 1215121113 1 dimefliilsilzineII j- Ifilo %g...
- N I the combustible organic fuel whether such mixture be a o I in rr ii rh ii iiiiri n ii i rio Ig N3 15m No No 1g true solution or a collo1 da1 d1spers1on.
- a self-igniting fuel obtained by mixing an inorganic oxidizing agent derived from an oxide of nitrogen and F a g fig g i ii g ia 2 9g :3: 53383 3 0 selected from the group consisting of concentrated nitric gre acid, fuming nitric acid, nitrogen tetraoxide and mixtures allyhc substituents 1s increased.
- R and R are each one of the radicals, hydrogen, methyl
- Tnlmmo Xylene 350Ig Gas01ine..- 350 White fuming HNO;,+12% Benzene..
- R and R are each one of the radicals, hydrogen, methyl and ethyl and R* is one of the radiinvention is particularly applicable in the field of jet procals, hydrogen and lower alkyl, said silane being present pulsion.
- I provide separate supplies of the oxidizing agent derived from the nitrogen oxide on the one hand and of the unsaturated hydrocarbon silane on the other in an amount efiective to cause instantaneous ignition of the mixture.
- a self-igniting fuel obtained by mixing an inorganic oxidizing agent derived from an oxide of nitrogen and hand and meter these materials continuously into the selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid and sulfuric acid with a liquid hydrocarbon having dispersed therein from 0.1 to 50% by weight of tetraallyl silane, said silane being present in an amount effective to cause instantaneous ignition of the mixture.
- a self-igniting fuel obtained by mixing an inorganic oxidizing agent derived from an oxide of nitrogen and selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid and sulfuric acid with a liquid bydrocarbon boiling in the range of 75-300 C. having dispersed therein from 0.1 to 50% by weight of tetra allyl silane, said silane being present in an amount effective to cause instantaneous ignition of the mixture.
- a self-igniting fuel obtained by mixing an inorganic oxidizing agent derived from an oxide of nitrogen and selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid and sulfuric acid with a liquid hydrocarbon boiling in the range of 75-300 C. having dispersed therein from 0.1 to 50% by weight of triallyl silane, said silane being present in an amount effective to cause instantaneous ignition of the mixture.
- a self-igniting fuel obtained by mixing an inorganic oxidizing agent selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide, and mixtures of fuming nitric acid and sulfuric acid, a liquid combustible organic material selected from the group consisting of hydrocarbons, alcohols, ethers, aldehydes, ketones, amines, hydrazine, and substituted hydrazines, and from 0.1 to 50% by weight based on said liquid combustible organic material of a poly-2- alkenyl silane of the type formula where n is 3 or 4, R and R are each one of the radicals, hydrogen, methyl and ethyl, and R* is one of the radicals, hydrogen and lower alkyl, said silane being present in an amount efiective to cause instantaneous ignition of the mixture.
- an inorganic oxidizing agent selected from the group consisting of concentrated nitric acid, fuming n
- an inorganic oxidizing agent selected from the
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Description
United States Patent 3,028,272 SELF-IGNITING ROCKET PROPELLANTS CON- TAINING ORGANIC SILANES Pliny 0. Tawney, Passaic, N.J., assignor to United States Rubber Company, New York, N.Y., a corporation of New Jersey No Drawing. Filed Nov. 17, 1948, Ser. No. 60,618 7 Claims. (Cl. 149-36) This invention concerns self-igniting fuels for combustion machinery and more particularly relates to the use of certain chemical igniters for fuels which are based on a mixture of an organic material and an oxidizing agent. Such fuels, e.g., gasoline-nitric acid mixtures, have been employed in a variety of combustion machines and particularly in the jet propulsion type of engines, e.g., rockets. However, in such applications, these fuels require ignition either by an electrical or mechanical device or by chemical means.
This invention also relates to a new method of causing spontaneous ignition and to a new method of spontaneously igniting hydrocarbon fuels, particularly in rocket propulsion.
