FR2680166A1 - Solid mixture of rocket fuels, in particular for the propulsion of vehicles such as rockets, and process for its preparation - Google Patents

Solid mixture of rocket fuels, in particular for the propulsion of vehicles such as rockets, and process for its preparation Download PDF

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FR2680166A1
FR2680166A1 FR9108382A FR9108382A FR2680166A1 FR 2680166 A1 FR2680166 A1 FR 2680166A1 FR 9108382 A FR9108382 A FR 9108382A FR 9108382 A FR9108382 A FR 9108382A FR 2680166 A1 FR2680166 A1 FR 2680166A1
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chemical formula
propulsion
chosen
vehicles
poly
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FR2680166B1 (en
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Mul Johannes Maria
Schoyer Herman Fedde Rein
Schnorhk Ared Jean Louis
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PRINS MAURITS LAB TNO
Agence Spatiale Europeenne
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PRINS MAURITS LAB TNO
Agence Spatiale Europeenne
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Priority to FR9108382A priority Critical patent/FR2680166B1/en
Priority to US08/347,349 priority patent/US5837930A/en
Priority to PCT/FR1992/000628 priority patent/WO1993001151A1/en
Priority to JP50202093A priority patent/JP3360177B2/en
Publication of FR2680166A1 publication Critical patent/FR2680166A1/en
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/02—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant
    • C06B47/08—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant a component containing hydrazine or a hydrazine derivative
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/02—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant
    • C06B47/10—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant a component containing free boron, an organic borane or a binary compound of boron, except with oxygen

Abstract

A solid mixture of rocket fuels, in particular for the propulsion of vehicles such as rockets, of the type consisting at least of an oxidiser chosen from the group including hydrazinium nitroformate (HNF) of chemical formula (N2H5C(NO2)3), nitrinium perchlorate (NP) of chemical formula (NO2ClO4), ammonium perchlorate (AP) of chemical formula (NH4ClO4), ammonium nitroformate (ANF) of chemical formula (NH4C(NO2)3), of a fuel chosen from the group including boron (B), aluminium (Al) and aluminium hydride (AlH3), of an energetic binder chosen from the group including polyglycidyl nitrate (PGN) of chemical formula (C3H5NO4)n and polynitromethoxymethyloxetane (poly(NIMMO)) of chemical formula (C5H9NO4)n.

Description

La présente invention concerne un mélange solide d'ergols, en particulier pour la propulsion d'engins tels que des fusées, du type constitué au moins d'un oxydant choisi dans le groupe comprenant le nitroformiate d'hydrazinium de formule chimique ((N2H5C(N02)3), le perchlorate de nitronium de formule chimique (N02C104) et le perchlorate d'ammonium de formule chimique (NH4Cl04), et d'un combustible choisi dans le groupe comprenant le bore (B), l'aluminium (Al) et l'hydrure d'aluminium (AlH3).  The present invention relates to a solid mixture of propellants, in particular for the propulsion of vehicles such as rockets, of the type consisting at least of an oxidant chosen from the group comprising hydrazinium nitroformate of chemical formula ((N2H5C ( N02) 3), nitronium perchlorate of chemical formula (N02C104) and ammonium perchlorate of chemical formula (NH4Cl04), and of a fuel chosen from the group comprising boron (B), aluminum (Al) and aluminum hydride (AlH3).

D'une manière générale, il existe des besoins importants en ergols ou mélanges d'ergols à hautes performances dans de nombreux domaines de l'industrie, en particulier dans l'aérospatiale où ces mélanges doivent pouvoir non seulement être stockés durablement dans un engin spatial par exemple pour être utilisés à tout moment pour modifier sa trajectoire, mais aussi servir à son lancement. In general, there are significant needs for propellants or mixtures of high-performance propellants in many fields of industry, in particular in aerospace where these mixtures must not only be able to be stored permanently in a spacecraft for example to be used at any time to modify its trajectory, but also to be used for its launch.

Jusqu'à présent, il est fait largement usage de mélanges cryogéniques à base d'oxygène et d'hydrogène liquide, qui s'avèrent très performants pour alimenter les moteurs des fusées qui placent notamment sur orbite des satellites de télécommunication et des engins spatiaux. So far, extensive use has been made of cryogenic mixtures based on oxygen and liquid hydrogen, which have proven to be very effective in supplying rocket engines which place telecommunications satellites and spacecraft in orbit.

