EP0705808B1 - Propellant based on phase-stabilized ammonium nitrate - Google Patents
Propellant based on phase-stabilized ammonium nitrate Download PDFInfo
- Publication number
- EP0705808B1 EP0705808B1 EP95112989A EP95112989A EP0705808B1 EP 0705808 B1 EP0705808 B1 EP 0705808B1 EP 95112989 A EP95112989 A EP 95112989A EP 95112989 A EP95112989 A EP 95112989A EP 0705808 B1 EP0705808 B1 EP 0705808B1
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- EP
- European Patent Office
- Prior art keywords
- solid propellant
- propellant according
- mass
- oxide
- energy
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- 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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- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 title claims description 21
- 239000003380 propellant Substances 0.000 title description 2
- 239000004449 solid propellant Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004014 plasticizer Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- -1 nitro- Chemical class 0.000 claims description 7
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 6
- QUAMCNNWODGSJA-UHFFFAOYSA-N 1,1-dinitrooxybutyl nitrate Chemical compound CCCC(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QUAMCNNWODGSJA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000028 HMX Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- 150000002823 nitrates Chemical class 0.000 claims description 5
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 claims description 5
- IPPYBNCEPZCLNI-UHFFFAOYSA-N trimethylolethane trinitrate Chemical group [O-][N+](=O)OCC(C)(CO[N+]([O-])=O)CO[N+]([O-])=O IPPYBNCEPZCLNI-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- ZQXWPHXDXHONFS-UHFFFAOYSA-N 1-(2,2-dinitropropoxymethoxy)-2,2-dinitropropane Chemical compound [O-][N+](=O)C([N+]([O-])=O)(C)COCOCC(C)([N+]([O-])=O)[N+]([O-])=O ZQXWPHXDXHONFS-UHFFFAOYSA-N 0.000 claims description 2
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910026551 ZrC Inorganic materials 0.000 claims description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- VIDWEALKNBGAFU-UHFFFAOYSA-N n-(1,5-diazidopentan-3-yl)nitramide Chemical compound [N-]=[N+]=NCCC(N[N+](=O)[O-])CCN=[N+]=[N-] VIDWEALKNBGAFU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims 2
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 claims 2
- 239000001692 EU approved anti-caking agent Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 230000002349 favourable effect Effects 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 241001649081 Dina Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KDEDDPRZIDYFOB-UHFFFAOYSA-N n-methyl-n-phenylnitramide Chemical compound [O-][N+](=O)N(C)C1=CC=CC=C1 KDEDDPRZIDYFOB-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 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
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/30—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with vegetable matter; with resin; with rubber
Definitions
- the invention relates to a solid fuel for rocket engines or gas generators, which contains phase-stabilized ammonium nitrate as an oxidizer.
- Solid fuels of the type mentioned generally have a low burning rate and a high pressure exponent.
- the burning rate can be increased by adding solid energetic substances, such as octogen (HMX) or hexogen (RDX), or metals with high heat of combustion, such as aluminum or boron.
- Combinations with high-energy binders serve the same goal. These include isocyanate-bound glycidyl azidopolymer (GAP), polymers containing nitrate esters, such as polyglycidyl nitrate and polynitratomethylethyloxetane, or nitroamino-substituted polymers. Even if this can increase the rate of combustion, the pressure exponent and the temperature coefficient are not or only slightly reduced. Additions of ammonium perchlorate, which increase the Burning rate lead to lower the pressure exponent at higher doses, but lead to the formation of hydrochloric acid in the exhaust gas and thus to strong smoke formation at high air humidity.
- the burning behavior can be influenced favorably by adding lead and copper salts or oxides in combination with soot, but these additives can only be used to a limited extent with fuels containing ammonium nitrate.
- the invention has for its object to improve the combustion behavior of solid fuels based on phase-stabilized ammonium nitrate.
- such a solid fuel consists of 35 to 80% by mass ammonium nitrate (AN) with an average grain size of 5 to 200 ⁇ m, which is phase-stabilized by chemical reaction with CuO or ZnO (PSAN), 15 to 50% by mass of a binder system made of a binder polymer and an energy-rich plasticizer and 0.2 to 5.0 mass% of a combustion moderator made of vanadium / molybdenum oxide as an oxide mixture or mixed oxide.
- AN ammonium nitrate
- PSAN phase-stabilized by chemical reaction with CuO or ZnO
- Solid fuels of this formulation show a very favorable burning behavior. Depending on the composition, burning rates of over 8mm / s at normal temperature and a combustion chamber pressure of 10 MPa are achieved. The pressure exponent in the range from 4 to 25 MPa, possibly 7 to 25 MPa, reaches values of n ⁇ 0.6, in the best case n ⁇ 0.5. This combustion behavior makes the solid fuel composed according to the invention particularly suitable for use in missiles for tactical or strategic missile defense.
- the solid propellants according to the invention are initially characterized by the phase-stabilized ammonium nitrate reacted with copper oxide or zinc oxide as the oxidizer, the metal oxides preferably being used in a quantity of 1 to 7% by mass. They stabilize the crystal phases of the AN and suppress larger volume changes in the grain in the temperature range from -40 to + 70 ° C.
- the incorporation into the crystal matrix of the AN takes place via a chemical reaction of copper or zinc oxide with the melt of the pure ammonium nitrate with elimination of water .
