EP0481838B1 - Insensitive ammunition containing an explosive multi-compositional charge and process for obtaining a blasting effect in water as well as in air - Google Patents

Insensitive ammunition containing an explosive multi-compositional charge and process for obtaining a blasting effect in water as well as in air Download PDF

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Publication number
EP0481838B1
EP0481838B1 EP91402612A EP91402612A EP0481838B1 EP 0481838 B1 EP0481838 B1 EP 0481838B1 EP 91402612 A EP91402612 A EP 91402612A EP 91402612 A EP91402612 A EP 91402612A EP 0481838 B1 EP0481838 B1 EP 0481838B1
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Prior art keywords
explosive
composite
charge
element according
load
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EP91402612A
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German (de)
French (fr)
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EP0481838A1 (en
Inventor
Michel Andre
Jean-Pierre Mazer
Bruno Nouguez
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Eurenco SA
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Societe Nationale des Poudres et Explosifs
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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
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones
    • C06B45/14—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones a layer or zone containing an inorganic explosive or an inorganic explosive or an inorganic thermic component

Definitions

  • the present invention is in the field of ammunition, in particular military, attenuated risks. It relates to a slightly vulnerable element of explosive ammunition consisting of a generally metallic envelope containing an explosive charge. This ammunition is particularly useful for generating a blast effect in the air or a bubble effect in the underwater environment.
  • the load and its envelope generally have an axial symmetry (surface of revolution), so as to generate symmetrical effects. Explosive ordnance, in particular during its storage or transport, can be subjected to attacks such as fire, impact and the penetration of fragments or bullets, detonation close to neighboring munitions.
  • composite explosive means a functionally detonable pyrotechnic composition, consisting of a solid polymer matrix, generally polyurethane or polyester, charged, said charge being pulverulent and containing predominantly an organic nitro explosive charge, for example l hexogen, octogen, ONTA, or a mixture of at least two of these compounds.
  • French patent FR 2 365 774 describes an approximately cylindrical element of explosive ammunition consisting of an envelope containing a multi-composition charge which may be a composite explosive.
  • This multi-composition charge comprises a plurality of adjacent coaxial annular layers, the peripheral layer having a content of powerful heavy explosive (hexogen, octogen) higher than that of the layer which is immediately adjacent to it and thus step by step up to the layer central axial which is full cylindrical and has the lowest content of heavy heavy explosive.
  • hexogen, octogen powerful heavy explosive
  • a person skilled in the art is therefore looking for a more satisfactory solution than those known above, making it possible to further reduce the vulnerability of the load, and better still that of the ammunition element consisting of said load and its priming relay. , while retaining the performance required in terms of the desired effect of breath and / or bubbles.
  • the present invention provides such a solution.
  • the Applicant has discovered that, unexpectedly, the vulnerability of an explosive ammunition element consisting of a generally and preferably metallic envelope containing a composite explosive consisting of a polyurethane or polyester polymer matrix loaded on the one hand, is reduced.
  • a powdery charge free of organic nitro explosive but comprising at least one mineral oxidant by distributing the organic nitro explosive and the charge free of organic nitro explosive in the polyurethane polymer matrix or polyester so as to produce a multi-composition charge, preferably bi-composition, the innermost layer of which is a composite explosive, the charge of which contains more than 40% by weight of organic nitro explosive, percentage expressed relative to the composite explosive , and whose peripheral layer is a pyrotechnic composition made up of a material this charged polyurethane or polyester polymer, said filler containing at least one mineral oxidant and less than 10% by weight of organic nitro explosive, percentage expressed relative to the pyrotechnic composition, while retaining practically the same level of performance, namely the same effect of breath and / or bubbles.
  • the pyrotechnic composition of the peripheral layer is from the family of composite solid propellants.
  • composite solid propellant is conventionally understood to mean a pyrotechnic composition used in the same way as that of a composite explosive, and consisting of a polymer matrix solid, generally polyurethane or polyester, charged, said charge being pulverulent and essentially consisting of a mineral oxidant and in general of a reducing metal.
  • the charge may also sometimes contain an organic nitro explosive.
  • solid composite propellants are functionally combustible and include various additives to control propulsion.
  • Composite solid propellants and how to obtain them are for example described by A. DAVENAS, Solid propellant technology, Ed. Masson, 1989.
  • the Applicant wishes not to qualify the peripheral layer of "Propellant” although the composition of this layer differs from that of the solid composite progergols only by the absence additives linked to the propellant function of the propellants (ballistic additives, combustion accelerators, etc.), and prefers to use the expression "Pyrotechnic composition of the family of solid composite propellants".
  • organic nitro explosive means an explosive chosen from the group consisting of explosives aromatic nitrates (comprising at least one C -NO2 group, the carbon atom being part of an aromatic ring), nitric ester explosives (comprising at least one C - O - NO2 group) and nitramine explosives (comprising at least a C - N - NO2 group).
  • this multicomposition configuration with a peripheral layer of pyrotechnic composition of the fault of the solid composite propellants whose charge contains at least one mineral oxidant and less than 10% by weight of organic nitro explosive, preferably 0%, gives the ammunition element a quasi-invulnerability to detonation close to neighboring munitions.
  • the element according to the invention is more easily bootable, by a relay in contact with the innermost layer of the multi-composition charge, than according to the massively equivalent configuration known from the prior art. Therefore, the element according to the invention can be initiated by a smaller relay which on the one hand further reduces the vulnerability of the envelope-load-relay assembly, and on the other hand allows the use explosives which are very difficult to initiate, which was previously prohibited because of the size of the priming relays required and the consequent risks.
  • the configuration according to the invention therefore simultaneously makes it possible to reduce the vulnerability of the load vis-à-vis detonation waves, generally lateral ones, caused by the detonation close to neighboring munitions, and to increase its frontal initiation eu with regard to a priming relay located on the axis of the load in contact with the innermost layer.
  • the present invention therefore relates to an explosive munition element consisting of a preferably metallic envelope containing a multicomposition explosive charge comprising a plurality of adjacent coaxial layers.
  • the envelope and each layer of the load may have any form of revolution, for example cylindrical, ovoid, ellipsoidal, spherical, conical or diabolo. All these forms may be only approximate.
  • the surfaces of revolution may in particular have irregularities, for example teeth or other recesses.
  • the layers may not be strictly coaxial.
  • the innermost layer is preferably full, but it can also have one or more recesses, for example a recess for housing the priming system.
  • the invention is characterized in that the innermost layer is a composite explosive consisting of a charged polyurethane or polyester polymer matrix, preferably polyurethane, the charge of which, pulverulent, contains an organic nitro explosive the content of which is greater than 40 % by weight with respect to the composite explosive, preferably between 40% and 90%, and in that the peripheral layer is a pyrotechnic composition from the family of solid composite propellants consisting of a charged polyurethane or polyester polymer matrix, preferably polyurethane, the pulverulent filler of which contains at least one inorganic oxidant and less than 10% by weight of organic nitro explosive, percentage expressed relative to the pyrotechnic composition of the family of solid composite propellants.
  • the explosive charge is a bi-composition charge, the internal layer being coated with an adjacent peripheral coaxial layer.
  • the intermediate layer or layers are preferably made of composite explosive, but certain layers, in particular those close to the peripheral layer, can be in pyrotechnic composition from the family of solid composite propellants.
  • the polymer matrix of the composite explosive constituting the innermost layer and the polymer matrix of the pyrotechnic composition constituting the peripheral layer of the charge are identical, preferably a polyurethane matrix.
  • the intermediate layers of composite explosive and / or of pyrotechnic composition from the family of solid composite propellants also have the same polymer matrix as the innermost layer and the peripheral layer.
  • the polymer matrices may optionally include a plasticizer, such as those usually used in the use of composite explosives and composite solid propellants.
  • the polyurethane polymer matrix is obtained by reaction of a prepolymer with hydroxyl endings with a polyisocyanate.
  • prepolymers with hydroxyl endings mention may be made of those whose backbone is a polyisobutylene, a polybutadiene, a polyether, a polyester, a polysiloxane.
  • polybutadiene with hydroxyl end groups is used.
  • polyisocyanates examples include isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexylmethylene diisocyanate (Hylene W), hexamethylene diisocyanate (HMDI), biuret trihexane isocyanate (BTHI), and mixtures thereof.
  • IPDI isophorone diisocyanate
  • TDI toluene diisocyanate
  • Hylene W dicyclohexylmethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • BTHI biuret trihexane isocyanate
  • the polymer matrix is a polyester matrix
  • a carboxyl-terminated prepolymer preferably a carboxyl-terminated polybutadiene (PBCT) or a carboxyl-terminated polyester
  • PBCT carboxyl-terminated polybutadiene
  • MAPO trimethylaziridinyl phosphine oxide
  • the charge of the pyrotechnic composition of the family of composite solid propellants constituting the peripheral layer contains an inorganic oxidant chosen from the group consisting of ammonium perchlorate, potassium perchlorate, nitrate of ammonium, sodium nitrate, and mixtures thereof, that is to say all mixtures of at least two aforementioned products.
  • the charge of the pyrotechnic composition of the family of solid composite propellants constituting the peripheral layer contains a reducing metal, preferably chosen from the group consisting of aluminum, zirconium, magnesium, boron and their mixtures , that is to say all mixtures of at least two of the four metals mentioned above.
  • the reducing metal is aluminum.
  • the charge of the pyrotechnic composition of the family of solid composite propellants constituting the peripheral layer is free of organic nitro explosive.
  • two particularly interesting sub-variants must be mentioned.
  • the charge of the pyrotechnic composition constituting the peripheral layer is a mineral charge, preferably chosen from the group consisting of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate and their mixtures.
  • the charge therefore does not contain any other compound.
  • the organic nitro explosive contained in the charge of the composite explosive constituting the innermost layer of the charge is chosen from the group consisting of hexogen, octogen, pentrite, 5-oxo 3-nitro 1,2,4-triazole, triaminotrinitrobenzene, nitroguanidine and their mixtures, that is to say all mixtures of at least two of the above-mentioned compounds.
  • this charge of organic nitro explosive is chosen from the group consisting of hexogen, octogen, 5-oxo 3-nitro 1,2,4-triazole and their mixtures.
  • the charge of the composite explosive constituting the innermost layer of the charge consists only organic nitro explosive.
  • this charge is preferably made up, and only made up, of the organic nitrated explosive in mixture with a charge chosen in the group consisting of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate, reducing metals, and mixtures thereof, i.e. all mixtures of at least two of the aforementioned compounds.
  • the charge of the composite explosive consists solely of the organic nitro explosive in admixture with a charge chosen from the group consisting of ammonium perchlorate, aluminum and their mixtures.
  • the percentage of aluminum is other than 0, this is preferably between 5% and 35% by weight.
  • the percentage of ammonium perchlorate is other than 0, this is preferably between 10% and 40% by weight.
  • the percentage of aluminum and ammonium perchlorate is zero, the percentage of organic nitro explosive is between 75% and 90% by weight.
  • Example 1 Reducing the Vulnerability of an Ammunition Element explosive, the explosive charge of which is a polyurethane composite explosive loaded with hexogen, ammonium perchlorate and aluminum.
  • composition of the charge in composite explosive whose vulnerability is to be reduced is as follows: - Polyurethane polymer matrix obtained by reaction of a polybutadiene with hydroxyl endings with IPDI 12% - Hexogenic 20% - Ammonium perchlorate 43% - Aluminum 25%
  • Such a load is used in particular in underwater mines and torpedoes.
  • the cylindrical metallic envelope containing the load is made of steel, 12.5 mm thick.
  • the diameter of the load is 248 mm and its length of 450 mm.
  • the charges are distributed in the polyurethane polymer matrix of the load so as to achieve a bi-composition loading massively equivalent to the previous one and having the same dimensions.
  • the composition of each layer and the relative mass proportion of the two layers so as to obtain equivalence result from simple and obvious calculations for those skilled in the art. Many solutions result from these calculations.
  • the bi-composition charge produced consists of a cylinder full of composite explosive having as axis that of the charge, of diameter 128 mm, of composition 88% by weight of hexogen and 12% by weight of the aforementioned polymer matrix, coated with a cylindrical crown in a pyrotechnic composition from the family of solid composite propellants, with an internal diameter of 128 mm, an external diameter of 248 mm, therefore of thickness 60 mm, of composition 55.6% by weight of ammonium perchlorate, 32, 4% by weight of aluminum and 12% by weight of the above-mentioned polymer matrix. Except for additives, this composition is that of a BUTALANE propellant (trademark registered by the SNPE).
  • This bi-composition loading was carried out according to the technique, well known to those skilled in the art, of producing composite explosives and solid composite multi-composition propellants by successive flows in molds followed by polymerizations.
  • the full cylinder in composite explosive is equipped with a priming system consisting of a plane wave generator of large diameter 50 mm and length 70 mm, located coaxially with respect to the load, in composite bi-composition explosive (binder polyurethane 14% and octogen 86% for the first and polyurethane binder 11.5%, pentrite 17% and minimum 71.5% for the second).
  • a priming system consisting of a plane wave generator of large diameter 50 mm and length 70 mm, located coaxially with respect to the load, in composite bi-composition explosive (binder polyurethane 14% and octogen 86% for the first and polyurethane binder 11.5%, pentrite 17% and minimum 71.5% for the second).
  • the relay was then primed and consequently that of the composite explosive constituting the full cylinder of the charge of the lower element, using a conventional detonator in contact with the relay.
  • the increase in the initiation of the charge is difficult to measure because the single-composition charge of composite explosive whose vulnerability is to be reduced is already very easily initiable.
  • EXAMPLE 2 Reduction of the Vulnerability and Increase of the Primability of an Element of Explosive Ammunition whose Explosive Load is a Polyurethane Composite Explosive Charged with ONTA, Octogen, Ammonium Perchlorate and Aluminum.
  • composition of the loading in composite explosive which one wants to lower the vulnerability and increase the bootability is as follows: - Polyurethane polymer matrix obtained by reaction of a polybutadiene with hydroxyl endings with IPDI hydroxyls with IPDI 15% - Octogenous 6% - HAVE A 31% - Ammonium perchlorate 38% - Aluminum 10%
  • the cylindrical metallic envelope containing the load is identical to that of Example 1.
  • This load has a very high critical diameter, greater than 10 cm. It is therefore very difficult to boot. Only very large relays can achieve this. However, the vulnerability of such relays prohibits in practice the use of such a load, in particular in mines, underwater torpedoes and bombs of general use.
  • the charges are distributed in the polyurethane polymer matrix of the load so as to produce a bi-composition load massively equivalent to the previous one and having the same dimensions.
  • This bi-composition charge consists of a cylinder full of composite explosive having as axis that of the charge, of diameter 168 mm, of composition 12% by weight of octogen, 72% by weight of ONTA and 16% by weight of the aforementioned polymer matrix, coated with a cylindrical crown in a pyrotechnic composition of the family of solid composite propellants, of internal diameter 168 mm, of external diameter 248 mm, therefore of thickness 40 mm, of composition 68% by weight of perchlorate d ammonium, 18% by weight of aluminum and 14% by weight of the aforementioned polymer matrix. Except for additives, this composition is that of a BUTALANE propellant.
  • This bi-composition loading was carried out using the same technique as that of Example 1.
  • the cylinder full of composite explosive is provided with a priming system consisting of a generator of plane waves, of large diameter 90 mm and length 80 mm, located co-axially with respect to the load, of the same nature as the generator used for example 1.
  • a stack of 3 ammunition elements thus formed that is to say comprising the casing, the bi-composition loading and the priming relay, was produced along a merlon.
  • the separation distance of the elements is 25 mm.
  • the relay was then primed and consequently that of the composite explosive constituting the full cylinder of the loading of the lower element, using a conventional detonator in contact with the relay.

