WO2007042735A2 - Rapid gas generating pyrotechnical composition and method for obtaining same - Google Patents

Rapid gas generating pyrotechnical composition and method for obtaining same Download PDF

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Publication number
WO2007042735A2
WO2007042735A2 PCT/FR2006/051026 FR2006051026W WO2007042735A2 WO 2007042735 A2 WO2007042735 A2 WO 2007042735A2 FR 2006051026 W FR2006051026 W FR 2006051026W WO 2007042735 A2 WO2007042735 A2 WO 2007042735A2
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WIPO (PCT)
Prior art keywords
nitrate
weight
dry
perchlorate
composition according
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PCT/FR2006/051026
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French (fr)
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WO2007042735A3 (en
Inventor
Frédéric MARLIN
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Snpe Materiaux Energetiques
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Application filed by Snpe Materiaux Energetiques filed Critical Snpe Materiaux Energetiques
Priority to US12/083,317 priority Critical patent/US20090308509A1/en
Priority to JP2008535078A priority patent/JP5273609B2/en
Priority to EP06820288A priority patent/EP1934158A2/en
Priority to CN200680043374.5A priority patent/CN101312930B/en
Publication of WO2007042735A2 publication Critical patent/WO2007042735A2/en
Publication of WO2007042735A3 publication Critical patent/WO2007042735A3/en

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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0066—Shaping the mixture by granulation, e.g. flaking
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0041—Shaping the mixture by compression
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • the present invention relates to the pyrotechnic generation of gas, in particular for inflating cushions used in occupant protection systems of a motor vehicle.
  • the present invention more specifically relates to so-called cold pyrotechnic compositions rapidly generating at acceptable temperatures for automotive safety (qualified low temperatures, that is to say less than 2200 K) clean and non-toxic gases.
  • the present invention also relates to a process for obtaining such pyrotechnic compositions.
  • the pyrotechnic compositions used in the gas generators must provide the quantity of gas required for the introduction of the airbag in an extremely short time, typically between 10 and 40 milliseconds.
  • the gases generated must be clean, that is to say free of solid particles (which may constitute hot spots that may damage the wall of said cushion) and non-toxic, that is to say, low in content. carbon monoxide, nitrogen oxides and chlorinated products.
  • compositions that appear to offer the best compromise in terms of gas temperature, gas yield, emitted particle content and toxicity contain, as main ingredients, guanidine nitrate (NG) and basic copper nitrate ( BCN).
  • NG guanidine nitrate
  • BCN basic copper nitrate
  • the material passing between them is compacted in the form of a flat plate.
  • Such an operation generates on the mixture a high compression and shear rate which improves the intimacy between the constituents.
  • the compacted product from the compactor is then broken and forced through a rasp to generate pellets.
  • Such granules generally prove to be easier to handle than the powders of departure.
  • a single device generally provides compacting and granulation successively.
  • the present invention thus relates to pyrotechnic gas generating compositions which combine two characteristics.
  • a second oxidizing charge in the form of at least one alkali metal perchlorate said charges representing at least 95% by weight (generally at least 98% by mass) of the charges present;
  • the pyrotechnic compositions of the invention containing a specific reducing charge (in the form of at least one nitrogen-containing organic compound) and a specific oxidizing charge (in the form of at least one basic metal nitrate), contain a limited quantity of a second specific oxidizing charge (in the form of at least one alkali metal perchlorate) and are obtained from a process which includes a step of dry-roller compaction of the powder mixture including said reducing and specific oxidants.
  • Dry roll compacting is carried out, in a known manner, in a roller compactor, generally at a compacting pressure of 10 8 to 6.10 8 Pa.
  • the method for obtaining the pyrotechnic compositions of the invention which typically includes a dry roll compacting step is further described in the present text. It can be implemented according to different variants (with a "simple" roller compacting characteristic step followed by at least one complementary step, with a roller compacting step coupled to a shaping step). and the pyrotechnic compositions of the invention therefore exist in different forms. In fact :
  • pellets After dry roller compacting followed by granulation and then pelletization (dry compression), pellets are obtained;
  • the granules according to the invention generally have a particle size (a median diameter) of between 200 and 800 ⁇ m
  • the pellets according to the invention generally have a thickness of between 1 and 3 mm; and that within the extruded monolithic blocks, the granules are found in a dry binder (gel).
  • part of the first object of the invention is in particular:
  • the at least one nitrogenous organic compound constituting the reducing charge can be chosen in particular from guanidine nitrate, nitroguanidine, guanyl urea dinitramide and mixtures thereof. It consists advantageously of guanidine nitrate (NG).
  • the at least one basic metal nitrate constituting the (first) oxidizing charge can be chosen in particular from nitrate basic copper, basic zinc nitrate, basic bismuth nitrate and their mixtures. It consists advantageously of the basic nitrate of copper (BCN).
  • the at least one alkali metal perchlorate may in particular be chosen from potassium perchlorate, sodium perchlorate and mixtures thereof. It consists advantageously of potassium perchlorate (KCIO 4 ).
  • the main constitutive ingredients of the compositions of the invention are therefore: guanidine nitrate (NG)
  • said at least one nitrogen-containing organic compound present in a proportion of 45 to 65% by weight
  • the pyrotechnic compositions of the invention contain;
  • NG guanidine nitrate
  • BCN basic copper nitrate
  • KCIO 4 potassium perchlorate
  • the pyrotechnic compositions of the invention in the form of formed articles, granules and pellets, consist essentially of (at least 95% by weight, generally at least 98% by weight) or even exclusively (at 100% by weight), the principal constitutive ingredients (charges) identified above: said at least one compound nitrogenous organic compound, said at least one basic metal nitrate and said at least one alkali metal perchlorate. Said ingredients can in fact alone constitute 100% the charges of said pyrotechnic compositions (this is generally the case), or even constitute 100% said pyrotechnic compositions.
  • compositions of the invention of other charges in minimum quantities can not be ruled out (in any event, the charges identified above represent at least 95% by mass, generally at least 98% by weight of the charges present) and / or that of at least one additive (auxiliary type of manufacture).
  • compositions of the invention in the form of extruded monolithic blocks, contain the main constituent ingredients (fillers) identified above (plus possibly other fillers in minimum amounts) in a dry gel.
  • This gel extrudable per se or mixed with a solvent, is used upstream to allow extrusion. It has intervened in an effective amount (to allow extrusion) but limited so as not to significantly affect the performance of the compositions of the invention.
  • extruded monolithic blocks of the invention generally do not contain more than 10% by weight of such a dry gel. They contain advantageously from 4 to 6% by weight. Within them, the synergy of the invention develops with the same intensity.
  • the presence of at least one additive is also not excluded from this context.
  • the main constituent ingredients (fillers) and the dry gel generally represent at least 95% by weight, very generally at least 98% by weight (or even 100% by weight) of said compositions.
  • Said gel is generally chosen from cellulosic gels, gels obtained from acrylic elastomers, ethylene-vinyl-acetate copolymers with a high acetate content (containing more than 60% by weight of acetate units), polyester polymers, and their mixtures.
  • Said gel advantageously consists of a sodium carboxymethylcellulose gel.
  • the present invention relates to the process for obtaining pyrotechnic compositions as described above; a process which typically includes dry compacting of powders.
  • the method comprises:
  • the dry mixture of powders (of fillers) consisting of at least 95% by weight of a pulverulent reducing filler in the form of at least one nitrogenous organic compound, a pulverulent oxidizing filler in the form of at least one basic nitrate of metal and less than 30% by weight of a second powdery oxidizing charge in the form of at least one alkali metal perchlorate; and dry-roller compacting the resulting powder mixture.