- the most favorable particle shape for the production of the fuel can then be obtained by spraying the melt and rapid cooling in a cold, cyclone-like air flow.
- the combustion behavior is significantly influenced by the grain size of the phase-stabilized ammonium nitrate.
- a finely crystalline form with an average grain size of 5 to 200 ⁇ m with a proportion of 35 to 80 mass% in the fuel is preferred.
- Particularly favorable burn-up values result when the AN fraction is predominantly in a smaller grain size of 5 to 80 ⁇ m and less in an average grain size of 100 to 160 ⁇ m.
- the solid propellant according to the invention may also contain high-energy substances, in particular nitramines, such as hexogen (RDX) or octogen (HMX) with an average grain size of 2 to 20 ⁇ m with a proportion of 1 to 20% by mass.
- nitramines such as hexogen (RDX) or octogen (HMX) with an average grain size of 2 to 20 ⁇ m with a proportion of 1 to 20% by mass.
- metals such as aluminum, magnesium or boron can be part of the fuel with 0.5 to 20% by mass.
- a grain size of 0.1 to 50 ⁇ m is recommended.
- stabilizers which act as nitrogen oxide and acid scavengers.
- These are preferably diphenylamine, 2-nitrodiphenylamine, N-methylnitroaniline, which are used alone or in combination with one another in concentrations of 0.4 to 2% by mass. These can be combined, in particular in the case of fuels containing nitric acid, with small amounts in the range of 0.5% by mass of the magnesium oxide acting in the same sense.
- the combustion moderators are preferably used as mixed oxides, in which molybdenum of the oxidation level + VI and vanadium of the oxidation level + IV and + V are present.
- Exemplary compositions of the mixed oxides are V 6 Mo 4 O 25 and V 6 Mo 15 O 60 .
- the combustion moderators can also have Crom III or Titan IV oxides as the carrier material.
- combustion moderators used according to the invention with 0.2 to 5.0 mass% are advantageously added to the fraction of the combustion moderator with carbon black or graphite in a proportion of 5 to 50 mass%.
- binder system consisting of a binder polymer and an energy-rich plasticizer.
- the binder polymer itself can be inert, preferably isocyanate-curing, bi- or trifunctional Hydroxy-substituted polyester or polyether prepolymers.
- high-energy polymers preferably isocyanate-curing, di- or trifunctional hydroxy-substituted glycidyl azidopolymer, can also be used.
- the high-energy plasticizers are preferably selected from the group of chemically stable nitrate esters, nitro, nitroamino or azido plasticizers.
- TMETN Trimethylolethane trinitrate
- BTTN butanetriol trinitrate
- DEGDN diethylene glycol dinitrate
- a 1: 1 mixture of bisdinitropropyl formal / acetal may be mentioned as an example of a nitro softener, while a 1: 1 mixture of N-ethyl and N-methylnitratoethylnitroamine (EtNENA or MeNENA) or Nn-butyl- N-nitratoethylnitroamine (BuNENA) or N, N'-dinitratoethylnitroamine (DINA) is suitable.
- EtNENA or MeNENA N-methylnitratoethylnitroamine
- BuNENA N-butyl- N-nitratoethylnitroamine
- DINA N, N'-dinitratoethylnitroamine
- GAP-A bisazido-terminated GAP oligomers
- DANPE 5-diazido-3-nitroaminopentane
- the polymer / plasticizer ratio is 1: 3 to 20: 1 mass%.
- the binder polymers can of course also be used in pure form.
- 0.1 to 1% by mass of its anti-caking agent fraction for example ultrafine (grain size about 0.02 ⁇ m) silica gel, sodium lauryl sulfonate, tricalcium phosphate or other surfactants are preferably added to the phase-stabilized ammonium nitrate.
- the vanadium / molybdenum oxide combustion moderators can be ideally combined with copper salts, oxides or complexes, which brings about a further increase in the combustion rate, especially in the low pressure range, combined with a further reduction in the pressure exponent.
- ammonium nitrate stabilized with copper oxide in combination with vanadium / molybdenum oxides therefore has a particularly favorable effect on the combustion behavior.
- the addition of 2 to 7% by mass of the phase-stabilizing CuO provided according to the invention results in significantly higher burn-up rates and low pressure exponents. This favorable combustion behavior can be seen above all in solid fuels whose binders contain up to 50% azido compounds in the form of energetic polymers and / or plasticizers.
- the combustion moderators have a grain size in the range from 1 to 60 ⁇ m, preferably 1 to 10 ⁇ m, and a high internal surface area of 5 to 100 m 2 / g, preferably 20 to 60 m 2 / g.
- Metal-free solid fuels of the type described are suitable for use in rocket engines due to their energy content, their low-smoke, hydrochloric acid-free combustion and their comparatively low, mechanical and detonative sensitivity, while lower-energy formulations with a higher proportion of binder are suitable for use as gas generator propellants.
- high-melting metal carbides or nitrates preferably silicon and / or zirconium carbide, with a concentration of 0.1 to 1 mass% are advantageously added as further additives.
- these additives suppress unstable oscillations in the combustion behavior.
- Table 1 shows five different formulations of ammonium nitrate, which is phase-stabilized with copper oxide or zinc oxide (PSAN).
