EP0705809A1 - Propelland based on phase-stabilized ammonium nitrate - Google Patents
Propelland based on phase-stabilized ammonium nitrate Download PDFInfo
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- EP0705809A1 EP0705809A1 EP95112990A EP95112990A EP0705809A1 EP 0705809 A1 EP0705809 A1 EP 0705809A1 EP 95112990 A EP95112990 A EP 95112990A EP 95112990 A EP95112990 A EP 95112990A EP 0705809 A1 EP0705809 A1 EP 0705809A1
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- 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
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- 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
Definitions
- the invention relates to a solid fuel for rocket engines or gas generators, which contains ammonium nitrate (AN) in pure or phase-stabilized form (PSAN) as an oxidizer.
- AN ammonium nitrate
- PSAN phase-stabilized form
- 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.
- the combustion 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 object of the invention is to improve the combustion behavior of solid fuels on the basis of pure and phase-stabilized ammonium nitrate.
- such a solid fuel consists of 35 to 80% by mass ammonium nitrate (AN) in pure form or phase-stabilized form (PSAN) with nickel oxide, potassium or cesium nitrate with an average grain size of 5 to 200 ⁇ m, 15 to 50% by mass of a binder system from one Binder polymer and a high-energy plasticizer as well as 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 form
- 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 3 ⁇ 4 0.6, in the favorable case n 3 ⁇ 4 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 distinguished by the fact that they contain pure AN as the oxidizer or phase-stabilized ammonium nitrate reacted with nickel oxide, potassium or cesium nitrate as the oxidizer, the nickel oxides preferably containing 1 to 7% by mass, potassium or cesium nitrate containing 3 to 15 % By mass are used. 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 the additives with the melt of the pure ammonium nitrate with elimination of water.
- AN is preferably used in pure form with a water content below 0.2% by mass or NiO-stabilized PSAN, while PSAN stabilized with potassium or cesium nitrate brings with it somewhat higher smoke proportions.
- the combustion behavior is significantly influenced by the grain size of the AN or PSAN.
- 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 or PSAN fraction predominantly in smaller ones Grain size from 10 to 80 ⁇ m and less in average grain size from 100 to 160 ⁇ m is available.
- the solid propellant according to the invention can also contain high-energy substances, in particular nitramines, such as hexogen (RDX) or octogen (HMX) with an average particle size of 2 to 200 ⁇ m with a proportion of 1 to 4% by mass.
- nitramines such as hexogen (RDX) or octogen (HMX) with an average particle size of 2 to 200 ⁇ m with a proportion of 1 to 4% 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 ester, with small amounts in the range of 0.5% by mass of the magnesium oxide acting in the same sense.
- combustion moderators made from vanadium / molybdenum oxide as oxide mixture or mixed oxide used according to the invention with 0.2 to 5.0 mass% are advantageously added with carbon black or graphite in a fraction of 5 to 20 mass% of the fraction of the combustion moderator.
- binder system consisting of a binder polymer and a high-energy plasticizer.
- the binder polymer itself can be inert, it preferably being an isocyanate-curing, bifunctional or trifunctional hydroxyl-substituted polyester or polyether prepolymer.
- 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
- nitro plasticizer is a 1: 1 mixture of bisdinitropropyl formal / acetal (BDNPF / A), while a nitro amino plasticizer is a 1: 1 mixture of N-ethyl and N-methylnitratoethylnitroamine (EtNENA, MeNENA) or Nn-butyl-N -nitratoethylnitroamine (BuNENA) or N, N'-dinitratoethylnitroamine (DINA) is suitable.
- EtNENA N-ethyl and N-methylnitratoethylnitroamine
- BuNENA Nn-butyl-N -nitratoethylnitroamine
- DINA N, N'-dinitratoethylnitroamine
- GAP-A bisazido-terminated GAP oligomers
- DANPE 5-diazido-3-nitroaminopentane
- the ratio polymer / plasticizer is 1: 3 to 20: 1 mass%.
- the binder polymers can of course also be used in pure form.