  • the constitutive ingredients of the desired pyrotechnic compositions occur in the form of powders.
  • said powders have a fine particle size, less than or equal to 40 microns. Said particle size (value of the median diameter) is generally between 3 and 40 microns.
  • the dry powder mixing and dry roll compacting steps of the resulting mixture are carried out in a conventional manner. With regard to dry roller compaction, it has been seen that it is implemented by passing the mixture of powders between two rolls, the pressure exerted then generally being between 10 8 and 6.10 8 Pa. a "simple" compaction with two cylinders having unmachined external surfaces or compaction coupled to a shaping with cylinders, the outer surface of at least one of which is machined to have cavities.
  • the process of the invention can be limited to these two successive stages of mixing and compacting with dry rollers, in the following context: that of the direct obtaining of formed objects, in the assumption of the implementation of a roller compacting coupled to a shaping (the outer surface of at least one of the compacting rolls having cells).
  • the method of the invention in addition to said two dry (“simple") dry roll mixing and compaction steps, may include: a) a dry granulation step (the compacted powder mixture is mechanically forced by a wet rotor; through a rasp exercising the sieve function whose mesh generally ranges from 500 microns to 3 mm). Roller compaction and granulation can be implemented in a single device or in two independent devices.
  • the pyrotechnic compositions obtained are then in the form of granules (see above); b) a dry granulation step (see above) followed by pelletizing (dry compression during which the granules undergo a pressure generally between 4.10 8 and 10 9 Pa.
  • the pyrotechnic compositions obtained are then in the form of pellets (see above); c) a dry granulation step (see above) followed by mixing the granules obtained with an extrudable binder and extruding said mixture.
  • the pyrotechnic compositions finally obtained are in the form of extruded monolithic blocks loaded with granules.
  • Variants of the process of the invention which include steps b) and c) above are particularly preferred.
  • the method of the invention includes the steps of compacting rollers ("simple") and dry granulation of the mixture of starting powders.
  • the powders (raw materials) used have a fine grain size: a median diameter of approximately 20 ⁇ m for KCIO 4 , 4.5 ⁇ m for BCN, 10 ⁇ m for NG.
  • Table I presented below shows examples of formulation as well as the thermodynamic and ballistic performances of pellets (about 2 mm thick) obtained by pelletizing (carried out at 5.10 8 Pa) of previously uncompressed compacted powder mixtures. .
  • Example 4 which offers the best compromise between combustion rate, gas yield and combustion temperature, was conditioned, for example 5, by implementing a roller compacting process (pressure between the rolls of 4.10 8 Pa) and granulation (forcing the compacted material by a rotor through a rasp equivalent to a sieve having a mesh of about 1 mm) dry process, upstream of the pelletizing.
  • the granules obtained at the end of the roller compacting and granulation stage had a median particle size of approximately 500 ⁇ m. They were pelletized (easily, to the extent that there is no more flow problem) under the same conditions as the powders of Examples 1 to 4 (pressure of 5.10 8 Pa).
  • Table II presented below shows the contribution of the roller compacting process to the ballistic performance of the composition.
  • Example 4 of the method of compacting rollers and dry granulation induces an increase in the combustion rate to 20 MPa of the order of 20%. This increased speed is attributed to a better intimacy of the ingredients after passing through the compactor.
  • the roller compacting phase induces on the mixture compressive and shear stresses which improves the quality of the mixture. Tests conducted with various pressures on the compactor confirmed this point. To a certain extent, the ballistics of the formulation is therefore adjustable by the pressure applied to the rollers during the compaction phase.
  • roller compacting and granulation phase generates fines (small particle size) called ironings that can be reintroduced into the system.
  • This reintroduction further generates an increase in the burning rate, which can reach 40 mm / s at 20 MPa, in the case of the composition of Example 5 with 20% ironing.
  • Pyrotechnic compositions having the formulation specified in Table III below, were prepared by extrusion using 4% by weight of sodium carboxymethylcellulose as binder. The same process of kneading and continuous extrusion is implemented.
  • Example 6 the powders are directly introduced (with the binder) into the device.
  • Example 7 said powders were previously compacted and granulated under the conditions specified above for Example 5 and the resulting granules are introduced (with the binder) into the device.
  • the intervention of the binder is certainly detrimental to the performance, in terms of rate of combustion, of the composition (of Example 7 compared to that similar to Example 5).
  • the implementation of the roller compacting on the dry powders leads to significantly improve said combustion rate.
  • the gain obtained is of the same order of magnitude, namely about 20%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)

Abstract

The invention concerns gas generating pyrotechnical compositions, of which at least 95 wt. % of the fillers consist of the following component ingredients: a reducing filler in the form of at least one nitrogen-containing organic compound; an oxidizing filler in the form of at least one basic metal nitrate; and at least 30 wt. % of a second oxidizing filler in the form of at least one alkali metal perchlorate. Said compositions are obtained via a step of dry process roller compacting of a powdery mixture consisting essentially of said ingredients in powder form. The invention also concerns the method for obtaining said compositions. The inventive compositions have advantageous combustion rates.

Description

Composition pyrotechnique génératrice de gaz rapide et procédé d'obtention.Fast gas generating pyrotechnic composition and method of obtaining
La présente invention concerne la génération pyrotechnique de gaz, notamment pour gonfler des coussins utilisés dans les systèmes de protection des occupants d'un véhicule automobile. La présente invention concerne plus précisément des compositions pyrotechniques dites froides générant rapidement à des températures acceptables pour la sécurité automobiles (températures qualifiées de basses, c'est-à-dire inférieures à 2 200 K) des gaz propres et non toxiques. La présente invention concerne également un procédé d'obtention de telles compositions pyrotechniques.The present invention relates to the pyrotechnic generation of gas, in particular for inflating cushions used in occupant protection systems of a motor vehicle. The present invention more specifically relates to so-called cold pyrotechnic compositions rapidly generating at acceptable temperatures for automotive safety (qualified low temperatures, that is to say less than 2200 K) clean and non-toxic gases. The present invention also relates to a process for obtaining such pyrotechnic compositions.
Dans le cadre de la sécurité automobile, les compositions pyrotechniques employées dans les générateurs de gaz doivent fournir la quantité de gaz nécessaire à la mise en place du coussin gonflable en un temps extrêmement court, typiquement compris entre 10 et 40 millisecondes. En outre, les gaz générés doivent être propres, c'est-à-dire exempts de particules solides (susceptibles de constituer des points chauds pouvant endommager la paroi dudit coussin) et non toxiques, c'est-à-dire à faible teneur en monoxyde de carbone, en oxydes d'azote et en produits chlorés.In the context of automotive safety, the pyrotechnic compositions used in the gas generators must provide the quantity of gas required for the introduction of the airbag in an extremely short time, typically between 10 and 40 milliseconds. In addition, the gases generated must be clean, that is to say free of solid particles (which may constitute hot spots that may damage the wall of said cushion) and non-toxic, that is to say, low in content. carbon monoxide, nitrogen oxides and chlorinated products.
Divers types de compositions pyrotechniques ont déjà été proposés à ce jour.Various types of pyrotechnic compositions have already been proposed to date.
Actuellement, les compositions pyrotechniques qui semblent offrir le meilleur compromis en termes de température de gaz, de rendement gazeux, de taux de particules émises et de toxicité contiennent, comme ingrédients principaux, du nitrate de guanidine (NG) et du nitrate basique de cuivre (BCN). Le brevet US 5 608 183 décrit de telles compositions, obtenues par voie humide.Currently, the pyrotechnic compositions that appear to offer the best compromise in terms of gas temperature, gas yield, emitted particle content and toxicity contain, as main ingredients, guanidine nitrate (NG) and basic copper nitrate ( BCN). US Pat. No. 5,608,183 describes such compositions, obtained by wet process.