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Abstract

A relatively insensitive component of explosive ammunition consisting of a casing containing a multicomposition explosive charge in which the innermost layer is a composite explosive consisting of a filled polyurethane or polyester polymeric matrix in which the filler contains more than 40 % by weight of organic nitro explosive and in which the peripheral layer is a pyrotechnic composition of the class of composite solid propellants, consisting of a filled polyurethane or polyester polymeric matrix in which the filler contains at least one inorganic oxidiser and less than 10 % by weight of organic nitro explosives. The blast and/or bubble effect produced is close to that produced by the much more sensitive charge of a single-composition composite explosive of equivalent mass. <??>The invention also relates to a process for obtaining a blast and/or bubble effect by release of gas in the casing of an abovementioned component of ammunition according to the invention followed by a rupture of the casing. The gas release is obtained by detonation of the innermost layer followed by a detonation-free reaction of the peripheral layer.

Description

La présente invention se situe dans le domaine des munitions, notamment militaires, à risques atténués. Elle est relative à un élément peu vulnérable de munition explosive constitué d'une enveloppe en général métallique contenant un chargement explosif. Ces munitions sont notamment utiles pour générer un effet de souffle en milieu aérien ou un effet de bulles en milieu sous-marin. Le chargement et son enveloppe ont en général une symétrie axiale (surface de révolution), de façon à générer des effets symétriques. Les munitions explosives, notamment lors de leur stockage ou de leur transport, peuvent être soumises à des agressions telles que l'incendie, l'impact et la pénétration de fragments ou balles, la détonation proche de munitions voisines.The present invention is in the field of ammunition, in particular military, attenuated risks. It relates to a slightly vulnerable element of explosive ammunition consisting of a generally metallic envelope containing an explosive charge. This ammunition is particularly useful for generating a blast effect in the air or a bubble effect in the underwater environment. The load and its envelope generally have an axial symmetry (surface of revolution), so as to generate symmetrical effects. Explosive ordnance, in particular during its storage or transport, can be subjected to attacks such as fire, impact and the penetration of fragments or bullets, detonation close to neighboring munitions.

Si les problèmes de l'incendie et des fragments peuvent être résolus pratiquement à l'aide des explosifs composites classiques, le problème de la détonation par influence, plus précisément de la vulnérabilité à la détonation proche de munitions voisines, n'a pas encore été résolu de façon satisfaisante.If the problems of the fire and fragments can be solved practically using conventional composite explosives, the problem of detonation by influence, more precisely of the vulnerability to detonation close to neighboring munitions, has not yet been solved. resolved satisfactorily.