Cependant, ces mélanges cryogéniques sont délicats à stocker et leur manipulation est dangereuse et souvent source d'accidents. However, these cryogenic mixtures are delicate to store and their handling is dangerous and often a source of accidents.

Pour pallier ces inconvénients, il est connu de remplacer ces mélanges cryogéniques par des mélanges d'ergols constitués au moins d'un agent oxydant et d'un agent combustible, qui peuvent être stockés facilement et durablement sans nécessiter des conditions de sécurité particulières, mais ces mélanges offrent généralement des performances très inférieures à celles offertes par les mélanges cryogéniques. To overcome these drawbacks, it is known to replace these cryogenic mixtures with mixtures of propellants consisting at least of an oxidizing agent and a combustible agent, which can be stored easily and durably without requiring any specific safety conditions, but these mixtures generally offer much lower performance than those offered by cryogenic mixtures.

A titre de comparaison, en considérant un des paramètres qui caractérise ces mélanges, à savoir l'impulsion spécifique (qui sera définie avec précision plus loin), cette impulsion est supérieure à 4000 m/s pour des mélanges cryogéniques, alors qu'elle est seulement d'environ 3000 m/s pour un mélange d'ergols constitué de tetroxyde d'azote (N204) et de monométhylhydrazine (N2H3CH3) par exemple. For comparison, considering one of the parameters which characterizes these mixtures, namely the specific pulse (which will be defined with precision below), this pulse is greater than 4000 m / s for cryogenic mixtures, whereas it is only about 3000 m / s for a mixture of propellants consisting of nitrogen tetroxide (N204) and monomethylhydrazine (N2H3CH3) for example.

Dans ces conditions, si une vitesse de 2000 m/s est nécessaire pour mettre sur orbite un engin spatial ou pour modifier sa trajectoire, la moitié de la masse de l'engin spatial doit être réservée à un agent propulsif capable de produire une impulsion spécifique de 2943 m/s. Par contre, avec une impulsion spécifique de 4415 m/s, la masse de l'agent propulsif serait ramenée à 37,5 %, offrant ainsi un gain en masse d'environ 12,5 * qui pourrait être avantageusement utilisé pour embarquer des satellites de télécommunication par exemple. Autrement dit, en augmentant l'impulsion spécifique, il est possible de réduire la masse de l'agent propulsif et d'augmenter la charge utile embarquée à bord de l'engin spatial. A titre d'exemple, pour un engin spatial de 2000 kg, l'augmentation de la charge utile est de l'ordre de 250 kg. Under these conditions, if a speed of 2000 m / s is necessary to put a spacecraft into orbit or to modify its trajectory, half of the mass of the spacecraft must be reserved for a propellant capable of producing a specific pulse. 2943 m / s. On the other hand, with a specific pulse of 4415 m / s, the mass of the propellant would be reduced to 37.5%, thus offering a mass gain of around 12.5 * which could be advantageously used to carry satellites telecommunications for example. In other words, by increasing the specific impulse, it is possible to reduce the mass of the propellant and to increase the payload on board the spacecraft. For example, for a 2000 kg spacecraft, the increase in payload is of the order of 250 kg.

Etant donné que seuls les mélanges cryogéniques permettaient d'obtenir des impulsions spécifiques supérieures à 4000 m/s, on a cherché à augmenter le pouvoir énergétique des mélanges d'ergols et conserver ainsi les avantages qu'ils présentent au niveau de leur stockage. Since only cryogenic mixtures made it possible to obtain specific impulses greater than 4000 m / s, attempts were made to increase the energy power of the propellant mixtures and thus retain the advantages which they present in terms of their storage.