Ces compositions présentent toutefois l'inconvénient d'avoir des vitesses de combustion relativement faibles, inférieures ou égales à 20 mm/s à 20 MPa et d'être difficiles à allumer. De manière corollaire, elles sont très difficilement utilisables dans les générateurs hybrides et sides, qui nécessitent des temps de fonctionnement très courts, compris entre 10 et 20 millisecondes. On a proposé, selon l'art antérieur, d'ajouter des perchlorates à de telles compositions pyrotechniques à base de nitrate de guanidine (NG) et de nitrate basique de cuivre (BCN) :However, these compositions have the disadvantage of having relatively low combustion rates, less than or equal to 20 mm / s at 20 MPa and of being difficult to ignite. As a corollary, they are very difficult to use in hybrid generators and sides, which require very short operating times, between 10 and 20 milliseconds. It has been proposed, according to the prior art, to add perchlorates to such pyrotechnic compositions based on guanidine nitrate (NG) and basic copper nitrate (BCN):
- dans la demande de brevet EP 1 526 121, on décrit l'ajout d'un perchlorate (notamment du perchlorate de potassium), à faible tauxin the patent application EP 1 526 121, the addition of a perchlorate (in particular potassium perchlorate), at low
(moins de 5 % en masse), pour améliorer l'allumage desdites compositions et diminuer l'émission d'oxydes d'azote ;(less than 5% by weight), to improve the ignition of said compositions and to reduce the emission of nitrogen oxides;
- dans le brevet US 6 893 517, on décrit l'ajout d'un perchlorate (notamment du perchlorate de potassium), à des taux relativement élevés (entre 30 et 45 % en masse), pour accroître la vitesse de combustion desdites compositions. De tels taux de perchlorate induisent des températures de combustion élevées, d'environ 2 400 K. Les compositions pyrotechniques en cause ne peuvent plus être considérées comme froides, au regard de la non-agression des coussins gonflables par les gaz de combustion.in US Pat. No. 6,893,517, the addition of a perchlorate (especially potassium perchlorate) at relatively high levels (between 30 and 45% by weight) is described for increasing the rate of combustion of said compositions. Such levels of perchlorate induce high combustion temperatures of about 2400 K. The pyrotechnic compositions in question can no longer be considered cold, with regard to the non-aggression of the airbags by the combustion gases.
En référence au problème technique de l'augmentation de la vitesse de combustion de compositions pyrotechniques à base de nitrate de guanidine (NG) et de nitrate basique de cuivre (BCN), l'ajout d'un perchlorate n'est donc pas, perse, une solution satisfaisante. On connaît par ailleurs le procédé de compactage à rouleaux et granulation par voie sèche, mis en œuvre dans différents contextes, pour conditionner des poudres, généralement des mélanges de poudres. De tels mélanges de poudres, issus d'un mélangeur de poudres à sec, sont transportés, par exemple par une vis de dosage, pour alimenter un compacteur à cylindres. Un tel compacteur est composé de deux cylindres rotatifs, mis en rotation à une vitesse définie, en sens inverse. Le mélange de poudre est poussé par la vis de dosage entre lesdits deux cylindres. Un effort connu est appliqué sur les cylindres. Ainsi, la matière qui passe entre eux, à un débit donné, est-elle compactée sous la forme d'une plaque plane. Une telle opération engendre sur le mélange un fort taux de compression et de cisaillement qui améliore l'intimité entre les constituants. Le produit compacté, issu du compacteur est ensuite cassé et forcé à travers une râpe pour générer des granulés. De tels granulés se révèlent en général d'une manipulation plus aisée que les poudres de départ. Un dispositif unique assure généralement successivement le compactage et la granulation.With reference to the technical problem of increasing the burning rate of pyrotechnic compositions based on guanidine nitrate (NG) and basic copper nitrate (BCN), the addition of a perchlorate is therefore not, Persian , a satisfactory solution. Also known is the process of compacting rollers and dry granulation, implemented in different contexts, for conditioning powders, generally powder mixtures. Such powder mixtures, derived from a dry powder mixer, are transported, for example by a dosing screw, to feed a roller compactor. Such a compactor is composed of two rotating cylinders, rotated at a defined speed in the opposite direction. The powder mixture is pushed by the metering screw between said two cylinders. A known effort is applied on the cylinders. Thus, the material passing between them, at a given flow rate, is compacted in the form of a flat plate. Such an operation generates on the mixture a high compression and shear rate which improves the intimacy between the constituents. The compacted product from the compactor is then broken and forced through a rasp to generate pellets. Such granules generally prove to be easier to handle than the powders of departure. A single device generally provides compacting and granulation successively.
Dans le cadre de la présente invention, l'inventeur a montré, en référence au problème technique de l'augmentation de la vitesse de combustion, le grand intérêt qu'il y a à mettre en œuvre un compactage à rouleaux à sec dans le contexte de l'élaboration de compositions pyrotechniques du type nitrate de guanidine et nitrate basique de cuivre. Une réelle synergie a, de façon surprenante, été observée ; l'effet positif (sur la vitesse de combustion) dû à l'intervention d'une quantité limitée de perchlorate (sans effet dommageable sur la température de combustion) est potentialisé par la mise en œuvre du compactage à rouleaux à sec; mise en œuvre qui, per se, en l'absence de perchlorate, n'a pas d'effet substantiel. A l'appui de cette affirmation, les données comparatives ci- après peuvent être fournies, de vitesse de combustion à 20 MPa : NG + BCN < 20 mm/sIn the context of the present invention, the inventor has shown, with reference to the technical problem of increasing the rate of combustion, the great interest in implementing dry roller compacting in the context of the invention. the development of pyrotechnic compositions of the guanidine nitrate and basic nitrate copper type. A real synergy has, surprisingly, been observed; the positive effect (on the rate of combustion) due to the intervention of a limited quantity of perchlorate (with no detrimental effect on the combustion temperature) is potentiated by the implementation of dry roller compaction; implementation which, per se, in the absence of perchlorate, has no substantial effect. In support of this statement, the following comparative data can be provided, burning rate at 20 MPa: NG + BCN <20 mm / s
NG + BCN + compactage 20 - 22 mm/sNG + BCN + compaction 20 - 22 mm / s
NG + BCN + KCIO4 (exemple 4 ci-après) 32 mm/sNG + BCN + KCIO 4 (example 4 below) 32 mm / s
NG + BCN + KCIO4 + compactage (exemple 5 ci-après) 38,2 mm/s. Selon son premier objet, la présente invention concerne donc des compositions pyrotechniques génératrices de gaz qui associent deux caractéristiques. Lesdites compositions pyrotechniques de gaz :NG + BCN + KCIO 4 + compaction (Example 5 below) 38.2 mm / s. According to its first object, the present invention thus relates to pyrotechnic gas generating compositions which combine two characteristics. Said pyrotechnic gas compositions:
+ renferment, à titre d'ingrédients (actifs) constitutifs principaux :+ contain, as main constituent ingredients (active ingredients):
- une charge réductrice sous la forme d'au moins un composé organique azoté ;a reducing charge in the form of at least one nitrogenous organic compound;
- une charge oxydante sous la forme d'au moins un nitrate basique de métal ; etan oxidizing charge in the form of at least one basic metal nitrate; and
- moins de 30 % en masse d'une seconde charge oxydante sous la forme d'au moins un perchlorate de métal alcalin, lesdites charges représentant au moins 95 % en masse (généralement au moins 98 % en masse) des charges présentes ; etless than 30% by weight of a second oxidizing charge in the form of at least one alkali metal perchlorate, said charges representing at least 95% by weight (generally at least 98% by mass) of the charges present; and
+ sont obtenues via une étape de compactage à rouleaux en voie sèche d'un mélange pulvérulent essentiellement constitué desdits ingrédients en poudre. Les compositions pyrotechniques de l'invention, renfermant une charge réductrice spécifique (sous la forme d'au moins un composé organique azoté) et une charge oxydante spécifique (sous la forme d'au moins un nitrate basique de métal), renferment une quantité limitée d'une seconde charge oxydante spécifique (sous la forme d'au moins un perchlorate de métal alcalin) et sont obtenues à l'issue d'un procédé qui inclut une étape de compactage à rouleaux à sec du mélange pulvérulent incluant lesdites charges réductrice et oxydantes spécifiques.+ are obtained via a step of dry roller compacting a powder mixture consisting essentially of said powdered ingredients. The pyrotechnic compositions of the invention, containing a specific reducing charge (in the form of at least one nitrogen-containing organic compound) and a specific oxidizing charge (in the form of at least one basic metal nitrate), contain a limited quantity of a second specific oxidizing charge (in the form of at least one alkali metal perchlorate) and are obtained from a process which includes a step of dry-roller compaction of the powder mixture including said reducing and specific oxidants.