- the purer or phase stabilized ammonium nitrate is preferably 0.1 to 1% by mass of its anti-caking agent fraction, e.g. ultra-fine (grain size about 0.02 ⁇ m) silica gel, sodium lauryl sulfonate, tricalcium phosphate or other surfactants are added.
- its anti-caking agent fraction e.g. ultra-fine (grain size about 0.02 ⁇ m) silica gel, sodium lauryl sulfonate, tricalcium phosphate or other surfactants are added.
- the vanadium / molybdenum oxide combustion moderators can be ideally combined with nickel and copper salts, oxides or complexes, which leads to a further increase in the combustion rate.
- the combustion moderators preferably consist of mixed oxides in which molybdenum is present in the + VI and + V oxidation states and vanadium in the + IV and + V oxidation states.
- Exemplary compositions of the mixed oxides are V6Mo4O25 and V6Mo15 O25O60.
- the mixed oxides can furthermore contain chromium (III) and titanium (IV) oxides as the inactive carrier material or one which also participates in the reaction.
- 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.
- the burning rate in the low pressure range can be increased further compared to coarser grain and the pressure exponent can be further reduced.
- the solid propellants according to the invention experience an advantageous further development in that high-melting Metal carbides or nitrides, preferably silicon and zirconium carbide in the concentration range from 0.1 to 1 mass% are added. Above all, this suppresses an unstable, oscillating combustion behavior when used in rocket engines. This is particularly important for low-smoke burning fuels without the addition of metal.
- Solid fuels of the type described in particular with oxidizers in the form of pure AN or Ni-PSAN, are suitable due to their energy content, their low-smoke, hydrochloric acid-free combustion and their comparatively low, mechanical and detonative sensitivity for use in rocket engines, while lower-energy formulations with a higher binder content are suitable for use as gas generator propellants.
- Table 1 shows nine different formulations with pure ammonium nitrate and a PSAN phase-stabilized with 3% nickel oxide.
- 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.
- AN3 to AN8 Due to the high plasticizer content, AN3 to AN8 have high specific impulses of 234s for AN6 and AN8 and 237s for AN3, AN4 and AN5 with a relaxation ratio of 70: 1.
- the synergistic effect of copper compounds and V / Mo oxide combustion moderators has proven to be particularly favorable. Copper phthalocyanate has proven to be the most favorable in the combination of increase in the rate of combustion, reduction in the pressure exponent and acceptable stability properties.
- the burning behavior of the formulation AN9 shows that the nickel diaminodinitrate as phase stabilizer in the AN also has a favorable effect on the burning behavior. This is also observed with the addition of nickel phthalocyanate in the AN8 formulation. The addition of RDX also increases the burning rate without, however, positively influencing the pressure exponent.
- Table 2 shows with the examples AN10, AN11 and AN12 AN / GAP fuel formulations in which the combustion moderator is contained in different grain sizes and grain distributions with otherwise the same composition.
- the lower part of the table clearly shows the increase in the burn-off rate achieved with the grain becoming smaller, while at the same time lowering the pressure exponent.
- AN13 shows the burning behavior when formulated with an azido softener
- AN14 is a formulation with the addition of zirconium carbide, with the help of which combustion oscillations are suppressed when the fuel is used in rocket engines.
- Figure 3 shows effective combustion control even with a high nitrate ester content in the fuel without RDX addition. This is due to the synergistic effect of Cu and Ni complexes with the V / Mo oxide combustion moderators.
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Abstract
Description
Die Erfindung betrifft einen Festtreibstoff für Raketenantriebe oder Gasgeneratoren, der als Oxidator Ammoniumnitrat (AN) in reiner oder phasenstabilisierter Form (PSAN) enthält.The invention relates to a solid fuel for rocket engines or gas generators, which contains ammonium nitrate (AN) in pure or phase-stabilized form (PSAN) 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.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.