Il est connu du document Es-0 350 136, déposé au nom de la Demanderesse, un mélange solide d'ergols du type constitué au moins d'un oxydant choisi dans le groupe comprenant le nitroformiate d'hydrazinium (HNF) de formule chimique (N2H5C(NO2)3), le perchlorate de nitronium de formule chimique (NO2C104) et le perchlorate d'ammonium de formule chimique (NH4Cl04), et d'un combustible choisi dans le groupe comprenant le bore (B), l'aluminium (Al) et l'hydrure d'aluminium (A1H3), mélange auquel on a ajouté un liant énergétique formé d'azoture de polyglycidyle de formule chimique (C3H5N30)n ou de poly-3,3bis(azidométhyl)oxétanne de formule chimique (C4H6N60)n, pour obtenir un agent propulsif ayant des performances voisines de celles des mélanges cryogéniques. It is known from document Es-0 350 136, filed in the name of the Applicant, a solid mixture of propellants of the type consisting at least of an oxidant chosen from the group comprising hydrazinium nitroformate (HNF) of chemical formula ( N2H5C (NO2) 3), nitronium perchlorate of chemical formula (NO2C104) and ammonium perchlorate of chemical formula (NH4Cl04), and of a fuel chosen from the group comprising boron (B), aluminum ( A1) and aluminum hydride (A1H3), a mixture to which an energy binder formed from polyglycidyl azide of chemical formula (C3H5N30) n or poly-3.3bis (azidomethyl) oxetane of chemical formula (C4H6N60) has been added ) n, to obtain a propellant having performances close to those of cryogenic mixtures.

Le but de l'invention est de concevoir un autre mélange solide d'ergols au moins aussi performant que celui décrit dans le document précité. The object of the invention is to design another solid mixture of propellants at least as effective as that described in the aforementioned document.

A cet effet, l'invention propose un mélange solide d'ergols du type précité en ce qui concerne le combustible et l'oxydant solide, caractérisé en ce l'oxydant peut également être du nitroformiate d'ammonium (ANF) de formule chimique NH4C(N02)3, et en ce qutil comprend également un liant énergétique choisi dans le groupe comprenant le nitrate de polyglycidyle (PGN) de formule chimique (C3H5N04)n et le polynitrométhoxyméthyloxétanne (poly(NIMMO)) de formule chimique (C5H9NO4) n.  To this end, the invention provides a solid mixture of propellants of the aforementioned type with regard to the fuel and the solid oxidant, characterized in that the oxidant can also be ammonium nitroformate (ANF) of chemical formula NH4C (N02) 3, and in that it also comprises an energy binder chosen from the group comprising polyglycidyl nitrate (PGN) of chemical formula (C3H5N04) n and polynitromethoxymethyloxetane (poly (NIMMO)) of chemical formula (C5H9NO4) n.

En donnant les abréviations de polyglycidyle suivantes - PGN pour le nitrate de polyglycidyle, - poly(NIMMO) pour le polynitrométhoxyméthyloxétanne, des mélanges préférentiels selon l'invention sont les suivants - N2H5(N02)3 + B + PGN ou poly(NIMMO), - N02C104 + B + PGN ou poly(NIMMO), - NH4C104 + B + PGN ou poly(NIMMO), - NH4C(N02)3 + B + PGN ou poly(NIMMO), - N2H5C(N02)3 + Al + PGN ou poly(NIMMO), - N02C104 + Al + PGN ou poly(NIMMO), - NH4C104 + Al + PGN ou poly(NIMMO), - NH4C(N02)3 + Al + PGN ou poly(NIMMO), - N02C104 + A1H3 + PGN ou poly(NIMMO), - N02C104 + A1H3 + PGN ou poly(NIMMO).  By giving the following polyglycidyl abbreviations - PGN for polyglycidyl nitrate, - poly (NIMMO) for polynitromethoxymethyloxetane, preferred mixtures according to the invention are the following - N2H5 (N02) 3 + B + PGN or poly (NIMMO), - N02C104 + B + PGN or poly (NIMMO), - NH4C104 + B + PGN or poly (NIMMO), - NH4C (N02) 3 + B + PGN or poly (NIMMO), - N2H5C (N02) 3 + Al + PGN or poly (NIMMO), - N02C104 + Al + PGN or poly (NIMMO), - NH4C104 + Al + PGN or poly (NIMMO), - NH4C (N02) 3 + Al + PGN or poly (NIMMO), - N02C104 + A1H3 + PGN or poly (NIMMO), - N02C104 + A1H3 + PGN or poly (NIMMO).