It has now been found that unsaturated organic silanes undergo spontaneous ignition when admixed with inorganic oxidizing agents, particularly those derived from nitrogen oxides, and it has been further discovered that such unsaturated silanes are particularly and unexpectedly efficacious as igniters for fuels based on mixtures of combustible organic materials and such inorganic oxidizing agents. This discovery is particularly surprising in view of the behavior of the corresponding saturated organic silanes which are relatively ineffective as igniters. Indeed even many of the unsaturated silanes containing atoms other than carbon, hydrogen and silicon, and particularly oxygen, nitrogen and sulfur are markedly inferior or completely useless for this purpose.
In practice, the blend of the combustible organic material and the unsaturated silane (preferably from 0.1 to 50% by Weight based on the organic fuel) is admixed in the combustion chamber of the engine with an appro priate oxidizing agent and ignition occurs instantaneously thereby initiating combustion of the fuel. Usually at least of the unsaturated silane based on the hydrocarbon is employed. The amount employed should be sufficient to efiect ignition. The amount required for ignition will depend upon the particular unsaturated silane used and can be readily determined by those skilled in the art in the light of this specification.
Since the use of these novel igniters obviates the necessity for a mechanical or electrical ignition system, the design and maintenance of the combustion machine is correspondingly simplified. Moreover it has been found that the use of these new chemical igniters introduce few or no additional problems such as corrosion, inflammability, toxicity, premature decomposition, etc. and hence propellant fuels based on these igniters can be employed in present installations and motors with little or no adaptation. Indeed the combustion reaction of my fuel deposits a protective refractory coating of finely divided silica on the walls of the combustion chamber, which retards the development of hot spots and other high temperature corrosion phenomena and thus prolongs the operational life cycle of the engine. This is particularly important in the art of jet propulsion since it permits sustained and protracted operation of such engines e.g., rockets, with a minimum of maintenance, repair and replacement.
The unsaturated silanes which are operable in this invention include both alkenyl and alkynyl silanes and the former are preferred. Of this class, the allylic-type silanes, i.e., those containing the group I I l I C=C-(|)-Sll are preferred on the basis of cost, availability and performance, particularly those silanes containing three or four of such allylic-type radicals e.g., allyl, Z-methylallyl, Z-ethylallyl and 3-methylallyl groups. This preferred group of silanes can be represented by the type formula -(R-CH=CR-CH ),,Si(R*)., where n is an integer having a value of 3 or 4, R and R are each one of the radicals, hydrogen and lower alkyl (e.g., methyl, ethyl) and R* is one of the radicals, hydrogen and alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl and decyl). R* is usually hydrogen or lower alkyl particularly methyl. Exemplary of such compounds are diallyl silane, tetra (Z-methallyl) silane, triallyl silane, tetraallyl silane, diallyl dimethyl silane, di(2-methylaliyl) dimethyl silane, allyl trimethyl silane and diallyl ethyl propyl silane. Tetraallyl silane and triallyl silane are especially preferred. These allylic-type silanes can be prepared by methods well-known to those skilled in the art, e.g., by the reaction of an allylic magnesium halide with a silicon halide.
The corresponding vinyl and isopropenyl silanes, e.g., divinyl silane, trivinyl silane and trivinylethyl silane are likewise operable but suffer the disadvantage of higher preparative costs. In addition to the above preferred class other unsaturated silanes include bis (trimethylsilyl) acetylene.
The above unsaturated silanes can be employed as igniters for a wide variety of combustible organic materials and inorganic oxidizing agents. Suitable combustible organic materials include those well-known to the art of jet-propulsion fuels such as hydrocarbons (e.g., propane, butane, butene, pentane, pentene-l, isopentane, cyclopentane, methylcyclopentane, hexane, isohexane, cyclohexane, heptane, octane, isooctane, mixtures thereof such as gasoline and kerosene, benzene, toluene and xylene), alcohols (e.g., methanol, ethanol, propanol, isopropanol, ethylene glycol, butanol and butanediol), ethers (e.g., dimethyl ether and dimethyl acetal), aldehydes (e.g., acetaldehyde, butyraldehyde and glyoxal), ketones (e.g., acetone, methyl ethyl ketone and butyl methyl ketone and acetophenone), amines (e.g., methyl amine, dimethyl amine, trimethyl amine, methyl ethyl amine, ethanol amine, aniline, N-methylaniline and p-phenylenediamine), hydrazines' (e.g., hydrazine, methyl hydrazine, dimethylhydrazine and phenylhydrazine). Among such organic materials the liquid compounds and/or mixtures thereof are preferred.