Il est bien connu d'utiliser des explosifs composites particulièrement peu sensibles chargés par exemple en 5-oxo 3-nitro 1,2,4-triazole (ONTA), en triaminotrinitrobenzène (TATB), ou nitroguanidine. Cette solution présente toutefois deux inconvénients majeurs. Le premier est que la vulnérabilité de la munition à la détonation proche de munitions voisines est alors dépendante de celle du système d'amorçage. Or, ces explosifs composites peu sensibles ont en général un diamètre critique élevé pouvant dépasser 10 cm, et ne peuvent être amorcés classiquement que par un relais puissant de grande taille, donc particulièrement sensible et vulnérable. Le deuxième inconvénient majeur est que même un explosif très insensible comme ceux précités peut détoner par influence à partir d'un certain calibre.It is well known to use particularly insensitive composite explosives loaded for example with 5-oxo 3-nitro 1,2,4-triazole (ONTA), triaminotrinitrobenzene (TATB), or nitroguanidine. This solution has two major drawbacks, however. The first is that the vulnerability of the munition to detonation close to neighboring munitions is then dependent on that of the priming system. However, these insensitive composite explosives generally have a high critical diameter which can exceed 10 cm, and can only be conventionally initiated by a large powerful relay, therefore particularly sensitive and vulnerable. The second major drawback is that even a very insensitive explosive like the above can detonate by influence from a certain caliber.

On entend de façon classique, par explosif composite, une composition pyrotechnique fonctionnellement détonable, constituée d'une matrice polymérique solide, en général polyuréthanne ou polyester, chargée, la dite charge étant pulvérulente et contenant majoritairement une charge explosive nitrée organique, par exemple de l'hexogène, de l'octogène, de l'ONTA, ou un mélange d'au moins deux de ces composés.Conventionally, the term “composite explosive” means a functionally detonable pyrotechnic composition, consisting of a solid polymer matrix, generally polyurethane or polyester, charged, said charge being pulverulent and containing predominantly an organic nitro explosive charge, for example l hexogen, octogen, ONTA, or a mixture of at least two of these compounds.

Les explosifs composites et la façon de les obtenir sont par exemple décrits par J. QUINCHON, les poudres, propergols et explosifs, tome 1, les explosifs, Technique et Documentation, 1982, pages 190-192.Composite explosives and how to obtain them are for example described by J. QUINCHON, powders, propellants and explosives, volume 1, explosives, Technique et Documentation, 1982, pages 190-192.

Le brevet français FR 2 365 774 décrit un élément approximativement cylindrique de munition explosive constitué d'une enveloppe contenant un chargement multicomposition pouvant être un explosif composite. Ce chargement multicomposition comporte une pluralité de couches annulaires coaxiales adjacentes, la couche périphérique ayant une teneur en explosif lourd puissant (hexogène, octogène) plus forte que celle de la couche qui lui est immédiatement adjacente et ainsi de proche en proche jusqu'à la couche axiale centrale qui est cylindrique pleine et comporte la teneur la plus faible en explosif lourd puissant. Un tel élément de munition explosive est donc particulièrement vulnérable.French patent FR 2 365 774 describes an approximately cylindrical element of explosive ammunition consisting of an envelope containing a multi-composition charge which may be a composite explosive. This multi-composition charge comprises a plurality of adjacent coaxial annular layers, the peripheral layer having a content of powerful heavy explosive (hexogen, octogen) higher than that of the layer which is immediately adjacent to it and thus step by step up to the layer central axial which is full cylindrical and has the lowest content of heavy heavy explosive. Such an explosive ordnance item is therefore particularly vulnerable.

Par ailleurs, l'article "Insensitive Munitions - A fire safety plus ?" paru en mai 1989 dans la revue "Military Fire Fighter" pages 74 à 81, enseigne qu'on peut diminuer la vulnérabilité d'un élément de munition chargé en explosif composite vulnérable en enrobant cet explosif par un explosif composite moins vulnérable. Toutefois, comme indiqué précédemment, les explosifs composites peu sensibles ne sont pas exempts de tout risque.In addition, the article "Insensitive Munitions - A fire safety plus?" published in May 1989 in the review "Military Fire Fighter" pages 74 to 81, teaches that one can reduce the vulnerability of an element of ammunition loaded with vulnerable composite explosive by coating this explosive with a less vulnerable composite explosive. However, as indicated above, insensitive composite explosives are not free from all risks.

L'homme du métier est donc à la recherche d'une solution plus satisfaisante que celles connues précitées, permettant d'abaisser encore la vulnérabilité du chargement, et mieux celle de l'élément de munition constitué dudit chargement et de son relais d'amorçage, tout en conservant les performances requises au niveau de l'effet recherché de souffle et/ou de bulles.A person skilled in the art is therefore looking for a more satisfactory solution than those known above, making it possible to further reduce the vulnerability of the load, and better still that of the ammunition element consisting of said load and its priming relay. , while retaining the performance required in terms of the desired effect of breath and / or bubbles.

La présente invention propose une telle solution. La Demanderesse a découvert que, de façon inattendue, on diminuait la vulnérabilité d'un élément de munition explosive constitué d'une enveloppe en général et de préférence métallique contenant un explosif composite constitué d'une matrice polymérique polyuréthanne ou polyester chargée d'une part en explosif nitré organique pulvérulent et d'autre part en une charge pulvérulente exempte d'explosif nitré organique mais comprenant au moins un oxydant minéral, en répartissant l'explosif nitré organique et la charge exempte d'explosif nitré organique dans la matrice polymérique polyuréthanne ou polyester de façon à réaliser un chargement multicomposition, de préférence bi-composition, dont la couche la plus interne est un explosif composite dont la charge contient plus de 40 % en poids d'explosif nitré organique, pourcentage exprimé par rapport à l'explosif composite, et dont la couche périphérique est une composition pyrotechnique constituée d'une matrice polymérique polyuréthanne ou polyester chargée, ladite charge contenant au moins un oxydant minéral et moins de 10 % en poids d'explosif nitré organique, pourcentage exprimé par rapport à la composition pyrotechnique, tout en conservant pratiquement le même niveau de performances, à savoir le même effet de souffle et/ou de bulles.The present invention provides such a solution. The Applicant has discovered that, unexpectedly, the vulnerability of an explosive ammunition element consisting of a generally and preferably metallic envelope containing a composite explosive consisting of a polyurethane or polyester polymer matrix loaded on the one hand, is reduced. in powdered organic nitro explosive and on the other hand in a powdery charge free of organic nitro explosive but comprising at least one mineral oxidant, by distributing the organic nitro explosive and the charge free of organic nitro explosive in the polyurethane polymer matrix or polyester so as to produce a multi-composition charge, preferably bi-composition, the innermost layer of which is a composite explosive, the charge of which contains more than 40% by weight of organic nitro explosive, percentage expressed relative to the composite explosive , and whose peripheral layer is a pyrotechnic composition made up of a material this charged polyurethane or polyester polymer, said filler containing at least one mineral oxidant and less than 10% by weight of organic nitro explosive, percentage expressed relative to the pyrotechnic composition, while retaining practically the same level of performance, namely the same effect of breath and / or bubbles.

La composition pyrotechnique de la couche périphérique est de la famille des propergols solides composites.The pyrotechnic composition of the peripheral layer is from the family of composite solid propellants.

On entend, de façon classique, par propergol solide composite, une composition pyrotechnique mise en oeuvre de façon identique à celle d'un explosif composite, et constituée d'une matrice polymérique solide, en général polyuréthanne ou polyester, chargée, ladite charge étant pulvérulente et essentiellement constituée d'un oxydant minéral et en général d'un métal réducteur. La charge peut également parfois contenir un explosif nitré organique. Ayant vocation à la propulsion, les propergols solides composites sont fonctionnellement combustibles et comprennent divers additifs pour maîtriser la propulsion. Les propergols solides composites et la façon de les obtenir sont par exemple décrits par A. DAVENAS, Technologie des propergols solides, Ed. Masson, 1989.The term “composite solid propellant” is conventionally understood to mean a pyrotechnic composition used in the same way as that of a composite explosive, and consisting of a polymer matrix solid, generally polyurethane or polyester, charged, said charge being pulverulent and essentially consisting of a mineral oxidant and in general of a reducing metal. The charge may also sometimes contain an organic nitro explosive. Being intended for propulsion, solid composite propellants are functionally combustible and include various additives to control propulsion. Composite solid propellants and how to obtain them are for example described by A. DAVENAS, Solid propellant technology, Ed. Masson, 1989.

Selon la présente invention, la fonction propulsive n'étant pas recherchée ni exercée, la Demanderesse souhaite ne pas qualifier la couche périphérique de "Propergol" bien que la composition de cette couche ne se différencie de celle des progergols solides composites que par l'absence des additifs liés à la fonction propulsive des propergols (additifs balistiques, accélérateurs de combustion, etc.), et préfère utiliser l'expression "Composition pyrotechnique de la famille des propergols solides composites".According to the present invention, the propellant function not being sought or exercised, the Applicant wishes not to qualify the peripheral layer of "Propellant" although the composition of this layer differs from that of the solid composite progergols only by the absence additives linked to the propellant function of the propellants (ballistic additives, combustion accelerators, etc.), and prefers to use the expression "Pyrotechnic composition of the family of solid composite propellants".