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.Additions of ammonium perchlorate, which lead to an increase in the rate of combustion, 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 in 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 begrenztem 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 combustion 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, das Abbrandverhalten von Festtreibstoffen auf der Basis von reinem und phasenstabilisiertem Ammoniumnitrat zu verbessern.The object of the invention is to improve the combustion behavior of solid fuels on the basis of pure and phase-stabilized ammonium nitrate.
Erfindungsgemäß besteht ein solcher Festtreibstoff aus 35 bis 80 Massen-% Ammoniumnitrat (AN) in reiner oder mit Nickeloxid, Kalium- oder Cäsiumnitrat phasenstabilisierter Form (PSAN) mit einer mittleren Korngröße von 5 bis 200µm, 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) in pure form or phase-stabilized form (PSAN) with nickel oxide, potassium or cesium nitrate with an average grain size of 5 to 200 µm, 15 to 50% by mass of a binder system from one Binder polymer and a high-energy plasticizer as well as 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 ¾ 0,6, im günstigen Fall n ¾ 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 ¾ 0.6, in the favorable case n ¾ 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 dadurch aus, daß sie als Oxidator reines AN oder mit Nickeloxid, Kalium- oder Cäsiumnitrat umgesetztes phasenstabilisiertes Ammoniumnitrat als Oxidator enthalten, wobei die Nickeloxide vorzugsweise mit 1 bis 7 Massen-%, Kalium- oder Cäsiumnitrat mit 3 bis 15 Massen-% eingesetzt werden. Sie stabiliseren 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 der Additive mit der Schmelze des reinen Ammoniumnitrats unter Abspaltung von Wasser. Die für die Herstellung des Treibstoffs günstigste Partikelform kann durch Versprühen der Schmelze und schnelles Abkühlen im kalten, zyklonartig geführten Luftstrom erhalten werden. Für raucharme Treibstoffe wird vorzugsweise AN in reiner Form mit einem Wassergehalt unter 0,2 Massen-% oder NiO-stabilisiertes PSAN eingesetzt, während mit Kalium- oder Cäsiumnitrat stabilisiertes PSAN etwas höhere Rauchanteile mit sich bringt.The solid propellants according to the invention are initially distinguished by the fact that they contain pure AN as the oxidizer or phase-stabilized ammonium nitrate reacted with nickel oxide, potassium or cesium nitrate as the oxidizer, the nickel oxides preferably containing 1 to 7% by mass, potassium or cesium nitrate containing 3 to 15 % By mass are used. 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 the additives with the melt of the pure ammonium nitrate with elimination of water. The most favorable particle shape for the production of the fuel can be obtained by spraying the melt and rapid cooling in a cold, cyclone-like air flow. For low-smoke fuels, AN is preferably used in pure form with a water content below 0.2% by mass or NiO-stabilized PSAN, while PSAN stabilized with potassium or cesium nitrate brings with it somewhat higher smoke proportions.
Das Abbrandverhalten wird maßgeblich durch die Korngröße des AN bzw. PSAN 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- bzw. PSAN-Fraktion überwiegend in kleinerer Korngröße von 10 bis 80µm und weniger in mittlerer Korngröße von 100 bis 160 µm vorliegt.The combustion behavior is significantly influenced by the grain size of the AN or PSAN. 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 or PSAN fraction predominantly in smaller ones Grain size from 10 to 80 µm and less in average grain size from 100 to 160 µm is available.
Der erfindungsgemäße Festtreibstoff kann ferner energiereiche Stoffe, insbesondere Nitramine enthalten, wie Hexogen (RDX) oder Oktogen (HMX) mit einer mittleren Korngröße von 2 bis 200 µm bei einem Anteil von 1 bis 4 Massen-%.The solid propellant according to the invention can also contain high-energy substances, in particular nitramines, such as hexogen (RDX) or octogen (HMX) with an average particle size of 2 to 200 μm with a proportion of 1 to 4% 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 salpetersäureesterhaltigen 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 ester, with small amounts in the range of 0.5% by mass of the magnesium oxide acting in the same sense.