Among the inorganic oxidizing agents those derived from nitrogen oxides e.g., concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid with sulfuric acid have proven satisfactory.
Some mixtures of the above fuels and oxidizing agents are themselves capable of spontaneous ignition, but even in such cases I have found that my unsaturated hydrocarbon silanes decrease the ignition time and improve the efficacy of such fuel mixtures, particularly with respect to the deposition of a protective silica deposit on the combustion chamber as described above.
The following examples disclose the invention in more detail.
EXAMPLE 1 The ignition ensuing from the reaction of the unsaturated silanes with various oxidizing agents derived from nitrogen oxides can be illustrated by adding 0.1 g. of the silane to 0.5 g. of the oxidizing agent. A number of these reactions are tabulated below (Table I) wherein the abbreviation Ig. signifies that ignition occurs while No Ig. means that no ignition is detected at the above concentrations.
combustion chamber in conjunction with the combustible organic fuel. The resulting mixture ignites spontaneously as soon as the materials are mixed.
The term inorganic oxidizing agent derived from an Table I oxide of nitrogen as used herein denotes either the oxides of nitrogen themselves, particularly nitrogen tetraoxide, oxidizing Agent and materials containing nitrogen tetraoxide especially turning nitric oxide, as well as materials containing the silane Red whit Wh te oxides of nitrogen in chemically combined form and ca- 253 fi f g f N20 f ig g i pable of releasing such oxides of nitrogen under the con- (sp,g (sp.g.= 12% ditions prevailing in the mixing chamber, for example, 1.59-1.00 1.40-1.50) H2504 concentrated nitric acid As used herein the term dispersion is used to denote g: the mixture of the unsaturated hydrocarbon silane and 1215121113 1 dimefliilsilzineII j- Ifilo %g... N I the combustible organic fuel whether such mixture be a o I in rr ii rh ii iiiiri n ii i rio Ig N3 15m No No 1g true solution or a collo1 da1 d1spers1on. (f) Tetrnethyl silane N0 Ig No Ig N0 Ig-.- N0 Ig I clalm as my nvent on:
1. A self-igniting fuel obtained by mixing an inorganic oxidizing agent derived from an oxide of nitrogen and F a g fig g i ii g ia 2 9g :3: 53383 3 0 selected from the group consisting of concentrated nitric gre acid, fuming nitric acid, nitrogen tetraoxide and mixtures allyhc substituents 1s increased. Moreover it W111 be of fuming nitric acid and Sulfuric acid with a liquid y noted that, in contrast, the saturated alkyl silanes of d I rocarbon having dispersed therein from 0.1 to 50% by 23 522 d'lsplay no igmuon' amvl'ty under these same weight of a poly-2-alkenyl silane of the type formula EXAMPLE 2 (R-CI-I=CR'-CH ),,Si(R*) where n is 3 or 4, R and R are each one of the radicals, hydrogen, methyl A number of the most active unsaturated silanes from ethyl one the TadiQaIS hydrogen and Table I above are employed as igniters for typical hydrogsz g gig 5 35 122232? Pt z s gf i h 11:33: 9 mlxmres by addfng a 2 A self-igniting fuel obt a i ned b mixin an nor a Solution of the silane in four representative hydrocarbon o d d f 1 Y g 1 8 me g .stsia fsiz aizzip .21.";saga tstaazaaai to g. o e oxi izing agent. e res ts, ta u ae below (Table II) are indicated by the same abbreviations gi i fig g f f E EE K animlgdures as g g n w e ........i.:.ti;t:. anatomist: tion g. meamng or er ne lgmtlon at at concentration has been added. The concentrations of the gg ig ii to 5 by Welght of a P l" silane in the hydrocarbon fuel are expressed in weight y S1 0 8 type ormula percent. 2)n *)4-n Table II Tetraallyl Triallyl Diallyl Ally] Oxidizing Agent Hydrocarbon silane, Cone. Silane, Cone. s gnimetchyl sffrimehyi i 0, one. 1 ane, one.