- the burning rate r (mm / s) at 20 ° C and at three different combustion chamber pressures is given in the lower part of the table for the individual formulations. Below this is the pressure exponent n for various pressure ranges given in brackets.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Inorganic Insulating Materials (AREA)
- Air Bags (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
Die Erfindung betrifft einen Festtreibstoff für Raketenantriebe oder Gasgeneratoren, der als Oxidator phasenstabilisiertes Ammoniumnitrat enthält.The invention relates to a solid fuel for rocket engines or gas generators, which contains phase-stabilized ammonium nitrate as an oxidizer.
Festtreibstoffe der genannten Art weisen in der Regel eine niedrige Abbrandgeschwindigkeit und einen hohen Druckexponenten auf. Die Abbrandgeschwindigkeit läßt sich durch Zusatz von festen energetischen Stoffen, wie Oktogen (HMX) oder Hexogen (RDX), oder von Metallen mit hoher Verbrennungswärme, wie Aluminium oder Bor steigern. Dem gleichen Ziel dienen auch Kombinationen mit energiereichen Bindern. Hierzu zählen isocyanat-gebundenes Glycidylazidopolymer (GAP), nitratesterhaltige Polymere, wie Polyglycidylnitrat und Polynitratomethylethyloxetan oder nitroamino-substituierte Polymere. Auch wenn sich hierdurch die Abbrandgeschwindigkeit steigern läßt, werden der Druckexponent und der Temperaturkoeffizient nicht oder nur wenig erniedrigt. Zusätze von Ammoniumperchlorat, die zu einer Steigerung der Abbrandgeschwindigkeit führen, senken zwar bei höherer Dosierung den Druckexponenten, führen jedoch zur Bildung von Salzsäure im Abgas und damit zu starker Rauchbildung bei hoher Luftfeuchtigkeit.Solid fuels of the type mentioned generally have a low burning rate and a high pressure exponent. The burning rate can be increased by adding solid energetic substances, such as octogen (HMX) or hexogen (RDX), or metals with high heat of combustion, such as aluminum or boron. Combinations with high-energy binders serve the same goal. These include isocyanate-bound glycidyl azidopolymer (GAP), polymers containing nitrate esters, such as polyglycidyl nitrate and polynitratomethylethyloxetane, or nitroamino-substituted polymers. Even if this can increase the rate of combustion, the pressure exponent and the temperature coefficient are not or only slightly reduced. Additions of ammonium perchlorate, which increase the Burning rate lead to lower the pressure exponent at higher doses, but lead to the formation of hydrochloric acid in the exhaust gas and thus to strong smoke formation at high air humidity.
Bei Doublebase- und Composit Doublebase-Festtreibstoffen läßt sich das Abbrandverhalten durch Zusatz von Blei- und Kupfersalzen oder -oxiden in Verbindung mit Ruß günstig beeinflußen, doch lassen sich diese Zusätze bei ammoniumnitrathaltigen Treibstoffen nur in begrenzten Maß einsetzen. Die genannten Salze und Oxide wirken wiederum vornehmlich im Sinne einer Steigerung der Abbrandgeschwindigkeit, können jedoch den Druckexponenten nicht ausreichend absenken.In doublebase and composite doublebase solid fuels, the burning behavior can be influenced favorably by adding lead and copper salts or oxides in combination with soot, but these additives can only be used to a limited extent with fuels containing ammonium nitrate. The salts and oxides mentioned in turn act primarily to increase the rate of combustion, but cannot reduce the pressure exponent sufficiently.
Der Erfindung liegt die Aufgabe zugrunde, daß Abbrandverhalten von Festtreibstoffen auf der Basis von phasenstabilisiertem Ammoniumnitrat zu verbessern.The invention has for its object to improve the combustion behavior of solid fuels based on phase-stabilized ammonium nitrate.
Erfindungsgemäß besteht ein solcher Festtreibstoff aus 35 bis 80 Massen-% Ammoniumnitrat (AN) mit einer mittleren Korngröße von 5 bis 200µm, das durch chemische Umsetzung mit CuO oder ZnO phasenstabilisiert ist (PSAN), 15 bis 50 Massen-% eines Bindersystems aus einem Binderpolymer und einem energiereichen Weichmacher sowie 0,2 bis 5,0 Massen-% eines Abbrandmoderators aus Vanadium/Molybdänoxid als Oxidmischung oder Mischoxid.According to the invention, such a solid fuel consists of 35 to 80% by mass ammonium nitrate (AN) with an average grain size of 5 to 200 µm, which is phase-stabilized by chemical reaction with CuO or ZnO (PSAN), 15 to 50% by mass of a binder system made of a binder polymer and an energy-rich plasticizer and 0.2 to 5.0 mass% of a combustion moderator made of vanadium / molybdenum oxide as an oxide mixture or mixed oxide.