Par ailleurs, étant donné que les dérivés nitrés aliphatiques n'ont encore donné lieu à aucune application industrielle majeure en tant qu'explosif, on entend de façon classique, par "explosif nitré organique", un explosif choisi dans le groupe constitué par les explosifs nitrés aromatiques (comportant au moins un groupement C -NO₂, l'atome de carbone faisant partie d'un cycle aromatique), les explosifs esters nitriques (comportant au moins un groupement C - O - NO₂) et les explosifs nitramines (comportant au moins un groupement C - N - NO₂).Furthermore, since the aliphatic nitro derivatives have not yet given rise to any major industrial application as an explosive, conventionally, the term "organic nitro explosive" means an explosive chosen from the group consisting of explosives aromatic nitrates (comprising at least one C -NO₂ group, the carbon atom being part of an aromatic ring), nitric ester explosives (comprising at least one C - O - NO₂ group) and nitramine explosives (comprising at least a C - N - NO₂ group).

La Demanderesse a également découvert, de façon plus générale, que le résultat surprenant précité est aussi obtenu lorsque la matrice polymérique de l'explosif composite est différente de celle de la composition pyrotechnique de la famille des propergols solides composites. Il faut rappeler que si fonctionnellement un explosif composite détone, un propergol solide composite brûle sans détoner. Les phénomènes de combustion et de détonation sont bien définis, différenciés, et connus de l'homme du métier. On peut par exemple se reporter à l'ouvrage précité de J.QUINCHON, pages 12 et 13.
L'homme du métier est donc tout surpris de constater qu'on conserve pratiquement le même niveau en effet de souffle et/ou de bulles comparativement à l'explosif composite massiquement équivalent qui détone en totalité,alors que la couche périphérique du chargement réagit sans détoner, et ce même lorsque des charges explosives telles que l'octogène et le perchlorate d'ammonium sont dans cette couche périphérique.The Applicant has also discovered, more generally, that the aforementioned surprising result is also obtained when the polymer matrix of the composite explosive is different from that of the pyrotechnic composition of the family of solid composite propellants. It must be remembered that if a composite explosive detonates functionally, a solid composite propellant burns without detonating. The combustion and detonation phenomena are well defined, differentiated, and known to those skilled in the art. We can for example refer to the aforementioned work by J. QUINCHON, pages 12 and 13.
A person skilled in the art is therefore quite surprised to observe that practically the same level of blast and / or bubble effect is maintained compared to the massively equivalent composite explosive which detonates entirely, while the peripheral layer of the charge reacts without detonate, even when explosive charges such as octogen and ammonium perchlorate are in this peripheral layer.

Par ailleurs cette configuration multicomposition avec une couche périphérique en composition pyrotechnique de la faille des propergols solides composites dont la charge contient au moins un oxydant minéral et moins de 10 % en poids d'explosif nitré organique, de préférence 0 %, confère à l'élément de munition une quasi-invulnérabilité à la détonation proche de munitions voisines.Furthermore, this multicomposition configuration with a peripheral layer of pyrotechnic composition of the fault of the solid composite propellants whose charge contains at least one mineral oxidant and less than 10% by weight of organic nitro explosive, preferably 0%, gives the ammunition element a quasi-invulnerability to detonation close to neighboring munitions.

De plus, l'élément selon l'invention est plus facilement amorçable, par un relais en contact avec la couche la plus interne du chargement multicomposition, que selon la configuration massiquement équivalente connue de l'état de la technique. De ce fait, l'élément selon l'invention peut être initié par un relais de plus faible taille ce qui d'une part diminue encore la vulnérabilité de l'ensemble enveloppe-chargement-relais, et d'autre part permet l'utilisation d'explosifs composites très difficilement amorçables qui était jusqu'alors prohibée du fait de la taille des relais d'amorçage nécessaires et des risques conséquents.In addition, the element according to the invention is more easily bootable, by a relay in contact with the innermost layer of the multi-composition charge, than according to the massively equivalent configuration known from the prior art. Therefore, the element according to the invention can be initiated by a smaller relay which on the one hand further reduces the vulnerability of the envelope-load-relay assembly, and on the other hand allows the use explosives which are very difficult to initiate, which was previously prohibited because of the size of the priming relays required and the consequent risks.

La configuration selon l'invention permet donc simultanément de diminuer la vulnérabilité du chargement vis-à-vis d'ondes de détonation, en général latérales, provoquées par la détonation proche de munitions voisines, et d'augmenter son amorçabilité frontale eu égard à un relais d'amorçage situé sur l'axe du chargement au contact de la couche la plus interne. Un tel résultat, à savoir diminuer la vulnérabilité d'un chargement tout en augmentant son amorçabilité, est surprenant pour l'homme du métier et permet l'obtention d'éléments de munitions enveloppe-chargement-relais quasi invulnérables et/ou l'obtention d'éléments de munitions enveloppe-chargement-relais peu vulnérables qu'il n'aurait pas été envisageable de réaliser jusqu'alors compte tenu de la faible amorçabilité du chargement.The configuration according to the invention therefore simultaneously makes it possible to reduce the vulnerability of the load vis-à-vis detonation waves, generally lateral ones, caused by the detonation close to neighboring munitions, and to increase its frontal initiation eu with regard to a priming relay located on the axis of the load in contact with the innermost layer. Such a result, namely reducing the vulnerability of a load while increasing its bootability, is surprising for those skilled in the art and makes it possible to obtain elements of almost invulnerable envelope-loading-relay munitions and / or obtaining elements of envelope-loading-relay ammunition that are not very vulnerable that it would not have been possible to carry out until now, given the low bootability of the loading.

La présente invention a donc pour objet un élément de munition explosive constitué d'une enveloppe de préférence métallique contenant un chargement explosif multicomposition comportant une pluralité de couches coaxiales adjacentes. L'enveloppe et chaque couche du chargement peuvent présenter toute forme de révolution, par exemple cylindrique, ovoïdale, ellipsoïdale, sphérique, conique ou de diabolo. Toutes ces formes peuvent n'être qu'approximatives. Les surfaces de révolution peuvent notamment présenter des irrégularités, par exemple des dents ou d'autres évidements. Les couches peuvent ne pas être rigoureusement coaxiales. Par ailleurs, la couche la plus interne est de préférence pleine, mais elle peut aussi présenter un ou des évidements, par exemple un évidement pour loger le système d'amorçage. L'invention est caractérisée en ce que la couche la plus interne est un explosif composite constitué d'une matrice polymérique polyurétanne ou polyester chargée, de préférence polyuréthanne, dont la charge, pulvérulente, contient un explosif nitré organique dont la teneur est supérieure à 40 % en poids par rapport à l'explosif composite, de préférence comprise entre 40 % et 90 %, et en ce que la couche périphérique est une composition pyrotechnique de la famille des propergols solides composites constituée d'une matrice polymérique polyuréthanne ou polyester chargée, de préférence polyuréthanne, dont la charge, pulvérulente, contient au moins un oxydant minéral et moins de 10 % en poids d'explosif nitré organique, pourcentage exprimé par rapport à la composition pyrotechnique de la famille des propergols solides composites.The present invention therefore relates to an explosive munition element consisting of a preferably metallic envelope containing a multicomposition explosive charge comprising a plurality of adjacent coaxial layers. The envelope and each layer of the load may have any form of revolution, for example cylindrical, ovoid, ellipsoidal, spherical, conical or diabolo. All these forms may be only approximate. The surfaces of revolution may in particular have irregularities, for example teeth or other recesses. The layers may not be strictly coaxial. Furthermore, the innermost layer is preferably full, but it can also have one or more recesses, for example a recess for housing the priming system. The invention is characterized in that the innermost layer is a composite explosive consisting of a charged polyurethane or polyester polymer matrix, preferably polyurethane, the charge of which, pulverulent, contains an organic nitro explosive the content of which is greater than 40 % by weight with respect to the composite explosive, preferably between 40% and 90%, and in that the peripheral layer is a pyrotechnic composition from the family of solid composite propellants consisting of a charged polyurethane or polyester polymer matrix, preferably polyurethane, the pulverulent filler of which contains at least one inorganic oxidant and less than 10% by weight of organic nitro explosive, percentage expressed relative to the pyrotechnic composition of the family of solid composite propellants.

Par "moins de 10 %" ; il faut normalement entendre que la teneur est soit comprise entre 0 et 10 %, soit nulle, c'est-à-dire, dans ce deuxième cas, d'ailleurs préféré, que la charge est exempte d'explosif nitré organique.By "less than 10%"; it should normally be understood that the content is either between 0 and 10%, or zero, that is to say, in this second case, moreover preferred, that the charge is free of organic nitro explosive.