0350111100-- 0 1g 50.0 No Ig.
Benzene B- 79 50.0 No Ig. Red fuming s 5 lg 22.0 B. Ig 50.0 No Ig.
Xylene 20.0 B. Ig--"- 50.0 No Ig. aasolmenu 15 50.0 B. Ig."..- 50.0 No Ig...." 50.0 No Ig.
25.0 B. Ig 50.0 No Ig.. 50.0 No Ig. 22.0 B. Ig.-..- 50.0 No Ig----- 50.0 No Ig.
Xylene 28.0 B. Ig--.. 50.0 No Ig."-.. 50.0 No Ig. 30.0 B. T!
{35 0 30.0 B. Ig White turning HNO;
Tnlmmo Xylene 350Ig Gas01ine..- 350 White fuming HNO;,+12% Benzene..
H150 35.0 Ig
Toluene..-- y Xylene {2518 10m The principles of my invention may be employed wherever it is desired to effect spontaneous ignition. My
where n is 3 or 4, R and R are each one of the radicals, hydrogen, methyl and ethyl and R* is one of the radiinvention is particularly applicable in the field of jet procals, hydrogen and lower alkyl, said silane being present pulsion. In the usual application of my invention to jet propulsion, I provide separate supplies of the oxidizing agent derived from the nitrogen oxide on the one hand and of the unsaturated hydrocarbon silane on the other in an amount efiective to cause instantaneous ignition of the mixture.
3. A self-igniting fuel obtained by mixing an inorganic oxidizing agent derived from an oxide of nitrogen and hand and meter these materials continuously into the selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid and sulfuric acid with a liquid hydrocarbon having dispersed therein from 0.1 to 50% by weight of tetraallyl silane, said silane being present in an amount effective to cause instantaneous ignition of the mixture.
4. A self-igniting fuel obtained by mixing an inorganic oxidizing agent derived from an oxide of nitrogen and selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid and sulfuric acid with a liquid bydrocarbon boiling in the range of 75-300 C. having dispersed therein from 0.1 to 50% by weight of tetra allyl silane, said silane being present in an amount effective to cause instantaneous ignition of the mixture.
5. A self-igniting fuel obtained by mixing an inorganic oxidizing agent derived from an oxide of nitrogen and selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid and sulfuric acid with a liquid hydrocarbon boiling in the range of 75-300 C. having dispersed therein from 0.1 to 50% by weight of triallyl silane, said silane being present in an amount effective to cause instantaneous ignition of the mixture.
6. A self-igniting fuel obtained by mixing an inorganic oxidizing agent selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide, and mixtures of fuming nitric acid and sulfuric acid, a liquid combustible organic material selected from the group consisting of hydrocarbons, alcohols, ethers, aldehydes, ketones, amines, hydrazine, and substituted hydrazines, and from 0.1 to 50% by weight based on said liquid combustible organic material of a poly-2- alkenyl silane of the type formula where n is 3 or 4, R and R are each one of the radicals, hydrogen, methyl and ethyl, and R* is one of the radicals, hydrogen and lower alkyl, said silane being present in an amount efiective to cause instantaneous ignition of the mixture.