Festtreibstoffe dieser Formulierung zeigen ein sehr günstiges Abbrandverhalten. Es werden je nach Zusammensetzung Abbrandgeschwindigkeiten über 8mm/s bei Normaltemperatur und einem Brennkammerdruck von 10 MPa erreicht. Der Druckexponent erreicht im Bereich von 4 bis 25 MPa, gegebenenfalls 7 bis 25 MPa, Werte von n < 0,6, im günstigen Fall n < 0,5. Dieses Abbrandverhalten verleiht dem erfindungsgemäß zusammengesetzten Festtreibstoff besondere Eignung zum Einsatz in Flugkörpern der taktischen oder strategischen Raketenabwehr.Solid fuels of this formulation show a very favorable burning behavior. Depending on the composition, burning rates of over 8mm / s at normal temperature and a combustion chamber pressure of 10 MPa are achieved. The pressure exponent in the range from 4 to 25 MPa, possibly 7 to 25 MPa, reaches values of n <0.6, in the best case n <0.5. This combustion behavior makes the solid fuel composed according to the invention particularly suitable for use in missiles for tactical or strategic missile defense.
Die erfindungsgemäßen Festtreibstoffe zeichnen sich zunächst durch das mit Kupferoxid oder Zinkoxid umgesetzte, phasenstabilisierte Ammoniumnitrat als Oxidator aus, wobei die Metalloxide vorzugsweise mit 1 bis 7 Massen-% eingesetzt werden. Sie stabilisieren die Kristallphasen des AN und unterdrücken größere Volumenänderungen des Korns im Temperaturbereich von -40 bis +70° C. Der Einbau in die Kristallmatrix des AN geschieht über eine chemische Reaktion von Kupfer- oder Zinkoxid mit der Schmelze des reinen Ammoniumnitrats unter Abspaltung von Wasser. Die für die Herstellung des Treibstoffs günstigste Partikelform kann dann durch Versprühen der Schmelze und schnelles Abkühlen im kalten, zyklonartig geführten Luftstrom erhalten werden.The solid propellants according to the invention are initially characterized by the phase-stabilized ammonium nitrate reacted with copper oxide or zinc oxide as the oxidizer, the metal oxides preferably being used in a quantity of 1 to 7% by mass. They stabilize the crystal phases of the AN and suppress larger volume changes in the grain in the temperature range from -40 to + 70 ° C. The incorporation into the crystal matrix of the AN takes place via a chemical reaction of copper or zinc oxide with the melt of the pure ammonium nitrate with elimination of water . The most favorable particle shape for the production of the fuel can then be obtained by spraying the melt and rapid cooling in a cold, cyclone-like air flow.
Das Abbrandverhalten wird maßgeblich durch die Korngröße des phasenstabilisierten Ammoniumnitrats beeinflußt. Bevorzugt wird eine feinkristalline Form mit einer mittleren Korngröße von 5 bis 200 µm bei einem Anteil von 35 bis 80 Massen-% im Treibstoff. Besonders günstige Abbrandwerte ergeben sich dann, wenn die AN-Fraktion überwiegend in kleinerer Korngröße von 5 bis 80 µm und weniger in mittlerer Korngröße von 100 bis 160 µm vorliegt.The combustion behavior is significantly influenced by the grain size of the phase-stabilized ammonium nitrate. A finely crystalline form with an average grain size of 5 to 200 μm with a proportion of 35 to 80 mass% in the fuel is preferred. Particularly favorable burn-up values result when the AN fraction is predominantly in a smaller grain size of 5 to 80 µm and less in an average grain size of 100 to 160 µm.
Der erfindungsgemäße Festtreibstoff kann ferner energiereiche Stoffe, insbesondere Nitramine enthalten, wie Hexogen (RDX) oder Oktogen (HMX) mit einer mittleren Korngröße von 2 bis 20 µm bei einem Anteil von 1 bis 20 Massen-%.The solid propellant according to the invention may also contain high-energy substances, in particular nitramines, such as hexogen (RDX) or octogen (HMX) with an average grain size of 2 to 20 μm with a proportion of 1 to 20% by mass.
Weiterhin können Metalle, wie Aluminium, Magnesium oder Bor mit 0,5 bis 20 Massen-% Bestandteil des Treibstoffs sein. Hierbei empfiehlt sich eine Korngröße von 0,1 bis 50 µm.Furthermore, metals such as aluminum, magnesium or boron can be part of the fuel with 0.5 to 20% by mass. A grain size of 0.1 to 50 µm is recommended.
Um dem Treibstoff eine ausreichende chemische Stabilität zu verleihen, werden ihm mit Vorteil Stabilisatoren zugesetzt, die als Stickoxid- und Säurefänger wirken. Hierbei handelt es sich vorzugsweise um Diphenylamin, 2-Nitrodiphenylamin, N-Methylnitroanilin, die jeweils allein oder in Kombination miteinander in Konzentrationen von 0,4 bis 2 Massen-% zum Einsatz kommen. Diese lassen sich insbesondere bei salpetersäurehaltigen Treibstoffen mit geringen Mengen im Bereich von 0,5 Massen % des im gleichen Sinne wirkenden Magnesiumoxids kombinieren.In order to give the fuel sufficient chemical stability, it is advantageous to add stabilizers which act as nitrogen oxide and acid scavengers. These are preferably diphenylamine, 2-nitrodiphenylamine, N-methylnitroaniline, which are used alone or in combination with one another in concentrations of 0.4 to 2% by mass. These can be combined, in particular in the case of fuels containing nitric acid, with small amounts in the range of 0.5% by mass of the magnesium oxide acting in the same sense.