Le compactage à rouleaux à sec est mis en œuvre, de façon connue per se, dans un compacteur à cylindres, généralement à une pression de compactage comprise entre 108 et 6.108 Pa.Dry roll compacting is carried out, in a known manner, in a roller compactor, generally at a compacting pressure of 10 8 to 6.10 8 Pa.
Le procédé d'obtention des compositions pyrotechniques de l'invention qui, de façon caractéristique, inclut une étape de compactage à rouleaux à sec, est décrit en détail plus avant dans le présent texte. II peut être mis en œuvre selon différentes variantes (avec une étape caractéristique de compactage à rouleaux "simple" suivie d'au moins une étape complémentaire, avec une étape caractéristique de compactage à rouleaux couplée à une étape de mise en forme...) et les compositions pyrotechniques de l'invention existent donc sous différentes formes. En fait :The method for obtaining the pyrotechnic compositions of the invention which typically includes a dry roll compacting step is further described in the present text. It can be implemented according to different variants (with a "simple" roller compacting characteristic step followed by at least one complementary step, with a roller compacting step coupled to a shaping step). and the pyrotechnic compositions of the invention therefore exist in different forms. In fact :
- à l'issue du compactage à rouleaux à sec couplé à une mise en forme (par utilisation d'au moins un cylindre de compactage, dont la surface externe présente des alvéoles), on obtient des plaques avec motifs en relief que l'on peut casser pour l'obtention directe d'objets pyrotechniques formés ;- At the end of the dry roller compacting coupled with shaping (using at least one compacting cylinder, the outer surface of which has cavities), plates with relief patterns are obtained. can break for direct obtaining pyrotechnic objects formed;
- à l'issue du compactage à rouleaux à sec suivi d'une granulation, on obtient des granulés ;- After dry roller compacting followed by granulation, granules are obtained;
- à l'issue du compactage à rouleaux à sec suivi d'une granulation puis d'un pastillage (compression à sec), on obtient des pastilles ;- After dry roller compacting followed by granulation and then pelletization (dry compression), pellets are obtained;
- à l'issue du compactage à rouleaux à sec suivi d'une granulation puis du mélange des granulés obtenus avec un liant extrudable et de l'extrusion dudit liant chargé en lesdits granulés, on obtient des blocs monolithiques extrudés (chargés soit en lesdits granulés). Les compositions pyrotechniques de l'invention sont donc susceptibles d'exister sous la forme ;at the end of the dry-roller compacting followed by granulation and then the mixture of the granules obtained with an extrudable binder and the extrusion of said binder loaded into said granules, extruded monolithic blocks (loaded either in said granules) are obtained; ). The pyrotechnic compositions of the invention are therefore likely to exist in the form;
- d'objets formés, directement issus du compactage à rouleaux (couplé à une mise en forme); - de granulés ;- formed objects, directly from roller compaction (coupled with a shaping); - granules;
- de pastilles ; et- pellets; and
- de blocs monolithiques extrudés (chargés en granulés). De façon nullement limitative, on peut indiquer ici :- Extruded monolithic blocks (loaded in granules). In no way limiting, we can indicate here:
- que les granulés selon l'invention présentent généralement une granulométrie (un diamètre médian) comprise entre 200 et 800 μmthat the granules according to the invention generally have a particle size (a median diameter) of between 200 and 800 μm
(ainsi qu'une masse volumique apparente comprise entre 0,8 et 1,2 cm3/g) ;(and a bulk density of between 0.8 and 1.2 cm 3 / g);
- que les pastilles selon l'invention présentent généralement une épaisseur comprise entre 1 et 3 mm ; et - qu'au sein des blocs monolithiques extrudés, on trouve les granulés dans un liant (un gel) sec.the pellets according to the invention generally have a thickness of between 1 and 3 mm; and that within the extruded monolithic blocks, the granules are found in a dry binder (gel).
On peut également indiquer ici que font notamment partie du premier objet de l'invention :It may also be indicated here that part of the first object of the invention is in particular:
- des pastilles dont la température de combustion est inférieure à 2 200 K, la vitesse de combustion à 20 MPa est supérieure à 30 mm/s et la balance en oxygène comprise entre -2 et -4 % ;pellets whose combustion temperature is below 2200 K, the combustion rate at 20 MPa is greater than 30 mm / s and the oxygen balance is between -2 and -4%;
- des blocs monolithiques extrudés dont la température de combustion est inférieure à 2 200 K, la vitesse de combustion à 20 MPa est supérieure à 24 mm/s et la balance en oxygène comprise entre -2 et -4 %.- Extruded monolithic blocks whose combustion temperature is less than 2200 K, the combustion rate at 20 MPa is greater than 24 mm / s and the oxygen balance between -2 and -4%.
On se propose maintenant d'apporter quelques précisions, non limitatives, sur les ingrédients constitutifs des compositions pyrotechniques de l'invention et leur taux d'intervention au sein desdites compositions. Le au moins un composé organique azoté, constitutif de la charge réductrice, peut notamment être choisi parmi le nitrate de guanidine, la nitroguanidine, le guanyl urée dinitramide et leurs mélanges. Il consiste avantageusement en le nitrate de guanidine (NG).It is now proposed to provide some nonlimiting details on the constituent ingredients of the pyrotechnic compositions of the invention and their rate of intervention within said compositions. The at least one nitrogenous organic compound constituting the reducing charge can be chosen in particular from guanidine nitrate, nitroguanidine, guanyl urea dinitramide and mixtures thereof. It consists advantageously of guanidine nitrate (NG).
Le au moins un nitrate basique de métal, constitutif de la (première) charge oxydante peut notamment être choisi parmi le nitrate basique de cuivre, le nitrate basique de zinc, le nitrate basique de bismuth et leurs mélanges. Il consiste avantageusement en le nitrate basique de cuivre (BCN).The at least one basic metal nitrate constituting the (first) oxidizing charge can be chosen in particular from nitrate basic copper, basic zinc nitrate, basic bismuth nitrate and their mixtures. It consists advantageously of the basic nitrate of copper (BCN).