De façon préférée, le chargement explosif est un chargement bi-composition, la couche interne étant revêtue d'une couche coaxiale adjacente périphérique. Dans les autres cas, c'est-à-dire lorsque le chargement comprend plus de 2 couches, la ou les couches intermédiaires sont de préférence en explosif composite, mais certaines couches, notamment celles proches de la couche périphérique, peuvent être en composition pyrotechnique de la famille des propergols solides composites.
De façon préférée, la matrice polymérique de l'explosif composite constituant la couche la plus interne et la matrice polymérique de la composition pyrotechnique constituant la couche périphérique du chargement, sont identiques, de préférence une matrice polyuréthanne. Selon cette variante, lorsque le chargement contient plus de 2 couches, les couches intermédiaires en explosif composite et/ou en composition pyrotechnique de la famille des propergols solides composites ont également la même matrice polymérique que la couche la plus interne et la couche périphérique. Les matrices polymériques peuvent éventuellement comprendre un plastifiant, tels que ceux habituellement utilisés dans la mise en oeuvre des explosifs composites et des propergols solides composites.Preferably, the explosive charge is a bi-composition charge, the internal layer being coated with an adjacent peripheral coaxial layer. In the other cases, that is to say when the charge comprises more than 2 layers, the intermediate layer or layers are preferably made of composite explosive, but certain layers, in particular those close to the peripheral layer, can be in pyrotechnic composition from the family of solid composite propellants.
Preferably, the polymer matrix of the composite explosive constituting the innermost layer and the polymer matrix of the pyrotechnic composition constituting the peripheral layer of the charge, are identical, preferably a polyurethane matrix. According to this variant, when the charge contains more than 2 layers, the intermediate layers of composite explosive and / or of pyrotechnic composition from the family of solid composite propellants also have the same polymer matrix as the innermost layer and the peripheral layer. The polymer matrices may optionally include a plasticizer, such as those usually used in the use of composite explosives and composite solid propellants.

De façon générale, dans le cadre de la présente invention, la matrice polymérique polyuréthanne est obtenue par réaction d'un prépolymère à terminaisons hydroxyles avec un polyisocyanate.
Comme exemples de prépolymères à terminaisons hydroxyles, on peut citer ceux dont le squelette est un polyisobutylène, un polybutadiène, un polyéther, un polyester, un polysiloxane. On utilise de préférence un polybutadiène à terminaisons hydroxyles.
Comme exemples de polyisocyanates, on peut citer l'isophorone diisocyanate (IPDI), le toluène diisocyanate (TDI), le dicyclohexylméthylène diisocyanate (Hylène W), l'hexaméthylène diisocyanate (HMDI), le biuret trihexane isocyanate (BTHI), et leurs mélanges.Generally, in the context of the present invention, the polyurethane polymer matrix is obtained by reaction of a prepolymer with hydroxyl endings with a polyisocyanate.
As examples of prepolymers with hydroxyl endings, mention may be made of those whose backbone is a polyisobutylene, a polybutadiene, a polyether, a polyester, a polysiloxane. Preferably, polybutadiene with hydroxyl end groups is used.
Examples of polyisocyanates that may be mentioned are isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexylmethylene diisocyanate (Hylene W), hexamethylene diisocyanate (HMDI), biuret trihexane isocyanate (BTHI), and mixtures thereof.

Lorsque la matrice polymérique est une matrice polyester, elle est en général obtenue par réaction d'un prépolymère à terminaisons carboxyles, de préférence un polybutadiène à terminaisons carboxyles (PBCT) ou un polyester à terminaisons carboxyles, avec un polyépoxyde, par exemple un condensat d'épichlorhydrine et de glycérol, ou un polyaziridine, par exemple le triméthylaziridinyl phosphine oxyde (MAPO).When the polymer matrix is a polyester matrix, it is generally obtained by reaction of a carboxyl-terminated prepolymer, preferably a carboxyl-terminated polybutadiene (PBCT) or a carboxyl-terminated polyester, with a polyepoxide, for example a condensate of epichlorohydrin and glycerol, or a polyaziridine, for example trimethylaziridinyl phosphine oxide (MAPO).

Selon une variante de l'invention, la charge de la composition pyrotechnique de la famille des propergols solides composites constituant la couche périphérique contient un oxydant minéral choisi dans le groupe constitué par le perchlorate d'ammonium, le perchlorate de potassium, le nitrate d'ammonium, le nitrate de sodium, et leurs mélanges, c'est-à-dire tous les mélanges d'au moins deux produits précités.According to a variant of the invention, the charge of the pyrotechnic composition of the family of composite solid propellants constituting the peripheral layer contains an inorganic oxidant chosen from the group consisting of ammonium perchlorate, potassium perchlorate, nitrate of ammonium, sodium nitrate, and mixtures thereof, that is to say all mixtures of at least two aforementioned products.

Selon une autre variante, la charge de la composition pyrotechnique de la famille des propergols solides composites constituant la couche périphérique contient un métal réducteur, de préférence choisi dans le groupe constitué par l'aluminium, le zirconium, le magnésium, le bore et leurs mélanges, c'est-à-dire tous les mélanges d'au moins deux des quatre métaux précités. De façon particulièrement préférée, le métal réducteur est l'aluminium.According to another variant, the charge of the pyrotechnic composition of the family of solid composite propellants constituting the peripheral layer contains a reducing metal, preferably chosen from the group consisting of aluminum, zirconium, magnesium, boron and their mixtures , that is to say all mixtures of at least two of the four metals mentioned above. In a particularly preferred manner, the reducing metal is aluminum.

Comme cela a déjà été mentionné, selon une variante préférée, la charge de la composition pyrotechnique de la famille des propergols solides composites constituant la couche périphérique est exempte d'explosif nitré organique. Selon cette variante préférée, il faut citer deux sous-variantes particulièrement intéressantes.As already mentioned, according to a preferred variant, the charge of the pyrotechnic composition of the family of solid composite propellants constituting the peripheral layer is free of organic nitro explosive. According to this preferred variant, two particularly interesting sub-variants must be mentioned.

Selon la première, la charge de la composition pyrotechnique constituant la couche périphérique est une charge minérale, de préférence choisie dans le groupe constitué par le perchlorate d'ammonium, le perchlorate de potassium, le nitrate d'ammonium, le nitrate de sodium et leurs mélanges. La charge ne contient donc aucun autre composé.According to the first, the charge of the pyrotechnic composition constituting the peripheral layer is a mineral charge, preferably chosen from the group consisting of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate and their mixtures. The charge therefore does not contain any other compound.

Selon la seconde, la charge de la composition pyrotechnique constituant la couche périphérique est constituée, et uniquement constituée, d'un mélange d'un métal réducteur, de préférence choisi dans le groupe constitué par l'aluminium, le zirconium, le magnésium, le bore et leurs mélanges, et d'un oxydant minéral de préférence choisi dans le groupe constitué par le perchlorate d'ammonium, le perchlorate de potassium, le nitrate d'ammonium, le nitrate de sodium et leurs mélanges. De préférence, la charge est un mélange de perchlorate d'ammonium et d'aluminium. Dans ce cas la couche périphérique est de préférence constituée de :

  • 10 % à 40 % en poids d'une matrice polymérique polyuréthanne
  • 5 % à 40 % en poids d'aluminium
  • 20 % à 85 % en poids de perchlorate d'ammonium,
la somme des pourcentages étant égale à 100.According to the second, the charge of the pyrotechnic composition constituting the peripheral layer consists, and only consists, of a mixture of a reducing metal, preferably chosen from the group consisting of aluminum, zirconium, magnesium, boron and their mixtures, and a mineral oxidant preferably chosen from the group consisting of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate and their mixtures. Preferably, the filler is a mixture of ammonium perchlorate and aluminum. In this case, the peripheral layer preferably consists of:
  • 10% to 40% by weight of a polyurethane polymer matrix
  • 5% to 40% by weight of aluminum
  • 20% to 85% by weight of ammonium perchlorate,
the sum of the percentages being equal to 100.

Selon une autre variante de l'invention, l'explosif nitré organique contenu dans la charge de l'explosif composite constituant la couche la plus interne du chargement est choisi dans le groupe constitué par l'hexogène, l'octogène, la pentrite, le 5-oxo 3-nitro 1,2, 4-triazole, le triaminotrinitrobenzène, la nitroguanidine et leurs mélanges, c'est-à-dire tous les mélanges d'au moins deux des composés précités. De préférence, cette charge en explosif nitré organique est choisie dans le groupe constitué par l'hexogène, l'octogène, le 5-oxo 3-nitro 1,2,4-triazole et leurs mélanges.According to another variant of the invention, the organic nitro explosive contained in the charge of the composite explosive constituting the innermost layer of the charge is chosen from the group consisting of hexogen, octogen, pentrite, 5-oxo 3-nitro 1,2,4-triazole, triaminotrinitrobenzene, nitroguanidine and their mixtures, that is to say all mixtures of at least two of the above-mentioned compounds. Preferably, this charge of organic nitro explosive is chosen from the group consisting of hexogen, octogen, 5-oxo 3-nitro 1,2,4-triazole and their mixtures.

Selon une variante préférée, la charge de l'explosif composite constituant la couche la plus interne du chargement est uniquement constituée de l'explosif nitré organique.According to a preferred variant, the charge of the composite explosive constituting the innermost layer of the charge consists only organic nitro explosive.