Die Abbrandmoderatoren werden vorzugsweise als Mischoxide eingesetzt, in denen Molybdän der Oxidationsstufe +VI und Vanadium der Oxidationsstufe +IV und +V vorliegen. Beispielhafte Zusammensetzungen der Mischoxide sind V6Mo4O25 und V6Mo15O60.The combustion moderators are preferably used as mixed oxides, in which molybdenum of the oxidation level + VI and vanadium of the oxidation level + IV and + V are present. Exemplary compositions of the mixed oxides are V 6 Mo 4 O 25 and V 6 Mo 15 O 60 .
Die Abbrandmoderatoren können ferner als Trägermaterial Crom III- oder Titan IV-Oxide aufweisen.The combustion moderators can also have Crom III or Titan IV oxides as the carrier material.
Die erfindungsgemäß mit 0,2 bis 5,0 Massen-% eingesetzten Abbrandmoderatoren werden vorteilhafterweise mit Ruß oder Graphit mit einem Anteil von 5 bis 50 Massen-% der Fraktion des Abbrandmoderators zugesetzt.The combustion moderators used according to the invention with 0.2 to 5.0 mass% are advantageously added to the fraction of the combustion moderator with carbon black or graphite in a proportion of 5 to 50 mass%.
Weiterer wesentlicher Bestandteil in Konzentrationen von 15 bis 50 Massen-% ist ein Bindersystem, bestehend aus einem Binderpolymer und einem energiereichen Weichmacher. Das Binderpolymer selbst kann inert sein, wobei es sich vorzugsweise um isocyanathärtende, bi- oder trifunktionell hydroxisubstituierte Polyester- oder Polyetherpräpolymere handelt. Stattdessen können auch energiereiche Polymere, vorzugsweise isocyanathärtendes, di- oder trifunktionelles hydroxisubstituiertes Glycidylazidopolymer eingesetzt werden.Another essential component in concentrations of 15 to 50% by mass is a binder system consisting of a binder polymer and an energy-rich plasticizer. The binder polymer itself can be inert, preferably isocyanate-curing, bi- or trifunctional Hydroxy-substituted polyester or polyether prepolymers. Instead, high-energy polymers, preferably isocyanate-curing, di- or trifunctional hydroxy-substituted glycidyl azidopolymer, can also be used.
Die energiereichen Weichmacher werden vorzugsweise aus der Gruppe der chemisch stabilen Nitratester, Nitro-, Nitroamino- oder Azidoweichmacher ausgewählt.The high-energy plasticizers are preferably selected from the group of chemically stable nitrate esters, nitro, nitroamino or azido plasticizers.
Als Nitratester kommen vor allem Trimethylolethantrinitrat (TMETN), Butantrioltrinitrat (BTTN) oder Diethylenglykoldinitrat (DEGDN) in Frage.Trimethylolethane trinitrate (TMETN), butanetriol trinitrate (BTTN) or diethylene glycol dinitrate (DEGDN) are particularly suitable as nitrate esters.
Als Beispiel für einen Nitroweichmacher sei ein 1:1 Gemisch von Bisdinitropropylformal/acetal (BDNPF/A) erwähnt, während als Nitroaminoweichmacher ein 1:1 Gemisch von N-Ethyl- und N- Methylnitratoethylnitroamin (EtNENA bzw. MeNENA) oder N-n-Butyl- N-nitratoethylnitroamin (BuNENA) oder N, N'-Dinitratoethylnitroamin (DINA) geeignet ist.A 1: 1 mixture of bisdinitropropyl formal / acetal (BDNPF / A) may be mentioned as an example of a nitro softener, while a 1: 1 mixture of N-ethyl and N-methylnitratoethylnitroamine (EtNENA or MeNENA) or Nn-butyl- N-nitratoethylnitroamine (BuNENA) or N, N'-dinitratoethylnitroamine (DINA) is suitable.
Als Azidoweichmacher kommen insbesondere kurzkettige, bisazidoterminierte GAP-Oligomere (GAP-A) oder das 1, 5-Diazido-3-nitroaminopentan (DANPE) in Frage.In particular, short-chain, bisazido-terminated GAP oligomers (GAP-A) or 1, 5-diazido-3-nitroaminopentane (DANPE) come into consideration as azide softeners.
Je nach Art, Verträglichkeit und Energie der Binderkomponenten beträgt das Verhältnis Polymer/Weichmacher 1:3 bis 20:1 Massen-%. Selbstverständlich können die Binderpolymere auch in reiner Form verwendet werden.Depending on the type, compatibility and energy of the binder components, the polymer / plasticizer ratio is 1: 3 to 20: 1 mass%. The binder polymers can of course also be used in pure form.
Dem phasenstabilisierten Ammoniumnitrat werden vorzugsweise 0,1 bis 1 Massen-% seiner Fraktion Antibackmittel, z.B. ultrafeines (Korngröße etwa 0,02 µm) Silicagel, Natriumlaurylsulfonat, Tricalciumphosphat oder andere Tenside zugesetzt.0.1 to 1% by mass of its anti-caking agent fraction, for example ultrafine (grain size about 0.02 μm) silica gel, sodium lauryl sulfonate, tricalcium phosphate or other surfactants are preferably added to the phase-stabilized ammonium nitrate.