Le au moins un perchlorate de métal alcalin peut notamment être choisi parmi le perchlorate de potassium, le perchlorate de sodium et leurs mélanges. Il consiste avantageusement en le perchlorate de potassium (KCIO4).The at least one alkali metal perchlorate may in particular be chosen from potassium perchlorate, sodium perchlorate and mixtures thereof. It consists advantageously of potassium perchlorate (KCIO 4 ).
Selon une variante préférée, les ingrédients constitutifs principaux des compositions de l'invention sont donc : - le nitrate de guanidine (NG)According to a preferred variant, the main constitutive ingredients of the compositions of the invention are therefore: guanidine nitrate (NG)
- le nitrate basique de cuivre (BCN) et- basic copper nitrate (BCN) and
- le perchlorate de potassium (KCIO4).potassium perchlorate (KCIO 4 ).
Pour ce qui concerne les quantités respectives de chacun desdits ingrédients, on a généralement, indépendamment et avantageu- sèment en combinaison :With regard to the respective amounts of each of said ingredients, there is generally, independently and advantageously in combination:
- ledit au moins un composé organique azoté présent à raison de 45 à 65 % en masse ;said at least one nitrogen-containing organic compound present in a proportion of 45 to 65% by weight;
- ledit au moins un nitrate basique de métal présent à raison de 15 à 35 % en masse ; - ledit au moins un perchlorate de métal alcalin (comme déjà indiqué, présent à moins de 30 % en masse. Son action bénéfique sur la vitesse de combustion s'exprime alors, avec potentialisation du fait du procédé de compactage, de façon appréciable et ceci sans élévation conséquente et préjudiciable de la température de combustion) présent à raison de 10 à 25 % en masse, avantageusement de 10 à 20 % en masse. Selon une variante préférée, les compositions pyrotechniques de l'invention renferment ;said at least one basic metal nitrate present in a proportion of 15 to 35% by weight; said at least one alkali metal perchlorate (as already indicated, present at less than 30% by weight) Its beneficial action on the rate of combustion is then expressed, with potentiation due to the compaction process, appreciably and this without a consequent and detrimental elevation of the combustion temperature) present in a proportion of 10 to 25% by weight, advantageously 10 to 20% by mass. According to a preferred variant, the pyrotechnic compositions of the invention contain;
- de 45 à 65 % en masse de nitrate de guanidine (NG),from 45 to 65% by weight of guanidine nitrate (NG),
- de 15 à 35 % en masse de nitrate basique de cuivre (BCN), - de 10 à 25 % en masse de perchlorate de potassium (KCIO4).from 15 to 35% by mass of basic copper nitrate (BCN), from 10 to 25% by weight of potassium perchlorate (KCIO 4 ).
Les compositions pyrotechniques de l'invention, sous forme d'objets formés, de granulés et pastilles, consistent essentiellement (à au moins 95 % en masse, généralement à au moins 98 % en masse) voire exclusivement (à 100 % en masse) en les ingrédients constitutifs principaux (charges) identifiés ci-dessus : ledit au moins un composé organique azoté, ledit au moins un nitrate basique de métal et ledit au moins un perchlorate de métal alcalin. Lesdits ingrédients peuvent en effet à eux seuls constituer à 100 % les charges desdites compositions pyrotechniques (c'est généralement le cas), voire constituer à 100 % lesdites compositions pyrotechniques. Il ne saurait toutefois être exclu la présence, au sein des compositions de l'invention, d'autres charges en des quantités minimales (en tout état de cause, les charges identifiées ci- dessus représentent au moins 95 % en masse, généralement au moins 98 % en masse des charges présentes) et/ou celle d'au moins un additif (type auxiliaire de fabrication).The pyrotechnic compositions of the invention, in the form of formed articles, granules and pellets, consist essentially of (at least 95% by weight, generally at least 98% by weight) or even exclusively (at 100% by weight), the principal constitutive ingredients (charges) identified above: said at least one compound nitrogenous organic compound, said at least one basic metal nitrate and said at least one alkali metal perchlorate. Said ingredients can in fact alone constitute 100% the charges of said pyrotechnic compositions (this is generally the case), or even constitute 100% said pyrotechnic compositions. However, the presence in the compositions of the invention of other charges in minimum quantities can not be ruled out (in any event, the charges identified above represent at least 95% by mass, generally at least 98% by weight of the charges present) and / or that of at least one additive (auxiliary type of manufacture).
Les compositions pyrotechniques de l'invention, sous forme de blocs monolithiques extrudés, renferment les ingrédients constitutifs principaux (charges) identifiés ci-dessus (plus éventuellement, d'autres charges en des quantités minimales) dans un gel sec. Ce gel, extrudable per se ou mélangé à un solvant, est intervenu en amont pour permettre l'extrusion. Il est intervenu en quantité efficace (pour permettre l'extrusion) mais limité de sorte à ne pas affecter considérablement les performances des compositions de l'invention.The pyrotechnic compositions of the invention, in the form of extruded monolithic blocks, contain the main constituent ingredients (fillers) identified above (plus possibly other fillers in minimum amounts) in a dry gel. This gel, extrudable per se or mixed with a solvent, is used upstream to allow extrusion. It has intervened in an effective amount (to allow extrusion) but limited so as not to significantly affect the performance of the compositions of the invention.
Les blocs monolithiques extrudés de l'invention ne renferment généralement pas plus de 10 % en masse d'un tel gel sec. Ils en renferment avantageusement de 4 à 6 % en masse. En leur sein, la synergie de l'invention se développe avec la même intensité.The extruded monolithic blocks of the invention generally do not contain more than 10% by weight of such a dry gel. They contain advantageously from 4 to 6% by weight. Within them, the synergy of the invention develops with the same intensity.
La présence d'au moins un additif n'est également pas exclue de ce contexte. Les ingrédients constitutifs principaux (charges) et le gel sec représentent généralement au moins 95 % en masse, très généralement au moins 98 % en masse (voire 100 % en masse) desdites compositions.The presence of at least one additive is also not excluded from this context. The main constituent ingredients (fillers) and the dry gel generally represent at least 95% by weight, very generally at least 98% by weight (or even 100% by weight) of said compositions.
Pour ce qui concerne la nature dudit gel, elle n'est pas per se originale. Ledit gel est généralement choisi parmi les gels cellulosiques, les gels obtenus à partir d'élastomères acryliques, de copolymères éthylène- vinyl-acétate à fort taux d'acétate (renfermant plus de 60% en masse de motifs acétate), de polymères polyester, et leurs mélanges. Ledit gel consiste avantageusement en un gel de carboxyméthylcellulose de sodium.As regards the nature of said gel, it is not per se original. Said gel is generally chosen from cellulosic gels, gels obtained from acrylic elastomers, ethylene-vinyl-acetate copolymers with a high acetate content (containing more than 60% by weight of acetate units), polyester polymers, and their mixtures. Said gel advantageously consists of a sodium carboxymethylcellulose gel.
Selon son second objet, la présente invention concerne le procédé d'obtention de compositions pyrotechniques telles que décrites ci-dessus ; procédé qui comprend, de façon caractéristique, le compactage à sec de poudres.According to its second subject, the present invention relates to the process for obtaining pyrotechnic compositions as described above; a process which typically includes dry compacting of powders.
Ledit procédé comprend en fait :The method comprises:
- le mélange à sec de poudres (de charges) consistant pour au moins 95 % en masse en une charge réductrice pulvérulente sous la forme d'au moins un composé organique azoté, une charge oxydante pulvérulente sous la forme d'au moins un nitrate basique de métal et moins de 30 % en masse d'une seconde charge oxydante pulvérulente sous la forme d'au moins un perchlorate de métal alcalin ; et - le compactage à rouleaux à sec du mélange de poudres résultant.- the dry mixture of powders (of fillers) consisting of at least 95% by weight of a pulverulent reducing filler in the form of at least one nitrogenous organic compound, a pulverulent oxidizing filler in the form of at least one basic nitrate of metal and less than 30% by weight of a second powdery oxidizing charge in the form of at least one alkali metal perchlorate; and dry-roller compacting the resulting powder mixture.