Dans les autres cas, c'est-à-dire lorsque la charge de l'explosif composite contient d'autres constituants, cette charge est de préférence constituée, et uniquement constituée, de l'explosif nitré organique en mélange avec une charge choisie dans le groupe constitué par le perchlorate d'ammonium, le perchlorate de potassium, le nitrate d'ammonium, le nitrate de sodium, les métaux réducteurs, et leurs mélanges, c'est-à-dire tous les mélanges d'au moins deux des composés précités. De façon particulièrement préférée, la charge de l'explosif composite est uniquement constituée de l'explosif nitré organique en mélange avec une charge choisie dans le groupe constitué par le perchlorate d'ammonium, l'aluminium et leurs mélanges.In the other cases, that is to say when the charge of the composite explosive contains other constituents, this charge is preferably made up, and only made up, of the organic nitrated explosive in mixture with a charge chosen in the group consisting of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate, reducing metals, and mixtures thereof, i.e. all mixtures of at least two of the aforementioned compounds. In a particularly preferred manner, the charge of the composite explosive consists solely of the organic nitro explosive in admixture with a charge chosen from the group consisting of ammonium perchlorate, aluminum and their mixtures.

La couche la plus interne en explosif composite est de préférence constituée de :

  • 10 % à 25 % en poids d'une matrice polymérique polyuréthanne
  • 40 % à 90 % en poids d'un explosif nitré organique choisi dans le groupe constitué par l'hexogène, l'octogène, le 5-oxo 3-nitro 1,2,4-triazole et leurs mélanges.
  • 0 % à 35 % en poids d'aluminium
  • 0 % à 45 % en poids de perchlorate d'ammonium,
la somme des pourcentages étant égale à 100.The innermost layer of composite explosive preferably consists of:
  • 10% to 25% by weight of a polyurethane polymer matrix
  • 40% to 90% by weight of an organic nitro explosive chosen from the group consisting of hexogen, octogen, 5-oxo 3-nitro 1,2,4-triazole and their mixtures.
  • 0% to 35% by weight of aluminum
  • 0% to 45% by weight of ammonium perchlorate,
the sum of the percentages being equal to 100.

Lorsque le pourcentage en aluminium est différent de 0, celui-ci est de préférence compris entre 5 % et 35 % en poids. Lorsque le pourcentage en perchlorate d'ammonium est différent de 0, celui-ci est de préférence compris entre 10 % et 40 % en poids. Lorsque le pourcentage en aluminium et en perchlorate d'ammonium est nul, le pourcentage en explosif nitré organique est compris entre 75 % et 90 % en poids.When the percentage of aluminum is other than 0, this is preferably between 5% and 35% by weight. When the percentage of ammonium perchlorate is other than 0, this is preferably between 10% and 40% by weight. When the percentage of aluminum and ammonium perchlorate is zero, the percentage of organic nitro explosive is between 75% and 90% by weight.

La présente invention a également pour objet un procédé d'obtention d'un effet de souffle et/ou de bulles par libération de gaz, en un temps très bref, dans l'enveloppe de préférence métallique d'un élément de munition explosive constitué de ladite enveloppe contenant un chargement explosif, puis rupture de l'enveloppe due à la pression du gaz formé. Selon l'invention, ce procédé est caractérisé en ce que :

  • l'élément de munition explosive est un élément précité selon la présente invention, à savoir un élément dont le chargement explosif comporte une pluralité de couches coaxiales adjacentes, de préférence deux couches, la couche la plus interne, de préférence pleine, étant en explosif composite constitué d'une matrice polymérique polyuréthanne ou polyester chargée dont la charge contient plus de 40 % en poids d'explosif nitré organique, pourcentage exprimé par rapport à l'explosif composite, la couche périphérique étant une composition pyrotechnique de la famille des propergols solides composites constituée d'une matrice polyuréthanne ou polyester chargée dont la charge contient au moins un oxydant minéral et moins de 10 % en poids d'explosif nitré organique, pourcentage exprimé par rapport à la composition pyrotechnique. De façon préférée ce pourcentage est nul, c'est-à-dire que la charge est exempte d'explosif nitré organique.
  • la libération de gaz est obtenue par détonation de l'explosif composite constituant la couche la plus interne du chargement, puis réaction sans détonation de la composition pyrotechnique de la famille des propergols solides composites constituant la couche périphérique, ladite réaction étant initiée par l'onde de détonation résultant de la détonation de l'explosif composite.
The present invention also relates to a process for obtaining a blast and / or bubble effect by releasing gas, in a very short time, in the preferably metallic casing of an explosive munition element consisting of said envelope containing an explosive charge, then rupture of the envelope due to the pressure of the gas formed. According to the invention, this process is characterized in that:
  • the explosive ordnance element is an aforementioned element according to the present invention, namely an element whose explosive charge comprises a plurality of adjacent coaxial layers, preferably two layers, the innermost layer, preferably full, being made of composite explosive consisting of a charged polyurethane or polyester polymer matrix, the charge of which contains more than 40% by weight of organic nitro explosive, percentage expressed relative to the composite explosive, the peripheral layer being a pyrotechnic composition of the family of solid composite propellants consisting of a charged polyurethane or polyester matrix, the charge of which contains at least one mineral oxidant and less than 10% by weight of organic nitro explosive, percentage expressed relative to the pyrotechnic composition. Preferably, this percentage is zero, that is to say that the charge is free of organic nitro explosive.
  • gas release is obtained by detonation of the composite explosive constituting the innermost layer of the charge, then reaction without detonation of the pyrotechnic composition of the family of solid composite propellants constituting the peripheral layer, said reaction being initiated by the wave detonation resulting from the detonation of the composite explosive.

Les exemples non limitatifs suivants illustrent l'invention et les avantages qu'elle procure.The following nonlimiting examples illustrate the invention and the advantages which it provides.

Exemple 1 Abaissement de la vulnérabilité d'un élément de munition explosive dont le chargement explosif est un explosif composite polyuréthanne chargé à l'hexogène, au perchlorate d'ammonium et à l'aluminium. Example 1 Reducing the Vulnerability of an Ammunition Element explosive, the explosive charge of which is a polyurethane composite explosive loaded with hexogen, ammonium perchlorate and aluminum.

La composition du chargement en explosif composite dont on veut abaisser la vulnérabilité est la suivante : - Matrice polymérique polyuréthanne obtenue par réaction d'un polybutadiène à terminaisons hydroxyles avec l'IPDI 12 % - Hexogène 20 % - Perchlorate d'ammonium 43 % - Aluminium 25 % The composition of the charge in composite explosive whose vulnerability is to be reduced is as follows: - Polyurethane polymer matrix obtained by reaction of a polybutadiene with hydroxyl endings with IPDI 12% - Hexogenic 20% - Ammonium perchlorate 43% - Aluminum 25%

Un tel chargement est notamment utilisé dans les mines et torpilles sous-marines.Such a load is used in particular in underwater mines and torpedoes.

L'enveloppe métallique cylindrique contenant le chargement est en acier, d'épaisseur 12,5 mm. Le diamètre du chargement (diamètre intérieur de l'enveloppe métallique) est de 248 mm et sa longueur de 450 mm.The cylindrical metallic envelope containing the load is made of steel, 12.5 mm thick. The diameter of the load (internal diameter of the metal envelope) is 248 mm and its length of 450 mm.

On a réalisé, le long d'un merlon, un empilement de 2 éléments de munition ainsi constitués, séparés de 25 mm, puis l'amorçage de l'élément inférieur à l'aide d'un relais de diamètre 63 mm et de longueur 120 mm en explosif composite de composition 40 % octogène, 44 % pentrite et 16 % liant polyuréthanne, et d'un détonateur DAVEY BICKFORD SA 4000.
On a constaté la détonation par influence de l'élément supérieur, pourtant dépourvu de relais d'amorcage.We carried out, along a merlon, a stack of 2 ammunition elements thus constituted, separated by 25 mm, then the priming of the lower element using a relay of diameter 63 mm and length 120 mm in composite explosive with 40% octogen composition, 44% pentrite and 16% polyurethane binder, and a DAVEY BICKFORD SA 4000 detonator.
The detonation by influence of the upper element has been observed, although it does not have a priming relay .

Selon l'invention, dans une enveloppe métallique identique, on a réparti les charges dans la matrice polymérique polyuréthanne du chargement de façon à réaliser un chargement bi-composition massiquement équivalent au précédent et ayant les mêmes dimensions. La composition de chaque couche et la proportion massique relative des deux couches de façon à obtenir l'équivalence résultent de calculs simples et évidents pour l'homme du métier. De nombreuses solutions résultent de ces calculs. Le chargement bi-composition réalisé est constitué d'un cylindre plein en explosif composite ayant comme axe celui du chargement, de diamètre 128 mm, de composition 88 % en poids d'hexogène et 12 % en poids de la matrice polymérique précitée, enrobé par une couronne cylindrique en une composition pyrotechnique de la famille des propergols solides composites, de diamètre intérieur 128 mm, de diamètre extérieur 248 mm, donc d'épaisseur 60 mm, de composition 55,6 % en poids de perchlorate d'ammonium, 32,4 % en poids d'aluminium et 12 % en poids de la matrice polymérique précitée. Aux additifs près,cette composition est celle d'un propergol BUTALANE (marque déposée par la SNPE). Ce chargement bi-composition a été réalisé selon la technique, bien connue de l'homme du métier, de réalisation des explosifs composites et propergols solides composites multi-compositions par coulées successives dans des moules suivies de polymérisations.According to the invention, in an identical metallic envelope, the charges are distributed in the polyurethane polymer matrix of the load so as to achieve a bi-composition loading massively equivalent to the previous one and having the same dimensions. The composition of each layer and the relative mass proportion of the two layers so as to obtain equivalence result from simple and obvious calculations for those skilled in the art. Many solutions result from these calculations. The bi-composition charge produced consists of a cylinder full of composite explosive having as axis that of the charge, of diameter 128 mm, of composition 88% by weight of hexogen and 12% by weight of the aforementioned polymer matrix, coated with a cylindrical crown in a pyrotechnic composition from the family of solid composite propellants, with an internal diameter of 128 mm, an external diameter of 248 mm, therefore of thickness 60 mm, of composition 55.6% by weight of ammonium perchlorate, 32, 4% by weight of aluminum and 12% by weight of the above-mentioned polymer matrix. Except for additives, this composition is that of a BUTALANE propellant (trademark registered by the SNPE). This bi-composition loading was carried out according to the technique, well known to those skilled in the art, of producing composite explosives and solid composite multi-composition propellants by successive flows in molds followed by polymerizations.

