EP0705808B1 - Propellant based on phase-stabilized ammonium nitrate - Google Patents

Propellant based on phase-stabilized ammonium nitrate Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
solid propellant
propellant according
mass
oxide
energy
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
Application number
EP95112989A
Other languages
German (de)
French (fr)
Other versions
EP0705808A1 (en
Inventor
Klaus Dr. Menke
Jutta Dr. Böhnlein-Mauss
Helmut Schmid
Klaus Martin Dr. Bucerius
Walther Dr. Engel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP0705808A1 publication Critical patent/EP0705808A1/en
Application granted granted Critical
Publication of EP0705808B1 publication Critical patent/EP0705808B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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.

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.

Beispielexample

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 lgr = f(lgp)

Figure imgb0001
für einen Treibstoff mit 68% Feststoffanteil, ein Ammoniumnitrat mit einem Korngrößenverhältnis 160/55 µm von 4:6 und einem Bindersystem GAP (Glycidylazidopolymer/Pl (Platicizer-Weichmacher) aufgezeigt. Hier wird einerseits deutlich der die Abbrandgeschwindigkeit begünstigende Einfluß der kleineren Korngröße (Cu2 gegenüber Cu1) bei gleichzeitiger Absenkung des Druckexponenten von n = 0,56 auf n = 0,49. Ferner ist bei Zn1 mit einem Druckexponenten, der immer noch unter 0,6 liegt, eine gleichwohl noch passable Abbrandgeschwindigkeit ersichtlich.In the diagram in Figure 1, the burning behavior of the formulations Cu1, Cu2 and Zn1 is a function lgr = f (lgp)
Figure imgb0001
 for a fuel with 68% solids, an ammonium nitrate with a grain size ratio of 160/55 µm of 4: 6 and a binder system GAP (glycidyl azidopolymer / Pl (plasticizer plasticizer). On the one hand the influence of the smaller grain size (Cu2 compared to Cu1) with simultaneous lowering of the pressure exponent from n = 0.56 to n = 0.49 Furthermore, with Zn1 with a pressure exponent that is still below 0.6, a burn rate that is still passable can still be seen.

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. Tabelle 1 Treibstofformulierungen und Abbrandeigenschaften Cu1 Cu2 Cu3 Cu4 Zn1 Cu PSAN 3% CuO 160µm 42 22 22 22 - Cu PSAN 3% CuO 55µm 18 33 33 33 - Zn PSAN 3% ZnO 160µm - - - - 22 Zn PSAN 3% ZnO 55µm - - - - 33 RDX 5 µm 10 10 10 10 10 GAP/N100 16,5 16 10 16 16 TMETN 10 15,5 7,5 15,5 15,5 BTTN - - 14 - - DPA 0,5 0,5 0,5 0,5 0,5 Cu-oxid - - - 1 - V/Mo-oxid 2,5 2,5 2,5 1,5 2,5 Ruß 0,5 0,5 0,5 0,5 0,5 Abbrandgeschw. bei 20°C (mm/s) r2MPA 2,8 3,5 3,4 4,3 2,7 r7MPa 7,6 8,3 7,7 8,6 6,9 r10MPa 9,2 9,6 9,6 10,0 8,3 Druckexponenten n (Bereich MPa) 0,57 (4-25) 0,48 (4-25) 0,62 (4-18) 0,51 (4-18) 0,59 (4-25) 0,95 (2-4) 0,80 (2-4) 0,90 (2-4) The diagram in Figure 2 shows the same dependencies for Cu3 with a high and Cu4 with a low proportion of nitrate ester plasticizer; the more favorable values for Cu4 in terms of both the rate of combustion and the pressure exponent are obvious. Table 1 Fuel formulations and burning properties Cu1 Cu2 Cu3 Cu4 Zn1 Cu PSAN 3% CuO 160µm 42 22 22 22 - Cu PSAN 3% CuO 55µm 18th 33 33 33 - Zn PSAN 3% ZnO 160µm - - - - 22 Zn PSAN 3% ZnO 55µm - - - - 33 RDX 5 µm 10th 10th 10th 10th 10th GAP / N100 16.5 16 10th 16 16 TMETN 10th 15.5 7.5 15.5 15.5 BTTN - - 14 - - DPA 0.5 0.5 0.5 0.5 0.5 Cu oxide - - - 1 - V / Mo oxide 2.5 2.5 2.5 1.5 2.5 soot 0.5 0.5 0.5 0.5 0.5 Burn rate at 20 ° C (mm / s) r 2MPA 2.8 3.5 3.4 4.3 2.7 r 7MPa 7.6 8.3 7.7 8.6 6.9 r 10MPa 9.2 9.6 9.6 10.0 8.3 Pressure exponent n (range MPa) 0.57 (4-25) 0.48 (4-25) 0.62 (4-18) 0.51 (4-18) 0.59 (4-25) 0.95 (2-4) 0.80 (2-4) 0.90 (2-4)