Avec de tels mélanges, il est possible d'obtenir des impulsions spécifiques supérieures à 4000 m/s, l'impulsion spécifique Isp qui caractérise notamment un agent propulsif étant exprimée par la formule

Figure img00040001

où: - . est le support de chaleur spécifique
Cv - Ro la constante molaire des gaz parfaits, - Tc la température de la flamme de combustion, - M la masse moléculaire moyenne des produits de combus
tion, - Pc la pression dans la chambre de combustion, - et Pe la pression de sortie de la tuyère.With such mixtures, it is possible to obtain specific impulses greater than 4000 m / s, the specific impulse Isp which in particular characterizes a propellant being expressed by the formula
Figure img00040001

or: - . is the specific heat support
Cv - Ro the molar constant of ideal gases, - Tc the temperature of the combustion flame, - M the average molecular weight of combustion products
tion, - Pc the pressure in the combustion chamber, - and Pe the nozzle outlet pressure.

Les proportions en poids de l'oxydant et du combustible entrant dans la constitution de ces mélanges ne sont pas critiques selon l'invention. Généralement, les constituants sont mélangés les aux autres avant leur durcissement dans des proportions telles que les rapports du mélange sont situés aux environs du rapport stoechiométrique afin d'obtenir une combustion la plus complète possible, et de bons résultats sont obtenus avec une quantité de liant énergétique PGN ou poly(NIMMO) qui n'excède pas 35 % du poids total du mélange. Avec une telle quantité du liant énergétique, on obtient des résistances mécaniques satisfaisantes. The proportions by weight of the oxidant and of the fuel used in the constitution of these mixtures are not critical according to the invention. Generally, the constituents are mixed with the others before their hardening in proportions such that the ratios of the mixture are located around the stoichiometric ratio in order to obtain the most complete combustion possible, and good results are obtained with an amount of binder. energy PGN or poly (NIMMO) which does not exceed 35% of the total weight of the mixture. With such an amount of the energy binder, satisfactory mechanical strengths are obtained.

D'une manière générale, on ajoute au mélange de préférence quelques % en poids de composants tels que des phthalates, des stéréates, des sels de plomb ou de cuivre, de la poudre noire, etc... Ces additifs sont connus en soi pour augmenter la stabilité du mélange sans en modifier les caractéristiques, notamment de combustion, et pour donner également au mélange des propriétés anti-corrosion.  In general, a few% by weight of components such as phthalates, stereates, lead or copper salts, black powder, etc. are added to the mixture preferably. These additives are known per se increase the stability of the mixture without modifying its characteristics, in particular its combustion characteristics, and also to give the mixture anti-corrosion properties.

De préférence, on exclut des composants additionnels les métaux et les hydrures métalliques. Preferably, metals and metal hydrides are excluded from additional components.

I1 est à noter que les gaz de combustion de ces mélanges sont plus propres, lorsque les oxydants utilisés (HNF ou ANF) ne contiennent pas de chlore, et il en résulte que le milieu extérieur n'est pas pollué avec de l'acide chlorhydrique. It should be noted that the combustion gases of these mixtures are cleaner, when the oxidants used (HNF or ANF) do not contain chlorine, and it follows that the external environment is not polluted with hydrochloric acid .

D'une manière générale, les mélanges selon l'invention sont stockés avant utilisation, selon des techniques connues, les constituants étant normalement déjà mélangés. In general, the mixtures according to the invention are stored before use, according to known techniques, the constituents being normally already mixed.

Les composants entrant dans la composition des mélanges selon l'invention sont bien connus en soi aussi bien pour leurs procédés de préparation que pour leurs propriétés physiques et chimiques.  The components used in the composition of the mixtures according to the invention are well known per se, both for their preparation processes and for their physical and chemical properties.

Claims (5)