Le cylindre plein en explosif composite est muni d'un système d'amorçage constitué d'un générateur d'ondes planes de grand diamètre 50 mm et de longueur 70 mm, situé coaxialement par rapport au chargement, en explosif composite bi-composition (liant polyuréthanne 14 % et octogène 86 % pour la première et liant polyuréthanne 11,5 %, pentrite 17 % et minium 71,5 % pour la seconde).The full cylinder in composite explosive is equipped with a priming system consisting of a plane wave generator of large diameter 50 mm and length 70 mm, located coaxially with respect to the load, in composite bi-composition explosive (binder polyurethane 14% and octogen 86% for the first and polyurethane binder 11.5%, pentrite 17% and minimum 71.5% for the second).

On a réalisé, le long d'un merlon, un enpilement de trois éléments de munition ainsi constitués, c'est-à-dire comprenant l'enveloppe, le chargement bi-composition et le relais d'amorçage. La distance de séparation des éléments est de 25 mm.There was produced, along a merlon, a stack of three ammunition elements thus formed, that is to say comprising the envelope, the bi-composition loading and the priming relay. The separation distance of the elements is 25 mm.

On a ensuite réalisé l'amorçage du relais et conséquement celui de l'explosif composite constituant le cylindre plein du chargement de l'élément inférieur, à l'aide d'un détonateur classique en contact avec le relais.The relay was then primed and consequently that of the composite explosive constituting the full cylinder of the charge of the lower element, using a conventional detonator in contact with the relay.

La détonation de l'explosif composite constituant le cylindre plein du chargement de l'élément inférieur a entraîné la réaction sans détonation de la composition type propergol BUTALANE constituant la couche périphérique adjacente annulaire en forme de couronne.The detonation of the composite explosive constituting the full cylinder of the loading of the lower element resulted in the reaction without detonation of the composition propellant type BUTALANE constituting the adjacent annular peripheral layer in the shape of a crown.

On a constaté la non détonation par influence des deux éléments récepteurs supérieurs, et ce, malgré la présence, dans ces deux éléments, d'un système d'amorçage identique à celui de l'élément donneur, ce qui démontre la quasi invulnérabilité de cet élément de munition vis-à-vis de l'onde de détonation, notamment lors du stockage, et l'intérêt de l'invention puisque le chargement monocomposition massiquement équivalent est vulnérable bien que dépourvu de tout système d'amorçage. Cet abaissement considérable de la vulnérabilité n'est pas obtenu au détriment des effets recherchés puisque l'élément précité bi-composition selon l'invention présente des effets de souffle et/ou de bulles voisins de ceux obtenus avec l'élément monocomposition massiquement équivalent. The detonation by influence of the two upper receptor elements has been observed , despite the presence in these two elements of an initiation system identical to that of the donor element, which demonstrates the almost invulnerability of this element. ammunition element vis-à-vis the detonation wave, in particular during storage, and the advantage of the invention since the massively equivalent single-composition loading is vulnerable although it does not have any priming system. This considerable reduction in vulnerability is not obtained to the detriment of the desired effects since the above-mentioned bi-composition element according to the invention exhibits breath and / or bubble effects close to those obtained with the massively equivalent monocomposition element.

Dans le cadre de cet exemple, l'augmentation de l'amorçabilité du chargement est difficilement mesurable du fait que le chargement monocomposition en explosif composite dont on veut abaisser la vulnérabilité est déjà très facilement amorçable.In the context of this example, the increase in the initiation of the charge is difficult to measure because the single-composition charge of composite explosive whose vulnerability is to be reduced is already very easily initiable.

Exemple 2 Abaissement de la vulnérabilité et augmentation de l'amorçabilité d'un élément de munition explosive dont le chargement explosif est un explosif composite polyuréthanne chargé à l'ONTA, a l'octogène, au perchlorate d'ammonium et à l'aluminium. EXAMPLE 2 Reduction of the Vulnerability and Increase of the Primability of an Element of Explosive Ammunition whose Explosive Load is a Polyurethane Composite Explosive Charged with ONTA, Octogen, Ammonium Perchlorate and Aluminum.

La composition du chargement en explositif composite dont on veut abaisser la vulnérabilité et augmenter l'amorçabilité est la suivante : - Matrice polymérique polyuréthanne obtenue par réaction d'un polybutadiène à terminaisons hydroxyles avec l'IPDI hydroxyles avec l'IPDI 15 % - Octogène 6 % - ONTA 31 % - Perchlorate d'ammonium 38 % - Aluminium 10 % The composition of the loading in composite explosive which one wants to lower the vulnerability and increase the bootability is as follows: - Polyurethane polymer matrix obtained by reaction of a polybutadiene with hydroxyl endings with IPDI hydroxyls with IPDI 15% - Octogenous 6% - HAVE A 31% - Ammonium perchlorate 38% - Aluminum 10%

L'enveloppe métallique cylindrique contenant le chargement est identique à celle de l'exemple 1.
Ce chargement a un diamètre critique très élevé, supérieur à 10 cm. Il est donc très difficilement amorçable. Seuls des relais de trés grande taille peuvent y parvenir. Toutefois la vulnérabilité de tels relais prohibe en pratique l'utilisation d'un tel chargement, notamment dans les mines, torpilles sous-marines et bombes d'emploi général.The cylindrical metallic envelope containing the load is identical to that of Example 1.
This load has a very high critical diameter, greater than 10 cm. It is therefore very difficult to boot. Only very large relays can achieve this. However, the vulnerability of such relays prohibits in practice the use of such a load, in particular in mines, underwater torpedoes and bombs of general use.

Selon l'invention, dans une enveloppe métallique identique, on a réparti les charges dans la matrice polymérique polyuréthanne du chargement de façon à réaliser un chargement bi-composition massiquement équivalent au précédent et ayant les mêmes dimensions. Ce chargement bi-composition est constitué d'un cylindre plein en explosif composite ayant comme axe celui du chargement, de diamètre 168 mm, de composition 12 % en poids d'octogène, 72 % en poids d'ONTA et 16 % en poids de la matrice polymérique précitée, enrobé par une couronne cylindrique en une composition pyrotechnique de la famille des propergols solides composites, de diamètre intérieur 168 mm, de diamètre extérieur 248 mm, donc d'épaisseur 40 mm, de composition 68 % en poids de perchlorate d'ammonium, 18 % en poids d'aluminium et 14 % en poids de la matrice polymérique précitée. Aux additifs près, cette composition est celle d'un propergol BUTALANE. Ce chargement bi-composition a été réalisé selon la même technique que celle de l'exemple 1.According to the invention, in an identical metal casing, the charges are distributed in the polyurethane polymer matrix of the load so as to produce a bi-composition load massively equivalent to the previous one and having the same dimensions. This bi-composition charge consists of a cylinder full of composite explosive having as axis that of the charge, of diameter 168 mm, of composition 12% by weight of octogen, 72% by weight of ONTA and 16% by weight of the aforementioned polymer matrix, coated with a cylindrical crown in a pyrotechnic composition of the family of solid composite propellants, of internal diameter 168 mm, of external diameter 248 mm, therefore of thickness 40 mm, of composition 68% by weight of perchlorate d ammonium, 18% by weight of aluminum and 14% by weight of the aforementioned polymer matrix. Except for additives, this composition is that of a BUTALANE propellant. This bi-composition loading was carried out using the same technique as that of Example 1.

Le cylindre plein en explosif composite est muni d'un système d'amorçage constitué d'un générateur d'ondes planes, de grand diamètre 90 mm et de longueur 80 mm, situé co-axialement par rapport au chargement, de même nature que le générateur utilisé pour l'exemple 1.The cylinder full of composite explosive is provided with a priming system consisting of a generator of plane waves, of large diameter 90 mm and length 80 mm, located co-axially with respect to the load, of the same nature as the generator used for example 1.

On a réalisé, le long d'un merlon, un empilement de 3 éléments de munition ainsi constitués, c'est-à-dire comprenant l'enveloppe, le chargement bi-composition et le relais d'amorçage. La distance de séparation des éléments est de 25 mm.A stack of 3 ammunition elements thus formed, that is to say comprising the casing, the bi-composition loading and the priming relay, was produced along a merlon. The separation distance of the elements is 25 mm.