Claims (23)

  1. 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.
  2. 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.
  3. 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.
  4. 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.
  5. 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.
  6. 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.
  7. 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.
  8. Solid propellant according to one of claims 1 to 6, in which the binding polymer is an energy-rich polymer.
  9. Solid propellant according to claim 8, in which the energy-rich polymer is an isocyanate-hardening bi- or tri-functional hydroxy-substituted glycidylazidopolymer (GAP).
  10. 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.
  11. Solid propellant according to claim 10, in which the nitrate ester is a trimethylolethane trinitrate (TMETN), butane trioltrinitrate (BTTN) or diethylene glycol dinitrate (DEGDN).
  12. Solid propellant according to claim 10, in which the nitroplasticiser is a 1:1 mixture of bisdinitropropylformal/bisdinitropropylacetal (BDNPF/BDNPA).
  13. 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).
  14. 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).
  15. 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.
  16. Solid propellant according to one of claims 1 to 15, the median granular size of the PSAN lying between 5 and 80 µm.
  17. 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.
  18. 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.
  19. 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.
  20. Solid propellant according to one of claims 1 to 19, the calcine moderators having as carrier material chromium (III) - or titanium (IV) - oxides.
  21. 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.
  22. 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.
  23. Solid propellant according to claim 22, characterised in that the additives are silicon- and/or zirconium carbide.
EP95112989A 1994-10-05 1995-08-18 Propellant based on phase-stabilized ammonium nitrate Expired - Lifetime EP0705808B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4435523A DE4435523C1 (en) 1994-10-05 1994-10-05 Solid fuel based on phase-stabilized ammonium nitrate
DE4435523 1994-10-05

Publications (2)

Publication Number Publication Date
EP0705808A1 EP0705808A1 (en) 1996-04-10
EP0705808B1 true EP0705808B1 (en) 1997-10-29

Family

ID=6529972

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95112989A Expired - Lifetime EP0705808B1 (en) 1994-10-05 1995-08-18 Propellant based on phase-stabilized ammonium nitrate

Country Status (5)

Country Link
US (1) US5589661A (en)
EP (1) EP0705808B1 (en)
DE (2) DE4435523C1 (en)
ES (1) ES2110285T3 (en)
NO (1) NO303983B1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
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