REVENDICATIONS 1. Ergol, en particulier pour la propulsion d'engins tels que des fusées, du type comprenant un oxydant, un combustible et un liant, caractérisé en ce que l'oxydant est choisi dans le groupe comprenant le nitroformiate d'hydrazinium (HNF) de formule chimique (N2H5C(N02)3), le perchlorate de nitronium (NP) de formule chimique (NO2ClO4), le perchlorate d'ammonium (AP) de formule chimique (NH4C104) et le nitroformiate d'ammonium (ANF) de formule chimique (NH4C(NO2)3), en ce que le combustible est choisi dans le groupe comprenant le bore (B), l'aluminium (Al) et l'hydrure d'aluminium (AlH3), et en ce que le liant énergétique est choisi dans le groupe comprenant le nitrate de polyglycidyle (PGN) de formule chimique (C3H5NO4)n et le polynitrométhoxyméthyloxétanne (poly(NIMMO)) de formule chimique ( C5HgN04) n.  1. Ergol, in particular for the propulsion of vehicles such as rockets, of the type comprising an oxidant, a fuel and a binder, characterized in that the oxidant is chosen from the group comprising hydrazinium nitroformate (HNF) of chemical formula (N2H5C (N02) 3), nitronium perchlorate (NP) of chemical formula (NO2ClO4), ammonium perchlorate (AP) of chemical formula (NH4C104) and ammonium nitroformate (ANF) chemical (NH4C (NO2) 3), in that the fuel is chosen from the group comprising boron (B), aluminum (Al) and aluminum hydride (AlH3), and in that the energy binder is chosen from the group comprising polyglycidyl nitrate (PGN) of chemical formula (C3H5NO4) n and polynitromethoxymethyloxetane (poly (NIMMO)) of chemical formula (C5HgN04) n. 2. Ergol selon la revendication 1, caractérisé en ce que le liant énergétique (PGN ou (poly(NIMMO)) représente un pourcentage en poids qui n'excède pas 35 %. 2. Ergol according to claim 1, characterized in that the energy binder (PGN or (poly (NIMMO)) represents a percentage by weight which does not exceed 35%. 3. Ergol selon la revendication 1 ou 2, caractérisé en ce qu'il contient des composants additionnels autres que des composants métalliques et des hydrures métalliques, qui jouent un rôle de stabilisants de l'ergol. 3. Ergol according to claim 1 or 2, characterized in that it contains additional components other than metallic components and metallic hydrides, which act as stabilizers of the propellant. 4. Procédé de préparation d'un ergol, en particulier pour la propulsion d'engins, caractérisé en ce qu'il consiste à mélanger au moins un oxydant solide, un combustible solide et un liant énergétique solide ayant les formulations énoncées à la revendication 1. 4. Process for the preparation of an propellant, in particular for the propulsion of vehicles, characterized in that it consists in mixing at least one solid oxidant, a solid fuel and a solid energy binder having the formulations set out in claim 1 . 5. Utilisation pour assurer la propulsion d'engins tels que des fusées, d'un ergol selon l'une quelconque des revendications 1 à 3.  5. Use for ensuring the propulsion of vehicles such as rockets, of a propellant according to any one of claims 1 to 3.
FR9108382A 1991-07-04 1991-07-04 SOLID MIXTURE OF ERGOLS, ESPECIALLY FOR THE PROPULSION OF MACHINERY SUCH AS ROCKETS, AND ITS PREPARATION METHOD. Expired - Lifetime FR2680166B1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
FR9108382A FR2680166B1 (en) 1991-07-04 1991-07-04 SOLID MIXTURE OF ERGOLS, ESPECIALLY FOR THE PROPULSION OF MACHINERY SUCH AS ROCKETS, AND ITS PREPARATION METHOD.
US08/347,349 US5837930A (en) 1991-07-04 1992-07-03 Propellants, in particular for the propulsion of vehicles such as rockets, and process for their preparation
PCT/FR1992/000628 WO1993001151A1 (en) 1991-07-04 1992-07-03 Ergols, particularly for propelling missiles such as rockets, and a method for preparing same
JP50202093A JP3360177B2 (en) 1991-07-04 1992-07-03 In particular, propellants for propelling transportation means such as rockets, and methods for producing the same

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FR9108382A FR2680166B1 (en) 1991-07-04 1991-07-04 SOLID MIXTURE OF ERGOLS, ESPECIALLY FOR THE PROPULSION OF MACHINERY SUCH AS ROCKETS, AND ITS PREPARATION METHOD.

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0350136A2 (en) * 1988-07-08 1990-01-10 European Space Agency High-performance propellant combinations for a rocket engine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0350136A2 (en) * 1988-07-08 1990-01-10 European Space Agency High-performance propellant combinations for a rocket engine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 68, no. 2, 8 Janvier 1968, Columbus, Ohio, US; abstract no. 3437N, KOJI KUBOTA ET AL: 'synthesis of "nitro resins"' page 343 ; *

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