Erfindungsgemäß lassen sich die Vanadium/Molybdänoxid-Abbrandmoderatoren in idealer Weise mit Kupfersalzen, -oxiden, oder -komplexen verbinden, was eine weitere Steigerung der Abbrandgeschwindigkeit vor allem im niedrigen Druckbereich, verbunden mit einer weiteren Senkung des Druckexponenten mit sich bringt.According to the invention, the vanadium / molybdenum oxide combustion moderators can be ideally combined with copper salts, oxides or complexes, which brings about a further increase in the combustion rate, especially in the low pressure range, combined with a further reduction in the pressure exponent.
Besonders günstig wirkt sich deshalb der Einsatz des mit Kupferoxid stabilisierten Ammoniumnitrats in Kombination mit Vanadium/Molybdänoxiden auf das Abbrandverhalten aus. Bei dem erfindungsgemäß vorgesehenen Zusatz von 2 bis 7 Massen-% der phasenstabilisierenden CuO ergeben sich deutlich höhere Abbrandgeschwindigkeiten und niedrige Druckexponenten. Dieses günstige Abbrandverhalten ist vor allem Festtreibstoffen festzustellen, deren Binder bis zu 50% Azidoverbindungen in Gestalt energetischer Polymere und/oder Weichmacher enthält.The use of ammonium nitrate stabilized with copper oxide in combination with vanadium / molybdenum oxides therefore has a particularly favorable effect on the combustion behavior. The addition of 2 to 7% by mass of the phase-stabilizing CuO provided according to the invention results in significantly higher burn-up rates and low pressure exponents. This favorable combustion behavior can be seen above all in solid fuels whose binders contain up to 50% azido compounds in the form of energetic polymers and / or plasticizers.
In weiterhin bevorzugter Ausgestaltung ist vorgesehen, daß die Abbrandmoderatoren eine Korngröße im Bereich von 1 bis 60 µm, vorzugsweise 1 bis 10 µm, und eine hohe innere Oberfläche von 5 bis 100m2/g, vorzugsweise 20 bis 60m2/g aufweisen.In a further preferred embodiment it is provided that the combustion moderators have a grain size in the range from 1 to 60 μm, preferably 1 to 10 μm, and a high internal surface area of 5 to 100 m 2 / g, preferably 20 to 60 m 2 / g.
Metallfreie Festtreibstoffe der beschriebenen Art eignen sich durch ihren Energieinhalt, ihren raucharmen, salzsäurefreien Abbrand und ihre vergleichsweise geringe, mechanische und detonative Empfindlichkeit für den Einsatz in Raketenmotoren, während energieärmere Formulierungen mit höherem Binderanteil für die Anwendung als Gasgeneratortreibsätze geeignet sind.Metal-free solid fuels of the type described are suitable for use in rocket engines due to their energy content, their low-smoke, hydrochloric acid-free combustion and their comparatively low, mechanical and detonative sensitivity, while lower-energy formulations with a higher proportion of binder are suitable for use as gas generator propellants.
Beim Einsatz der beschriebenen Festtreibstoffe in Raketenmotoren werden als weitere Additive mit Vorteil hochschmelzende Metallkarbide oder -nitrate, vorzugsweise Silicium- und/oder Zirkonkarbid mit einer Konzentration von 0,1 bis 1 Massen-% zugesetzt. Diese Additive sorgen in der erfindungsgemäßen Formulierung ohne Metallzusatz für die Unterdrückung instabiler Oszillationen im Abbrandverhalten.When the solid fuels described are used in rocket engines, high-melting metal carbides or nitrates, preferably silicon and / or zirconium carbide, with a concentration of 0.1 to 1 mass% are advantageously added as further additives. In the formulation according to the invention without metal addition, these additives suppress unstable oscillations in the combustion behavior.
Tabelle 1 zeigt in ihrem oberen Teil fünf verschiedene Formulierungen von Ammoniumnitrat, das mit Kupferoxid bzw. Zinkoxid phasenstabilisiert ist (PSAN). Im unteren Teil der Tabelle ist zu den einzelnen Formulierungen die Abbrandgeschwindigkeit r (mm/s) bei 20° C und bei drei verschiedenen Brennkammerdrucken angegeben. Darunter findet sich der Druckexponent n für verschiedene, in Klammern angegebene Druckbereiche.The upper part of Table 1 shows five different formulations of ammonium nitrate, which is phase-stabilized with copper oxide or zinc oxide (PSAN). The burning rate r (mm / s) at 20 ° C and at three different combustion chamber pressures is given in the lower part of the table for the individual formulations. Below this is the pressure exponent n for various pressure ranges given in brackets.