7. A propulsion fuel consisting of a liquid combustible organic material selected from the group consisting of hydrocarbons, alcohols, ethers, aldehydes, ketones, amines, hydrazine, and substituted hydrazines and from 0.1 to by weight based on said combustible organic material of a poly-2-alkeny1 silane of the type formula (R--CH=CR-CH ),,Si(R*) where n is 3 or 4, R and R are each one of the radicals, hydrogen, methyl and ethyl, and R* is one of the radicals, hydrogen and lower alkyl, said silane being present in an amount effective to cause instantaneous ignition of said fuel when it is admixed with an inorganic oxidizing agent selected from the group consisting of concentrated nitric acid, fuming nitric acid, nitrogen tetraoxide and mixtures of fuming nitric acid and sulfuric acid.
References Cited in the file of this patent UNITED STATES PATENTS 2,298,255 Hopkins Oct. 6, 1942 2,356,476 Shappirio Aug. 22, 1944 2,388,161 Kropa Oct. 30, 1945 2,474,183 King June 21, 1949
Claims (1)
- 7. A PROPULSION FUEL CONSISTING OF A LIQUID COMBUSTIBLE ORGANIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF HYDROCARBONS, ALCOHOLS, ETHERS, ALDEHYDES, KETONES, AMINES, HYDRAZINE, AND SUBSTITUTED HYDRAZINES AND FROM 0.1 TO 50% BY WEIGHT BASED ON SAID COMBUSTIBLE ORGANIC MATERIAL OF A POLY-2-ALKENYL SILANE OF THE TYPE FORMULA (R-CH=CR''-CH2)NSI(R*)4-N WHERE N IS 3 OR 4, R AND R'' ARE EACH ONE OF THE RADICALS, HYDROGEN, METHYL AND ETHYL, AND R* IS ONE OF THE RADICALS, HYDROGEN AND LOWER ALKYL, SAID SILANE BEING PRESENT IN AN AMOUNT EFFECTIVE TO CAUSE INSTANTANEOUS IGNITION OF SAID FUEL WHEN IT IS ADMIXED WITH AN INORGANIC OXIDIZING AGENT SELECTED FROM THE GROUP CONSISTING OF CONCENTRATED NITRIC ACID, FUMING NITRIC ACID, NITROGEN TETRAOXIDE AND MIXTURES OF FUMING NITRIC ACID AND SULFURIC ACID.
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| US60618A US3028272A (en) | 1948-11-17 | 1948-11-17 | Self-igniting rocket propellants containing organic silanes |
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| US60618A US3028272A (en) | 1948-11-17 | 1948-11-17 | Self-igniting rocket propellants containing organic silanes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5435224A (en) * | 1979-04-04 | 1995-07-25 | The United States Of America As Represented By The Secretary Of The Navy | Infrared decoy |
| US20050076560A1 (en) * | 2001-08-27 | 2005-04-14 | Wiley David B. | Alkynylsilanes as fuels and rocket propellants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2298255A (en) * | 1939-05-08 | 1942-10-06 | Hopkins Nevil Monroe | Liquid explosive |
| US2356476A (en) * | 1941-06-28 | 1944-08-22 | Shappirio Sol | Motor fuels |
| US2388161A (en) * | 1944-07-31 | 1945-10-30 | American Cyanamid Co | Tetra-allyl silicane and process of preparing the same |
| US2474183A (en) * | 1949-06-21 | Rocket propulsion by reacting |
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1948
- 1948-11-17 US US60618A patent/US3028272A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2474183A (en) * | 1949-06-21 | Rocket propulsion by reacting | ||
| US2298255A (en) * | 1939-05-08 | 1942-10-06 | Hopkins Nevil Monroe | Liquid explosive |
| US2356476A (en) * | 1941-06-28 | 1944-08-22 | Shappirio Sol | Motor fuels |
| US2388161A (en) * | 1944-07-31 | 1945-10-30 | American Cyanamid Co | Tetra-allyl silicane and process of preparing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5435224A (en) * | 1979-04-04 | 1995-07-25 | The United States Of America As Represented By The Secretary Of The Navy | Infrared decoy |
| US20050076560A1 (en) * | 2001-08-27 | 2005-04-14 | Wiley David B. | Alkynylsilanes as fuels and rocket propellants |
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