Die erfindungsgemäß mit 0,2 bis 5,0 Massen-% eingesetzten Abbrandmoderatoren aus Vanadium/Molybdänoxid als Oxidmischung oder Mischoxid werden vorteilhafterweise mit Ruß oder Graphit mit einem Anteil von 5 bis 20 Massen-% der Fraktion des Abbrandmoderators zugesetzt.The combustion moderators made from vanadium / molybdenum oxide as oxide mixture or mixed oxide used according to the invention with 0.2 to 5.0 mass% are advantageously added with carbon black or graphite in a fraction of 5 to 20 mass% of the fraction of the combustion moderator.
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 könnnen auch energiereiche Polymere, vorzugsweise isocyanathärtendes, di- oder trifunktionelles hydroxisubstituiertes Glycidylazidopolymer eingesetzt werden.Another essential component in concentrations of 15 to 50 mass% is a binder system consisting of a binder polymer and a high-energy plasticizer. The binder polymer itself can be inert, it preferably being an isocyanate-curing, bifunctional or trifunctional hydroxyl-substituted polyester or polyether prepolymer. 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, MeNENA) oder N-n-Butyl-N-nitratoethylnitroamin (BuNENA) oder N, N'-Dinitratoethylnitroamin (DINA) geeignet ist.An example of a nitro plasticizer is a 1: 1 mixture of bisdinitropropyl formal / acetal (BDNPF / A), while a nitro amino plasticizer is a 1: 1 mixture of N-ethyl and N-methylnitratoethylnitroamine (EtNENA, 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 Inhalt, Verträglichkeit und Energieinhalt 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 content, compatibility and energy content of the binder components, the ratio polymer / plasticizer is 1: 3 to 20: 1 mass%. The binder polymers can of course also be used in pure form.
Dem reineren oder phasenstabilisierten Ammoniumnitrat werden vorzugsweise 0,1 bis 1 Massen-% seiner Fraktion Antibackmittel, z.B. ultrafeines (Korngröße etwa 0,02µm) Silicagel, Natriumlaurylsulfonat, Tricalciumphosphat oder andere Tenside zugesetzt.The purer or phase stabilized ammonium nitrate is preferably 0.1 to 1% by mass of its anti-caking agent fraction, e.g. ultra-fine (grain size about 0.02 µm) silica gel, sodium lauryl sulfonate, tricalcium phosphate or other surfactants are added.
Erfindungsgemäß lassen sich die Vanadium/Molybdänoxid-Abbrandmoderatoren in idealer Weise mit Nickel und Kupfer-Salzen, -Oxiden, oder -Komplexen verbinden, was eine weitere Steigerung der Abbrandgeschwindigkeit mit sich bringt.According to the invention, the vanadium / molybdenum oxide combustion moderators can be ideally combined with nickel and copper salts, oxides or complexes, which leads to a further increase in the combustion rate.
Die Abbrandmoderatoren bestehen vorzugsweise aus Mischoxiden, in denen Molybdän in der Oxidationsstufe +VI und Vanadium in den Oxidationsstufen +IV und +V vorliegen. Beispielhafte Zusammensetzungen der Mischoxide sind V₆Mo₄O₂₅ und V₆Mo₁₅ O₂₅O₆₀.
Die Mischoxide können ferner Chrom (III)- sowie Titan (IV)-Oxide als inaktives oder ebenfalls am Reaktionsgeschehen teilnehmendes Trägermaterial enthalten.The combustion moderators preferably consist of mixed oxides in which molybdenum is present in the + VI and + V oxidation states and vanadium in the + IV and + V oxidation states. Exemplary compositions of the mixed oxides are V₆Mo₄O₂₅ and V₆Mo₁₅ O₂₅O₆₀.
The mixed oxides can furthermore contain chromium (III) and titanium (IV) oxides as the inactive carrier material or one which also participates in the reaction.