Der Vergleich der Formulierung Cu1 und Cu2 zeigt, wie mit kleiner werdender Korngröße die Wirkung des Abbrandmoderators im Sinne einer Steigerung der Abbrandgeschwindigkeit und einer Senkung des Druckexponenten deutlich verbessert wird. Hingegen verschlechtern sich die Verhältnisse, wenn, wie bei Cu3, der Anteil energetischer Nitratesterweichmacher den GAP-Anteil des Binders übersteigt. Dies ist insbesondere beim Druckexponenten auffällig. Cu4 veranschaulicht die abbrandsteigernde Wirkung von zusätzlich zugegebenem Kupferoxid. Schließlich zeigt Zn1 bei gleicher Korngröße des PSAN, daß mit Vanadium/Molybdänoxid Abbrandmoderatoren auch ohne Kupferverbindungen Druckexponenten n < 0,6 und Abbrandgeschwindigkeiten r > 8 mm/s bei 10 MPa Brennkammerdruck erreicht werden können.The comparison of the formulation Cu1 and Cu2 shows how, with smaller grain size, the effect of the combustion moderator in the sense of an increase in the combustion speed and a reduction in the pressure exponent is significantly improved. On the other hand, the situation deteriorates if, as with Cu3, the proportion of energetic nitrate ester plasticizers exceeds the GAP proportion of the binder. This is particularly noticeable with pressure exponents. Cu4 illustrates the burn-increasing effect of additionally added copper oxide. Finally, with the same grain size of the PSAN, Zn1 shows that with vanadium / molybdenum oxide combustion moderators, even without copper compounds, pressure exponents n <0.6 and combustion speeds r> 8 mm / s can be achieved at 10 MPa combustion chamber pressure.
In dem Diagramm gemäß Abbildung 1 ist das Abbrandverhalten der Formulierungen Cu1, Cu2 und Zn1 als Funktion
Im Diagramm gemäß Abbildung 2 sind die gleichen Abhängigkeiten für Cu3 mit hohem und Cu4 mit niedrigem Anteil an Nitratester-Weichmacher gezeigt; die günstigeren Werte bei Cu4 sowohl hinsichtlich Abbrandgeschwindigkeit als auch Druckexponent sind augenfällig.
Claims (23)
- Solid propellant for rocket drives or gas generators comprising 35 to 80% by mass of ammonium nitrate (AN) with a median granular size of 5 to 200 µm, which is phase-stabilised by chemical conversion with CuO or ZnO (PSAN), 15 to 50% by mass of a binder system consisting of a binding polymer and an energy-rich plasticiser and 0.2 to 5.0% by mass of a calcine moderator of vanadium oxide/molybdenum oxide as an oxide mixture or mixed oxide.
- Solid propellant according to claim 1, in which the proportion of phase-stabilised CuO or ZnO comes to 1 to 7% by mass of the ammonium nitrate fraction and is incorporated in the crystal matrix of AN by chemical reaction with the AN melt, releasing water.
- Solid propellant according to claim 1 or 2, with a further proportion of 1 to 20% by mass of energy-rich nitramines, selected from hexogen and octogen, with a median granular size of 1 to 20 µm.
- Solid propellant according to one of claims 1 to 3, with a further proportion of 0.5 to 20% by mass of metal selected from aluminium, magnesium and boron, with a granular size of 0,1 to 50 µm.
- Solid propellant according to one of claims 1 to 4, with a further proportion of 0.4 to 2% by mass of a stabiliser acting as a catching agent for nitrogen oxide and acid, comprising diphenylamine, 2-nitrodiphenylamine or N-methylnitoraniline or a combination of the same.
- Solid propellant according to one of claims 1 to 5, with an addition of carbon black or graphite with 5 to 50% by mass of the fraction of the calcine moderator.
- Solid propellant according to one of claims 1 to 6, in which the binding polymer is an isocyanate-hardening bi-or tri-functional hydroxy-substituted polyester or polyether prepolymer.
- Solid propellant according to one of claims 1 to 6, in which the binding polymer is an energy-rich polymer.
- Solid propellant according to claim 8, in which the energy-rich polymer is an isocyanate-hardening bi- or tri-functional hydroxy-substituted glycidylazidopolymer (GAP).
- Solid propellant according to one of claims 1 to 9, in which the energy-rich plasticiser is selected from the group of chemically stable nitrate esters, nitro-, nitroamino- or azido plasticisers.
- Solid propellant according to claim 10, in which the nitrate ester is a trimethylolethane trinitrate (TMETN), butane trioltrinitrate (BTTN) or diethylene glycol dinitrate (DEGDN).
- Solid propellant according to claim 10, in which the nitroplasticiser is a 1:1 mixture of bisdinitropropylformal/bisdinitropropylacetal (BDNPF/BDNPA).
- Solid propellant according to claim 10, in which the nitroamino plasticiser is a 1:1 mixture of N-ethyl and N-methylnitratoethylnitroamine (EtNENA and MeNENA) or N-n-butyl-N-nitratoethyl nitroamine (BuNENA) or N, N' dinitratoethyl nitroamine (DINA).
- Solid propellant according to claim 10, in which the acidoplasticer comprises short-chain GAP-oligomers (GAP-A) with terminal bisazido groups, or comprising 1, 5 diazido-3-nitroamino pentane (DANPE).
- Solid propellant according to one of claims 1 to 14, characterised in that the binding polymers and the plasticisers are present in a ratio of 1:3 to 3:1% by plasticisers are present in a ratio of 1:3 to 3:1% by mass in dependence on the type, compatibility and energy content in the binder system.
- Solid propellant according to one of claims 1 to 15, the median granular size of the PSAN lying between 5 and 80 µm.