Des précisions sur la nature des ingrédients en cause et leur taux de présence respectif ont été données en amont dans le présent texte. Les ingrédients constitutifs des compositions pyrotechniques recherchées interviennent à l'état de poudres. Avantageusement, lesdites poudres présentent une granulométrie fine, inférieure ou égale à 40 μm. Ladite granulométrie (valeur du diamètre médian) est généralement comprise entre 3 et 40 μm. Les étapes de mélange à sec des poudres et de compactage à rouleaux à sec du mélange obtenu sont mises en œuvre de façon classique. Pour ce qui concerne le compactage à rouleaux à sec, on a vu qu'il est mis en œuvre par passage du mélange des poudres entre deux cylindres, la pression exercée étant alors généralement comprise entre 108 et 6.108 Pa. On met en œuvre un compactage "simple" avec deux cylindres présentant des surfaces externes non usinées ou un compactage couplé à une mise en forme avec des cylindres, dont la surface externe d'au moins l'un des deux est usinée pour présenter des alvéoles.Details of the nature of the ingredients involved and their respective presence rates have been given earlier in this text. The constitutive ingredients of the desired pyrotechnic compositions occur in the form of powders. Advantageously, said powders have a fine particle size, less than or equal to 40 microns. Said particle size (value of the median diameter) is generally between 3 and 40 microns. The dry powder mixing and dry roll compacting steps of the resulting mixture are carried out in a conventional manner. With regard to dry roller compaction, it has been seen that it is implemented by passing the mixture of powders between two rolls, the pressure exerted then generally being between 10 8 and 6.10 8 Pa. a "simple" compaction with two cylinders having unmachined external surfaces or compaction coupled to a shaping with cylinders, the outer surface of at least one of which is machined to have cavities.
On rappelle incidemment ici que l'originalité de l'invention revendiquée ne repose pas sur l'originalité per se du procédé en cause mais sur l'originalité de la mise en œuvre dudit procédé avec des mélanges de poudres particuliers.Incidentally, it is recalled here that the originality of the claimed invention does not rest on the originality per se of the process in question but on the originality of the implementation of said process with particular powder mixtures.
Le procédé de l'invention peut se limiter à ces deux étapes successives de mélange et de compactage à rouleaux à sec, dans le contexte ci-après : celui de l'obtention directe d'objets formés, dans l'hypothèse de la mise en œuvre d'un compactage à rouleaux couplé à une mise en forme (la surface externe d'au moins l'un des cylindres de compactage présentant des alvéoles).The process of the invention can be limited to these two successive stages of mixing and compacting with dry rollers, in the following context: that of the direct obtaining of formed objects, in the assumption of the implementation of a roller compacting coupled to a shaping (the outer surface of at least one of the compacting rolls having cells).
Le procédé de l'invention, outre lesdites deux étapes de mélange et de compactage à rouleaux à sec ("simple"), peut inclure : a) une étape de granulation à sec (le mélange de poudres compacté est forcé mécaniquement par un rotor à travers une râpe exerçant la fonction de tamis dont la maille varie généralement de 500 μm à 3 mm). Le compactage à rouleaux et la granulation peuvent être mis en œuvre au sein d'un unique dispositif ou au sein de deux dispositifs indépendants. Les compositions pyrotechniques obtenues se présentent alors sous la forme de granulés (voir ci-dessus) ; b) une étape de granulation à sec (voir ci-dessus) suivie d'un pastillage (compression à sec pendant laquelle les granulés subissent une pression généralement comprise entre 4.108 et 109 Pa. On note incidemment ici que l'alimentation des empreintes de pastillages est beaucoup plus aisément mise en œuvre avec les granulés qu'avec les poudres de départ). Les compositions pyrotechniques obtenues se présentent alors sous la forme de pastilles (voir ci-dessus) ; c) une étape de granulation à sec (voir ci-dessus) suivi du mélange des granulés obtenus avec un liant extrudable et de l'extrusion dudit mélange. Les compositions pyrotechniques finalement obtenues se présentent sous la forme de blocs monolithiques extrudés chargées en granulés. Les variantes du procédé de l'invention qui incluent les étapes b) et c) ci-dessus sont particulièrement préférées. Dans le cadre desdites deux variantes, le procédé de l'invention inclut les étapes de compactage à rouleaux ("simple") et granulation à sec du mélange des poudres de départ. Quelle que soit la variante exacte de mise en œuvre du procédé de l'invention, il s'est révélé opportun, notamment en référence à l'augmentation de la vitesse de combustion de la composition pyrotechnique préparée, de recycler au moins en partie les fines ou repasses générées à l'étape de compactage et/ou à celle de granulation, lorsque ladite étape de granulation est mise en œuvre. On préconise la mise en œuvre de taux de repasse compris entre 10 et 30%.The method of the invention, in addition to said two dry ("simple") dry roll mixing and compaction steps, may include: a) a dry granulation step (the compacted powder mixture is mechanically forced by a wet rotor; through a rasp exercising the sieve function whose mesh generally ranges from 500 microns to 3 mm). Roller compaction and granulation can be implemented in a single device or in two independent devices. The pyrotechnic compositions obtained are then in the form of granules (see above); b) a dry granulation step (see above) followed by pelletizing (dry compression during which the granules undergo a pressure generally between 4.10 8 and 10 9 Pa. It is noted here incidentally that the feeding of the prints pellets is much more easily implemented with the granules than with the starting powders). The pyrotechnic compositions obtained are then in the form of pellets (see above); c) a dry granulation step (see above) followed by mixing the granules obtained with an extrudable binder and extruding said mixture. The pyrotechnic compositions finally obtained are in the form of extruded monolithic blocks loaded with granules. Variants of the process of the invention which include steps b) and c) above are particularly preferred. In the context of said two variants, the method of the invention includes the steps of compacting rollers ("simple") and dry granulation of the mixture of starting powders. Whatever the exact variant of implementation of the method of the invention, it has been found advisable, particularly with reference to increasing the burning rate of the prepared pyrotechnic composition, to recycle at least part of the fines. or ironings generated in the compaction and / or granulation stage, when said granulation step is carried out. It is recommended the implementation of ironing rates between 10 and 30%.
L'invention est maintenant illustrée, de façon nullement limitative, par les exemples ci-après. Plus précisément, des exemples, illustrant deux variantes de l'invention (compositions pyrotechniques sous la forme de pastilles (exemple 5) et de blocs monolithiques extrudés (exemple 7)), sont proposés, à considérer en parallèle avec des exemples comparatifs.The invention is now illustrated, in no way limiting, by the examples below. More specifically, examples illustrating two variants of the invention (pyrotechnic compositions in the form of pellets (Example 5) and extruded monolithic blocks (Example 7)) are proposed, to be considered in parallel with comparative examples.
Les poudres (matières premières) utilisées présentent une granulométrie fine : un diamètre médian d'environ 20 μm pour KCIO4, 4,5 μm pour BCN, 10 μm pour NG.The powders (raw materials) used have a fine grain size: a median diameter of approximately 20 μm for KCIO 4 , 4.5 μm for BCN, 10 μm for NG.
De telles poudres ne s'écoulent pas et ne sont donc pas, per se, utilisables en pastillage industriel (il est très difficile de remplir les empreintes de pastillage).Such powders do not flow and are therefore not, per se, used in industrial pelletization (it is very difficult to fill the pelletizing prints).