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19581542T1 (en) 1994-12-21 1999-04-01 Daicel Chem Gas generating composition
DE19712820A1 (en) * 1997-03-26 1998-10-01 Basf Ag Burning moderators for gas-generating mixtures
DE19742203A1 (en) * 1997-09-24 1999-03-25 Trw Airbag Sys Gmbh Particle-free gas-generating mixture
US6019861A (en) * 1997-10-07 2000-02-01 Breed Automotive Technology, Inc. Gas generating compositions containing phase stabilized ammonium nitrate
US6143103A (en) * 1998-01-27 2000-11-07 Trw Inc. Gas generating material for vehicle occupant protection device
AU2573399A (en) * 1998-02-03 1999-08-16 Talley Defense Systems, Inc. Very thin inflator and method of making and using same
US6143104A (en) * 1998-02-20 2000-11-07 Trw Inc. Cool burning gas generating composition
US6231702B1 (en) * 1998-02-20 2001-05-15 Trw Inc. Cool burning ammonium nitrate based gas generating composition
US6136113A (en) * 1998-08-07 2000-10-24 Atlantic Research Corporation Gas generating composition
US6066213A (en) * 1998-09-18 2000-05-23 Atlantic Research Corporation Minimum smoke propellant composition
US6126763A (en) * 1998-12-01 2000-10-03 Atlantic Research Corporation Minimum smoke propellant composition
US6103030A (en) 1998-12-28 2000-08-15 Autoliv Asp, Inc. Burn rate-enhanced high gas yield non-azide gas generants
US6592691B2 (en) * 1999-05-06 2003-07-15 Autoliv Asp, Inc. Gas generant compositions containing copper ethylenediamine dinitrate
US6149746A (en) * 1999-08-06 2000-11-21 Trw Inc. Ammonium nitrate gas generating composition
WO2001025169A1 (en) 1999-10-06 2001-04-12 Nof Corporation Gas generator composition
US6136112A (en) * 1999-10-26 2000-10-24 Trw Inc. Smokeless gas generating composition for an inflatable vehicle occupant protection device
US6156137A (en) * 1999-11-05 2000-12-05 Atlantic Research Corporation Gas generative compositions
US6372191B1 (en) 1999-12-03 2002-04-16 Autoliv Asp, Inc. Phase stabilized ammonium nitrate and method of making the same
US6224697B1 (en) 1999-12-03 2001-05-01 Autoliv Development Ab Gas generant manufacture
US6802533B1 (en) * 2000-04-19 2004-10-12 Trw Inc. Gas generating material for vehicle occupant protection device
US6436211B1 (en) 2000-07-18 2002-08-20 Autoliv Asp, Inc. Gas generant manufacture
US6652682B1 (en) * 2001-10-17 2003-11-25 The United States Of America As Represented By The Secretary Of The Navy Propellant composition comprising nano-sized boron particles
DE10224859A1 (en) * 2002-06-05 2003-12-24 Fraunhofer Ges Forschung Production of free-running perchlorate, used as propellant, explosive and oxidant, e.g. in solid propellant or pyrotechnics, involves mixing with anticaking agent, transfer to inert carrier gas stream and hammer milling
US6872265B2 (en) 2003-01-30 2005-03-29 Autoliv Asp, Inc. Phase-stabilized ammonium nitrate
CN101642709B (en) * 2008-08-04 2011-07-20 深圳大学 CuO-PbO/carbon nano-tube composite powder and preparation method thereof
CN103191748B (en) * 2013-04-11 2014-10-15 北京科技大学 Preparation method of sisal hemp-shaped CuO-ZnO composite oxide
RU2580735C2 (en) * 2014-09-09 2016-04-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Алтайский государственный технический университет им. И.И. Ползунова" (АлтГТУ) Solid fuel metallised composition based on ammonium nitrate
WO2018186923A2 (en) 2017-01-16 2018-10-11 Spectre Enterprises, Inc. Propellant
US11112222B2 (en) 2019-01-21 2021-09-07 Spectre Materials Sciences, Inc. Propellant with pattern-controlled burn rate
CN114539012A (en) * 2020-11-25 2022-05-27 北京理工大学 Composite energetic plasticizer suitable for GAP-based casting explosive and propellant and preparation method and application thereof
US11650037B2 (en) 2021-02-16 2023-05-16 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