- Solid propellant according to one of claims 1 to 16, there being added to the PSAN 0.1 to 1% by mass of its fraction of ultrafine silica gel (granular size about 0.2 µm), sodium lauryl sulphonate, tricalcium phosphate or other tensides as anticaking agents.
- Solid propellant according to one of claims 1 to 17, in which the vanadium oxide/molybdenum oxide-calcin moderators are used in conjunction with copper salts, oxides or complexes.
- Solid propellant according to one of claims 1 to 18, the calcine moderators containing mixed oxides of molybdenum of the oxidation stage +VI and vanadium of the oxidation stages +IV and +V.
- Solid propellant according to one of claims 1 to 19, the calcine moderators having as carrier material chromium (III) - or titanium (IV) - oxides.
- Solid propellant according to one of claims 1 to 20, characterised in that the calcine moderators have a granular size of 1 to 60 µm, preferably 1 to 10 µm and a large internal surface of 5 to 100m2/g, preferably 20 to 60m2/g.
- Solid propellant according to one of claims 1 to 21, characterised in that when used in rocket motors, there is added thereto 0.1 to 1% by mass of high-melting metal carbides or nitrides as additives for suppressing an unstable, oscillating burning behaviour.
- Solid propellant according to claim 22, characterised in that the additives are silicon- and/or zirconium carbide.
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DE4435523A DE4435523C1 (en) | 1994-10-05 | 1994-10-05 | Solid fuel based on phase-stabilized ammonium nitrate |
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EP (1) | EP0705808B1 (en) |
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AU2022223569B2 (en) | 2021-02-16 | 2023-09-14 | Spectre Materials Sciences, Inc. | Primer for firearms and other munitions |
CN113376208B (en) * | 2021-06-09 | 2023-04-25 | 四川弘博新材科技股份有限公司 | Application of molybdenum in improving reactivity of boron-containing energetic material |
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US2995429A (en) * | 1956-03-26 | 1961-08-08 | Phillips Petroleum Co | Solid composite rubber base ammonium nitrate propellant cured with metal oxide |
US2949352A (en) * | 1956-10-01 | 1960-08-16 | North American Aviation Inc | Propellant composition |
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US3822154A (en) * | 1962-10-01 | 1974-07-02 | Aerojet General Co | Suppression of unstable burning using finely divided metal oxides |
US3340111A (en) * | 1963-03-26 | 1967-09-05 | Aerojet General Co | Solid propellant catalyzed with copper-chromium complex |
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DE2644211B2 (en) * | 1976-09-30 | 1978-12-07 | Bayern-Chemie Gesellschaft Fuer Flugchemische Antriebe Mbh, 8261 Aschau | Composite solid propellant |
US4158583A (en) * | 1977-12-16 | 1979-06-19 | Nasa | High performance ammonium nitrate propellant |
US4411717A (en) * | 1983-02-02 | 1983-10-25 | The United States Of America As Represented By The Secretary Of The Air Force | Solid rocket propellants comprising guignet's green pigment |
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DE3704305A1 (en) * | 1987-02-12 | 1988-08-25 | Bayern Chemie Gmbh Flugchemie | COMPOSITE SOLID FUEL |
US5074938A (en) * | 1990-05-25 | 1991-12-24 | Thiokol Corporation | Low pressure exponent propellants containing boron |
US5076868A (en) * | 1990-06-01 | 1991-12-31 | Thiokol Corporation | High performance, low cost solid propellant compositions producing halogen free exhaust |
US5271778A (en) * | 1991-12-27 | 1993-12-21 | Hercules Incorporated | Chlorine-free solid rocket propellant for space boosters |
FR2692257B1 (en) * | 1992-06-12 | 1995-05-05 | Divbag Snc | Pyrotechnic composition generating non-toxic hot gases and its use in a device for protecting the occupants of a motor vehicle. |
EP0584899A3 (en) * | 1992-08-05 | 1995-08-02 | Morton Int Inc | Additive approach to ballistic and slag melting point control of azide-based gas generant compositions. |
US5292387A (en) * | 1993-01-28 | 1994-03-08 | Thiokol Corporation | Phase-stabilized ammonium nitrate and method of making same |
-
1994
- 1994-10-05 DE DE4435523A patent/DE4435523C1/en not_active Expired - Fee Related
-
1995
- 1995-08-18 DE DE59500909T patent/DE59500909D1/en not_active Expired - Fee Related
- 1995-08-18 ES ES95112989T patent/ES2110285T3/en not_active Expired - Lifetime
- 1995-08-18 EP EP95112989A patent/EP0705808B1/en not_active Expired - Lifetime
- 1995-09-29 US US08/536,640 patent/US5589661A/en not_active Expired - Fee Related
- 1995-10-03 NO NO953922A patent/NO303983B1/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101468935B (en) * | 2007-12-24 | 2012-05-09 | 南京理工大学 | Preparation of polymer modified phase stable ammonium nitrate |
Also Published As
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US5589661A (en) | 1996-12-31 |
NO303983B1 (en) | 1998-10-05 |
NO953922D0 (en) | 1995-10-03 |
DE4435523C1 (en) | 1996-06-05 |
DE59500909D1 (en) | 1997-12-04 |
EP0705808A1 (en) | 1996-04-10 |
ES2110285T3 (en) | 1998-02-01 |
NO953922L (en) | 1996-04-09 |
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