Le tableau I présenté ci-dessous montre des exemples de formulation ainsi que les performances thermodynamiques et balistiques de pastilles (d'environ 2 mm d'épaisseur) obtenues par pastillage (mis en œuvre à 5.108 Pa) des mélanges de poudre non préalablement compactées.Table I presented below shows examples of formulation as well as the thermodynamic and ballistic performances of pellets (about 2 mm thick) obtained by pelletizing (carried out at 5.10 8 Pa) of previously uncompressed compacted powder mixtures. .
Tableau I (pastillage direct)Table I (direct pelleting)
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000011_0001
Figure imgf000012_0001
* Vc ≈ Vitesse de combustion ** OB = balance en oxygène* Vc ≈ Burning rate ** OB = oxygen balance
• La composition de l'exemple 4, qui offre le meilleur compromis entre vitesse de combustion, rendement gazeux et température de combustion, a été conditionnée, pour l'exemple 5, par mise en œuvre d'un procédé de compactage à rouleaux (pression entre les rouleaux de 4.108 Pa) et granulation (forçage de la matière compactée par un rotor au travers d'une râpe équivalente à un tamis présentant une maille d'environ 1 mm) voie sèche, en amont du pastillage. Les granulés obtenus, à l'issue de l'étape de compactage à rouleaux et granulation, présentaient une granulométrie médiane d'environ 500 μm. Ils ont été pastillés (aisément, dans la mesure où il n'y a plus de problème d'écoulement) dans les mêmes conditions que les poudres des exemples 1 à 4 (pression de 5.108 Pa).The composition of Example 4, which offers the best compromise between combustion rate, gas yield and combustion temperature, was conditioned, for example 5, by implementing a roller compacting process (pressure between the rolls of 4.10 8 Pa) and granulation (forcing the compacted material by a rotor through a rasp equivalent to a sieve having a mesh of about 1 mm) dry process, upstream of the pelletizing. The granules obtained at the end of the roller compacting and granulation stage had a median particle size of approximately 500 μm. They were pelletized (easily, to the extent that there is no more flow problem) under the same conditions as the powders of Examples 1 to 4 (pressure of 5.10 8 Pa).
Le tableau II présenté ci-dessous montre l'apport du procédé de compactage à rouleaux sur les performances balistiques de la composition.Table II presented below shows the contribution of the roller compacting process to the ballistic performance of the composition.
Tableau IITable II
Figure imgf000012_0002
L'application à la composition suivant l'exemple 4 du procédé de compactage à rouleaux et de granulation voie sèche induit un accroissement de la vitesse de combustion à 20 MPa de l'ordre de 20 %. Cette vitesse accrue est attribuée à une meilleure intimité des ingrédients après passage dans le compacteur. La phase de compactage à rouleaux induit sur le mélange des contraintes de compression et de cisaillement qui améliore la qualité du mélange. Des essais conduits avec diverses pressions sur le compacteur ont permis de confirmer ce point. Dans une certaine mesure, la balistique de la formulation est donc réglable par la pression appliquée sur les rouleaux lors de la phase de compactage.
Figure imgf000012_0002
Application to the composition according to Example 4 of the method of compacting rollers and dry granulation induces an increase in the combustion rate to 20 MPa of the order of 20%. This increased speed is attributed to a better intimacy of the ingredients after passing through the compactor. The roller compacting phase induces on the mixture compressive and shear stresses which improves the quality of the mixture. Tests conducted with various pressures on the compactor confirmed this point. To a certain extent, the ballistics of the formulation is therefore adjustable by the pressure applied to the rollers during the compaction phase.
En outre, la phase de compactage à rouleaux et de granulation génère des fines (de faible granulométrie) appelées repasses qui peuvent être réintroduites dans le système. Cette réintroduction génère encore une augmentation de la vitesse de combustion, qui peut atteindre 40 mm/s à 20 MPa, dans le cas de la composition de l'exemple 5 avec 20% de repasse.In addition, the roller compacting and granulation phase generates fines (small particle size) called ironings that can be reintroduced into the system. This reintroduction further generates an increase in the burning rate, which can reach 40 mm / s at 20 MPa, in the case of the composition of Example 5 with 20% ironing.
• Des compositions pyrotechniques, présentant la formulation précisée dans le tableau III ci-après, ont été préparées par extrusion en faisant intervenir 4 % en masse de carboxyméthylcellulose de sodium à titre de liant. Le même procédé de malaxage et extrusion en continu est mis en œuvre.Pyrotechnic compositions, having the formulation specified in Table III below, were prepared by extrusion using 4% by weight of sodium carboxymethylcellulose as binder. The same process of kneading and continuous extrusion is implemented.
Selon l'exemple 6, les poudres sont directement introduites (avec le liant) dans le dispositif. Selon l'exemple 7, lesdites poudres ont été préalablement compactées et granulées dans les conditions précisées ci-dessus pour l'exemple 5 et les granulés résultants sont introduits (avec le liant) dans le dispositif.According to Example 6, the powders are directly introduced (with the binder) into the device. According to Example 7, said powders were previously compacted and granulated under the conditions specified above for Example 5 and the resulting granules are introduced (with the binder) into the device.
Les performances des deux compositions, conditionnées sous la forme de blocs monolithiques, figurent également dans le tableau III ci- dessous. Tableau IIIThe performances of the two compositions, packaged in the form of monolithic blocks, are also shown in Table III below. Table III
Figure imgf000014_0001
Figure imgf000014_0001
Densité théorique 1,88 1,88 Exposant de pression 0,44 0,42 Vc à 20 MPa (mm/s) 24,2 28,8Theoretical Density 1.88 1.88 Pressure Exponent 0.44 0.42 Vc at 20 MPa (mm / s) 24.2 28.8
OB (%) -3,2 -3,2OB (%) -3.2 -3.2
T combustion à 20 MPa (K) 2078 2078 Rendement gazeux à 1000 KT combustion at 20 MPa (K) 2078 2078 Gaseous yield at 1000 K
(mole/kg) 28,8 28,8 Taux de résidus solides (%) 27 27(mole / kg) 28.8 28.8 Solid residue rate (%) 27 27
L'intervention du liant est certes préjudiciable à la performance, en terme de vitesse de combustion, de la composition (de l'exemple 7 par rapport à celle similaire de l'exemple 5). Toutefois, également dans ce contexte de produit extrudé (comme pour le produit pastillé), la mise en œuvre du compactage à rouleaux sur les poudres sèches conduit à améliorer significativement ladite vitesse de combustion. Le gain obtenu est du même ordre de grandeur, à savoir d'environ 20 %. The intervention of the binder is certainly detrimental to the performance, in terms of rate of combustion, of the composition (of Example 7 compared to that similar to Example 5). However, also in this context of extruded product (as for the pelletized product), the implementation of the roller compacting on the dry powders leads to significantly improve said combustion rate. The gain obtained is of the same order of magnitude, namely about 20%.

Claims

REVENDICATIONS
1. Composition pyrotechnique génératrice de gaz, dont au moins 95 % en masse des charges sont constituées des ingrédients constitutifs ci-après :1. Pyrotechnic gas-generating composition, at least 95% by weight of the charges of which consist of the following constitutive ingredients:
- une charge réductrice sous la forme d'au moins un composé organique azoté ;a reducing charge in the form of at least one nitrogenous organic compound;
- une charge oxydante sous la forme d'au moins un nitrate basique de métal ; et - moins de 30 % en masse d'une seconde charge oxydante sous la forme d'au moins un perchlorate de métal alcalin ; et qui est obtenue via une étape de compactage à rouleaux en voie sèche d'un mélange pulvérulent essentiellement constitué desdits ingrédients en poudre. an oxidizing charge in the form of at least one basic metal nitrate; and less than 30% by weight of a second oxidizing charge in the form of at least one alkali metal perchlorate; and which is obtained via a dry roll compacting step of a powder mixture essentially consisting of said powdered ingredients.