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US3027282A (en) * 1958-12-29 1962-03-27 Phillips Petroleum Co Composite propellants containing modifying agents
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
US3609115A (en) * 1963-09-30 1971-09-28 North American Rockwell Propellant binder
US3629019A (en) * 1964-08-11 1971-12-21 Aerojet General Co Solid propellant composition containing polyesters and an inorganic oxide burning rate catalyst
US4318270A (en) * 1968-04-11 1982-03-09 The United States Of America As Represented By The Secretary Of The Navy Additives for suppressing the radar attenuation of rocket propellant exhaust plumes
US4166045A (en) * 1973-05-02 1979-08-28 United Technologies Corporation Purification of combustion catalysts and solid propellant compositions containing the same
US3924405A (en) * 1973-06-07 1975-12-09 Aerojet General Co Solid propellants with stability enhanced additives of particulate refractory carbides or oxides
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
DE3523953A1 (en) * 1985-07-04 1987-01-15 Fraunhofer Ges Forschung METHOD AND DEVICE FOR PRODUCING SOLID FUELS
DE3642850C1 (en) * 1986-12-16 1988-02-18 Fraunhofer Ges Forschung Process for the production of particulate ammonium nitrate for solid fuels or explosives
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

Cited By (1)

* Cited by examiner, † Cited by third party
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

Publication number Publication date
US5589661A (en) 1996-12-31
NO953922D0 (en) 1995-10-03
NO303983B1 (en) 1998-10-05
DE59500909D1 (en) 1997-12-04
EP0705808A1 (en) 1996-04-10
NO953922L (en) 1996-04-09
ES2110285T3 (en) 1998-02-01
DE4435523C1 (en) 1996-06-05

Similar Documents

Publication Publication Date Title
EP0705808B1 (en) Propellant based on phase-stabilized ammonium nitrate
EP0705809B1 (en) Propelland based on phase-stabilized ammonium nitrate
DE3835854C2 (en)
DE60003429T2 (en) FUEL COMPOSITION CONTAINING DINITRAMIDE
DE3131445A1 (en) IMPROVED DRIVING AGENTS CONTAINING TRIAMINOGUANIDINE NITRATE
DE4002157A1 (en) Thermoplastic bonded energetic material, used in e.g. explosive welding, comprises polymeric binder comprising intimate mixture of copolymer(s) of ethylene and vinyl acetate and copolymer(s) of butadiene and acrylonitrile
WO2000022291A2 (en) Castable double base solid rocket propellant containing ballistic modifier pasted in an inert polymer
DE2820969C1 (en) Solid composite fuel with stable combustion
DE2263860C3 (en) Solid projectile propellant charge
EP1932817A1 (en) Nitratoethyl nitroamine propellant for automobile safety systems
DE2820783C1 (en) Solid composite fuel with stable combustion
DE2900020A1 (en) MULTI-BASED DRIVE CARGO POWDER
DE10027413B4 (en) A method of making a blowing agent composition using a dry blending method
EP3939952A1 (en) Fast burning solid propellant comprising an oxidizer, an energetic binder and a metallic burn-off modifier and method for its preparation
DE1446919A1 (en) Powder for propellant charges, ignition charges, additional charges or the like.
DE2329558A1 (en) Castable non-hygroscopic gas-generating propellant - with good mechanical props and burning with low flame temps
DE69921816T2 (en) HIGH PERFORMANCE FUEL ON THE BASIS OF HYDRAZINE NITROFORM
DE2754855C2 (en) Process for improving the pressure dependency of the combustion behavior of solid propellants or gun propellants and use of the propellants produced by the process
DE102004004529B4 (en) Plasticizer for a propellant with ambient temperature independent burnup
DE3244444C1 (en) Dibasic propellant blocks with increased nitramine content and process for their preparation
DE3316676A1 (en) FUEL COMPOSITIONS
DE102011100113B4 (en) Gas generator fuel composition, process for its preparation and its use
US3996080A (en) Ballistic modifiers
DE4026468C2 (en) Solid fuels with a binder of non-crystalline polyether / high-energy plasticizer
DE3811840A1 (en) AGING-BONUS BASED POWDER, METHOD FOR THE PRODUCTION THEREOF, AND ITS USE IN GAS GENERATORS

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB NL

17P Request for examination filed

Effective date: 19960725

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19961106

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB NL

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19971031

REF Corresponds to:

Ref document number: 59500909

Country of ref document: DE

Date of ref document: 19971204

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2110285

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050803

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20050818

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050819

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20050829

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070301

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060818

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20070301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070430

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20060819

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060819

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20071029

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090303