In bevorzugter Ausführung weisen die Abbrandmoderatoren eine Korngröße im Bereich von 1 bis 60µm, vorzugsweise 1 bis 10µm und eine hohe innere Oberfläche von 5 bis 100m²/g, vorzugsweise 20 bis 60m²/g auf.In a preferred embodiment, 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
Bei einer mittleren Korngröße unter 10µm und gleichbleibender, hoher innerer Oberfläche lassen sich gegenüber groberem Korn die Abbrandgeschwindigkeit im niederen Druckbereich weiter anheben und der Druckexponent weiter absenken.With an average grain size of less than 10 µm and a constant, high inner surface, the burning rate in the low pressure range can be increased further compared to coarser grain and the pressure exponent can be further reduced.
Die erfindungsgemäßen Festtreibstoffe erfahren eine vorteilhafte Weiterentwicklung dadurch, daß hochschmelzende Metallcarbide oder -nitride, vorzugsweise Silicium- und Zirkoncarbid im Konzentrationsbereich von 0,1 bis 1 Massen-% zugegeben werden. Damit wird vor allem ein instabiles oszillierendes Abbrandverhalten bei der Anwendung in Raketenmotoren unterdrückt. Dies ist vor allem für raucharm brennende Treibstoffe ohne Metallzusatz von Bedeutung.The solid propellants according to the invention experience an advantageous further development in that high-melting Metal carbides or nitrides, preferably silicon and zirconium carbide in the concentration range from 0.1 to 1 mass% are added. Above all, this suppresses an unstable, oscillating combustion behavior when used in rocket engines. This is particularly important for low-smoke burning fuels without the addition of metal.
Festtreibstoffe der beschriebenen Art, insbesondere mit Oxidatoren in Gestalt von reinem AN oder Ni-PSAN, 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.Solid fuels of the type described, in particular with oxidizers in the form of pure AN or Ni-PSAN, are suitable due to their energy content, their low-smoke, hydrochloric acid-free combustion and their comparatively low, mechanical and detonative sensitivity for use in rocket engines, while lower-energy formulations with a higher binder content are suitable for use as gas generator propellants.
Tabelle 1 zeigt in ihrem oberen Teil neun verschiedene Fomulierungen mit reinem Ammoniumnitrat und eine mit 3% Nickeloxid phasenstabilisierten 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 nine different formulations with pure ammonium nitrate and a PSAN phase-stabilized with 3% nickel oxide. 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.
Neben der Abhängigkeit von der Art des zugegebenen Abbrandmoderators ist dabei auch eine Abhängigkeit vom Grob/Fein-Anteil des eingesetzten Ammoniumnitrats sowie vom Gehalt des Azidopolymeren in Relation zum Weichmacherteil beobachtbar. Mit überwiegendem Anteil von AN der mittleren Korngröße 160 µm werden mit V/Mo-Oxid Abbrandmoderatoren bei AN1 nur kanpp 8 mm/s bei 10 MPa Brennkammerdruck erreicht. Ohne oder mit konventionellen Abbrandmoderatoren auf der Basis von Bleisalzen und Ruß sind es bei gleicher Formulierung nur 6,6 mm/s. Demgegenüber tritt bei AN2 mit überwiegendem Feinanteil des Ammoniumnitrats eine deutliche Steigerung der Abbrandgeschwindigkeit mit weiterer Senkung des Druckexponenten ein.In addition to the dependency on the type of combustion moderator added, a dependency on the coarse / fine fraction of the ammonium nitrate used and on the content of the azidopolymer in relation to the plasticizer part can also be observed. With a predominant share of AN The
AN3 bis AN8 besitzen durch den hohen Weichmacheranteil hohe spezifische Impulse von 234s bei AN6 und AN8 sowie 237s bei AN3, AN4 und AN5 bei einem Enspannungsverhältnis von 70:1. Als besonders günstig hat sich in diesem Fall die synergistische Wirkung von Kupferverbindungen und V/Mo-Oxid-Abbrandmoderatoren erwiesen. Am günstigsten in der Kombination von Abbrandgeschwindigkeitssteigerung, Senkung des Druckexponenten und annehmbaren Stabilitätseigenschaften hat sich dabei Kupferphthalocyanat erwiesen.Due to the high plasticizer content, AN3 to AN8 have high specific impulses of 234s for AN6 and AN8 and 237s for AN3, AN4 and AN5 with a relaxation ratio of 70: 1. In this case, the synergistic effect of copper compounds and V / Mo oxide combustion moderators has proven to be particularly favorable. Copper phthalocyanate has proven to be the most favorable in the combination of increase in the rate of combustion, reduction in the pressure exponent and acceptable stability properties.