2. Composition selon Ia revendication 1, se présentant sous la forme d'objets formés, de granulés, de pastilles ou de blocs monolithiques extrudés.2. Composition according to claim 1, which is in the form of shaped objects, granules, pellets or extruded monolithic blocks.
3. Composition selon la revendication 1 ou 2, caractérisée en ce que ledit au moins un composé organique azoté est choisi parmi le nitrate de guanidine, la nitroguanidine, le guanyl urée dinitramide et leurs mélanges ; en ce que ledit au moins un composé organique azoté consiste avantageusement en le nitrate de guanidïne.3. Composition according to claim 1 or 2, characterized in that said at least one nitrogenous organic compound is selected from guanidine nitrate, nitroguanidine, guanyl urea dinitramide and mixtures thereof; in that said at least one nitrogenous organic compound advantageously consists of guanidine nitrate.
4. Composition selon l'une quelconque des revendications 1 à 3, caractérisée en ce que ledit au moins un nitrate basique de métal est choisi parmi le nitrate basique de cuivre, le nitrate basique de zinc, le nitrate basique de bismuth et leurs mélanges ; en ce que ledit au moins un nitrate basique de métal consiste avantageusement en le nitrate basique de cuivre.4. Composition according to any one of claims 1 to 3, characterized in that said at least one basic metal nitrate is selected from basic copper nitrate, basic zinc nitrate, basic bismuth nitrate and mixtures thereof; in that said at least one basic metal nitrate advantageously consists of basic copper nitrate.
5. Composition selon l'une quelconque des revendications 1 à 4, caractérisée en ce que ledit au moins un perchlorate de métal alcalin est choisi parmi le perchlorate de potassium, le perchlorate de sodium et leurs mélanges ; en ce que ledit au moins un perchlorate de métal alcalin consiste avantageusement en le perchlorate de potassium. 5. Composition according to any one of claims 1 to 4, characterized in that said at least one alkali metal perchlorate is selected from potassium perchlorate, sodium perchlorate and mixtures thereof; in that said at least one alkali metal perchlorate is advantageously potassium perchlorate.
6. Composition selon l'une quelconque des revendications 1 à 5, caractérisée en ce que ledit au moins un composé organique azoté est présent en raison de 45 à 65 % en masse.6. Composition according to any one of claims 1 to 5, characterized in that said at least one nitrogenous organic compound is present at from 45 to 65% by weight.
7. Composition selon l'une quelconque des revendications 1 à 6, caractérisée en ce que ledit au moins un nitrate basique de métal est présent à raison de 15 à 35 % en masse.7. Composition according to any one of claims 1 to 6, characterized in that said at least one basic metal nitrate is present in a proportion of 15 to 35% by weight.
8. Composition selon l'une quelconque des revendications 1 à 7, caractérisée en ce que ledit au moins un perchlorate de métal alcalin est présent à raison de 10 à 25 % en masse. 8. Composition according to any one of claims 1 to 7, characterized in that said at least one alkali metal perchlorate is present in a proportion of 10 to 25% by weight.
9. Composition selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'elle se présente sous la forme de blocs monolithiques extrudés et en ce que lesdits blocs renferment jusqu'à 10 % en masse d'un gel sec.9. Composition according to any one of claims 1 to 8, characterized in that it is in the form of extruded monolithic blocks and in that said blocks contain up to 10% by weight of a dry gel.
10. Composition selon la revendication 9, caractérisée en ce que ledit gel est choisi parmi les gels cellulosiques, les gels obtenus à partir d'élastomères acryliques, de copolymères éthylène-vinyl-acétate à fort taux d'acétate, de polymères polyesters et leurs mélanges.10. The composition as claimed in claim 9, characterized in that said gel is chosen from cellulose gels, gels obtained from acrylic elastomers, ethylene-vinyl-acetate copolymers with a high acetate content, polyester polymers and their mixtures.
11. Composition selon la revendication 9 ou 10, caractérisée en ce que ledit gel est un gel de carboxyméthylœllulose de sodium. 11. The composition of claim 9 or 10, characterized in that said gel is a sodium carboxymethylcellulose gel.
12. Procédé d'obtention d'une composition pyrotechnique génératrice de gaz, caractérisé en ce qu'il comprend :12. Process for obtaining a pyrotechnic composition generating gas, characterized in that it comprises:
- le mélange à sec de poudres consistant pour au moins 95 % en masse en une charge réductrice pulvérulente sous la forme d'au moins un composé organique azoté, une charge oxydante pulvérulente sous la forme d'au moins un nitrate basique de métal et moins de 30 % en masse d'une seconde charge oxydante pulvérulente sous la forme d'au moins un perchlorate de métal alcalin ;the dry powder mixture consisting of at least 95% by weight of pulverulent reducing filler in the form of at least one nitrogenous organic compound, a pulverulent oxidizing filler in the form of at least one basic metal nitrate and less 30% by weight of a second powdery oxidizing charge in the form of at least one alkali metal perchlorate;
- le compactage à rouleaux à sec du mélange de poudres résultant. dry roller compacting of the resulting powder mixture.
13. Procédé selon la revendication 12, caractérisé en ce que lesdites poudres présentent une granulométrie inférieure ou égale à 40 μm.13. The method of claim 12, characterized in that said powders have a particle size less than or equal to 40 microns.
14. Procédé selon la revendication 12 ou 13, caractérisé en ce qu'il comprend en outre la granulation à sec du mélange de poudres compacté pour générer des granulés. 14. The method of claim 12 or 13, characterized in that it further comprises dry granulation compacted powder mixture to generate granules.
15. Procédé selon la revendication 14, caractérisé en ce qu'il comprend en outre le pastillage desdits granulés.15. The method of claim 14, characterized in that it further comprises pelletizing said granules.
16. Procédé selon la revendication 14, caractérisé en ce qu'il comprend en outre le mélange desdits granulés à un gel et l'extrusion dudit gel chargé desdits granulés.16. The method of claim 14, characterized in that it further comprises the mixture of said granules to a gel and the extrusion of said gel charged with said granules.
17. Procédé selon l'une quelconque des revendications 12 à 16, caractérisé en ce qu'il comprend le recyclage de repasses générées lors de la phase de compactage à sec et/ou lors de la phase de granulation. 17. Method according to any one of claims 12 to 16, characterized in that it comprises the recycling of ironings generated during the dry compaction phase and / or during the granulation phase.
PCT/FR2006/051026 2005-10-13 2006-10-12 Rapid gas generating pyrotechnical composition and method for obtaining same WO2007042735A2 (en)

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JP2008535078A JP5273609B2 (en) 2005-10-13 2006-10-12 High-speed gas generating agent and method for producing the same
EP06820288A EP1934158A2 (en) 2005-10-13 2006-10-12 Rapid gas generating pyrotechnical composition and method for obtaining same
CN200680043374.5A CN101312930B (en) 2005-10-13 2006-10-12 Rapid gas generating pyrotechnical composition and method for obtaining same

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FR2892117A1 (en) 2007-04-20
US20090308509A1 (en) 2009-12-17
JP5273609B2 (en) 2013-08-28
CN101312930A (en) 2008-11-26
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EP1934158A2 (en) 2008-06-25
WO2007042735A3 (en) 2007-06-21

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