Das Abbrandverhalten der Formulierung AN9 zeigt, daß auch das Nickeldiaminodinitrat als Phasenstabilisator im AN eine günstige Wirkung auf das Abbrandverhalten ausübt. Ebenso wird dies beim Zusatz von Nickelphthalocyanat in der Formulierung AN8 beobachtet. Der Zusatz von RDX bewirkt ebenfalls eine Steigerung der Abbrandgeschwindigkeit, ohne jedoch den Druckexponenten positiv zu beeinflußen.The burning behavior of the formulation AN9 shows that the nickel diaminodinitrate as phase stabilizer in the AN also has a favorable effect on the burning behavior. This is also observed with the addition of nickel phthalocyanate in the AN8 formulation. The addition of RDX also increases the burning rate without, however, positively influencing the pressure exponent.
Tabelle 2 zeigt mit den Beispielen AN10, AN11 und AN12 AN/GAP-Treibstofformulierungen, bei denen der Abbrandmoderator in unterschiedlicher Korngröße und Kornverteilung bei sonst gleicher Zusammensetzung enthalten ist. Im unteren Teil der Tabelle ist die mit kleiner werdendem Korn erzielte Steigerung der Abbrandgeschwindigkeit bei gleichzeitiger Absenkung des Druckexponenten deutlich ersichtlich. AN13 zeigt das Abbrandverhalten bei einer Formulierung mit Azidoweichmacher, während AN14 eine Formulierung mit Zusatz von Zirkoncarbid ist, mit dessen Hilfe Abbrandoszillationen beim Einsatz des Treibstoffs in Raketenmotoren unterdrückt werden.Table 2 shows with the examples AN10, AN11 and AN12 AN / GAP fuel formulations in which the combustion moderator is contained in different grain sizes and grain distributions with otherwise the same composition. in the The lower part of the table clearly shows the increase in the burn-off rate achieved with the grain becoming smaller, while at the same time lowering the pressure exponent. AN13 shows the burning behavior when formulated with an azido softener, while AN14 is a formulation with the addition of zirconium carbide, with the help of which combustion oscillations are suppressed when the fuel is used in rocket engines.
In den Diagrammen ist das Abbrandverhalten als Funktion
Der Vergleich von Abbildung 1 und 2 zeigt, daß bei gleichem RDX-Gehalt von 10% die Wirkung des Abbrandmoderators bei hohem Weichmacheranteil weniger ausgeprägt ist als bei hohem GAP-Anteil (
Claims (25)
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DE4435524A DE4435524C2 (en) | 1994-10-05 | 1994-10-05 | Solid fuel based on pure or phase-stabilized ammonium nitrate |
DE4435524 | 1994-10-05 |
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EP (1) | EP0705809B1 (en) |
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RU2541265C1 (en) * | 2013-12-02 | 2015-02-10 | Открытое акционерное общество "Федеральный научно-производственный центр "Алтай" | Method of producing high-energy composite |
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Also Published As
Publication number | Publication date |
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DE4435524C2 (en) | 1996-08-22 |
NO953923L (en) | 1996-04-09 |
EP0705809B1 (en) | 1997-07-02 |
NO303909B1 (en) | 1998-09-21 |
DE4435524A1 (en) | 1996-04-11 |
ES2105826T3 (en) | 1997-10-16 |
DE59500344D1 (en) | 1997-08-07 |
NO953923D0 (en) | 1995-10-03 |
US5596168A (en) | 1997-01-21 |
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