On a ensuite réalisé l'amorçage du relais et conséquement celui de l'explosif composite constituant le cylindre plein du chargement de l'élément inférieur, à l'aide d'un détonateur classique en contact avec le relais.The relay was then primed and consequently that of the composite explosive constituting the full cylinder of the loading of the lower element, using a conventional detonator in contact with the relay.

La détonation de l'explosif composite constituant le cylindre plein du chargement de l'élément inférieur a entraîné la réaction sans détonation de la composition type propergol BUTALANE constituant la couche périphérique adjacente annulaire.The detonation of the composite explosive constituting the full cylinder of the loading of the lower element led to the reaction without detonation of the composition propellant type BUTALANE constituting the adjacent annular peripheral layer.

On a constaté la non détonation par influence des 2 éléments récepteurs supérieurs, et ce, malgré la présence , dans ces 2 éléments, d'un système d'amorçage identique à celui de l'élément donneur. The detonation by influence of the 2 upper receptor elements has been observed , despite the presence in these 2 elements of an initiation system identical to that of the donor element.

Cet essai démontre la quasi invulnérabilité de l'élément de munition "enveloppe-chargement-relais" vis-à-vis de l'onde de détonation, notamment lors du stockage, et l'intérêt de l'invention puisque le chargement monocomposition massiquement équivalent, trop difficilement amorçable, ne peut en pratique pas être utilisé, pour les raisons précitées.This test demonstrates the almost invulnerability of the "envelope-loading-relay" munition element with respect to the detonation wave, in particular during storage, and the advantage of the invention since the massively equivalent single-composition loading , too difficult to boot, cannot in practice be used, for the aforementioned reasons.

Ce résultat n'est pas obtenu au détriment des effets recherchés puisque l'élément précité bi-composition selon l'invention présente des effets de souffle et/ou de bulles voisins de ceux obtenus avec l'élément monocomposition massiquement équivalent.This result is not obtained at the expense of the desired effects since the aforementioned bi-composition element according to the invention exhibits blast and / or bubble effects close to those obtained with the massively equivalent monocomposition element.

Claims (20)

  1. Explosive munition element consisting of a casing, preferably of metal, containing a multi-composition explosive charge having a plurality of adjacent coaxial layers, characterised in that the innermost layer, which is preferably solid, is a composite explosive consisting of a loaded polyurethane or polyester polymer matrix, whose load contains more than 40% by weight of organic nitrate explosive, this percentage being expressed in relation to the composite explosive, and in that the peripheral layer is a pyrotechnic composition from the class of composite solid propellants consisting of a loaded polyurethane or polyester polymer matrix whose load contains at least one mineral oxidant and less than 10% in weight of organic nitrate explosive, this percentage being expressed with respect to the pyrotechnic composition from the class of composite solid propellants.
  2. Explosive munition element according to Claim 1, characterised in that the polymer matrix of the composite explosive forming the innermost layer and the polymer matrix of the pyrotechnic composition from the class of composite solid propellants forming the peripheral layer of the charge are identical.
  3. Explosive munition element according to any one of the preceding claims, characterised in that the polymer matrix of the composite explosive forming the innermost layer and the polymer matrix of the pyrotechnic composition from the class of composite solid propellants forming the peripheral layer of the charge are polyurethane matrices.
  4. Explosive munition element according to any one of the preceding claims, characterised in that the polyurethane polymer matrix is obtained by reacting a polybutadiene with hydroxyl terminations with a polyisocyanate.
  5. Explosive munition element according to any one of the preceding claims, characterised in that the explosive charge is a dual-composition charge, the inner layer being covered with an adjacent peripheral coaxial layer.
  6. Explosive munition element according to any one of the preceding claims, characterised in that the load of the pyrotechnic composition forming the peripheral layer contains a mineral oxidant chosen from the group composed of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate and mixtures thereof.
  7. Explosive munition element according to any one of the preceding claims, characterised in that the load of the pyrotechnic composition forming the peripheral layer contains a reducing metal.
  8. Explosive munition element according to Claim 7, characterised in that the reducing metal is chosen from the group composed of aluminium, zirconium, magnesium, boron and mixtures thereof, preferably aluminium.
  9. Explosive munition element according to any one of the preceding claims, characterised in that the load of the pyrotechnic composition forming the peripheral layer is free of organic nitrate explosive.
  10. Explosive munition element according to any one of Claims 1 to 6 and 9, characterised in that the load of the pyrotechnic composition forming the peripheral layer is a mineral oxidant chosen from the group composed of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate and mixtures thereof.
  11. Explosive munition element according to any one of Claims 1 to 9, characterised in that the load of the pyrotechnic composition forming the peripheral layer is a mixture of a reducing metal, preferably chosen from the group composed of aluminium, zirconium, magnesium, boron and mixtures thereof, and of a mineral oxidant chosen from the group consisting of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate and mixtures thereof.
  12. Explosive munition element according to any one of Claims 1 to 9 and 11, characterised in that the load of the pyrotechnic composition forming the peripheral layer is a mixture of ammonium perchlorate and aluminium.
  13. Explosive munition element according to any one of Claims 1 to 9, 11 and 12, characterised in that the peripheral layer consists of:
    - 10% to 40% by weight of a polyurethane polymer matrix
    - 5% to 40% by weight of aluminium
    - 20% to 85% by weight of ammonium perchlorate, the sum of the percentages being equal to 100%.
  14. Explosive munition element according to any one of the preceding claims, characterised in that the organic nitrate explosive contained in the load of the composite explosive forming the innermost layer of the charge is chosen from the group composed of hexogen, octogen, pentrite, 5-oxo 3-nitro 1,2,4-triazole, triaminotrinitrobenzene, nitroguanidine and mixtures thereof.
  15. Explosive munition element according to any one of the preceding claims, characterised in that the organic nitrate explosive contained in the load of the composite explosive forming the innermost layer of the charge is chosen from the group composed of hexogen, octogen, 5-oxo 3-nitro 1,2,4-triazole and mixtures thereof.
  16. Explosive munition element according to any one of the preceding claims, characterised in that the load of the composite explosive forming the innermost layer of the charge consists solely of organic nitrate explosive.
  17. Explosive munition element according to any one of Claims 1 to 15, characterised in that the load of the composite explosive forming the innermost layer of the charge consists of organic nitrate explosive in a mixture with a load chosen from the group composed of ammonium perchlorate, potassium perchlorate, ammonium nitrate, sodium nitrate, reducing metals and mixtures thereof.
  18. Explosive munition element according to any one of Claims 1 to 15 and 17, characterised in that the load of the composite explosive forming the innermost layer of the charge consists of organic nitrate explosive in a mixture with a load chosen from the group composed of ammonium perchlorate, aluminium and mixtures thereof.
  19. Explosive munition element according to any one of the preceding claims, characterised in that the innermost layer of composite explosive consists of:
    - 10% to 25% by weight of a polyurethane polymer matrix
    - 40% to 90% by weight of an organic nitrate explosive chosen from the group consisting of hexogen, octogen, 5-oxo 3-nitro 1,2,4-triazole and mixtures thereof
    - 0% to 35% by weight of aluminium
    - 0% to 45% by weight of ammonium perchlorate,
    the sum of the percentages being equal to 100.
  20. Process for obtaining a blast and/or bubble effect through the release of gas in the casing of an explosive munition element consisting of a casing containing an explosive charge, and then the rupture of the casing due to the pressure of the gas, characterised in that the explosive munition element is an element according to any one of the Claims 1 to 19, and in that the release of gas is obtained by the detonation of the composite explosive forming the innermost layer of the charge, and then the reaction without detonation of the pyrotechnic composition from the class of composite solid propellants forming the peripheral layer, a reaction initiated by the detonation wave resulting from the detonation of the composite explosive.
EP91402612A 1990-10-17 1991-10-01 Insensitive ammunition containing an explosive multi-compositional charge and process for obtaining a blasting effect in water as well as in air Expired - Lifetime EP0481838B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9012797A FR2668146B1 (en) 1990-10-17 1990-10-17 LITTLE VULNERABLE ELEMENT OF EXPLOSIVE AMMUNITION COMPRISING A MULTI-COMPOSITION EXPLOSIVE LOADING AND METHOD FOR OBTAINING A BREATH AND / OR BUBBLE EFFECT.
FR9012797 1990-10-17

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EP0481838A1 EP0481838A1 (en) 1992-04-22
EP0481838B1 true EP0481838B1 (en) 1995-03-29

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US (1) US5189247A (en)
EP (1) EP0481838B1 (en)
JP (1) JP3004779B2 (en)
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AU (1) AU645120B2 (en)
CA (1) CA2053501C (en)
DE (1) DE69108507T2 (en)
DK (1) DK0481838T3 (en)
ES (1) ES2071258T3 (en)
FI (1) FI105473B (en)
FR (1) FR2668146B1 (en)
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US5320043A (en) * 1990-10-17 1994-06-14 Snpe Inc. Low-vulnerability explosive munitions element including a multicomposition explosive charge, and method for obtaining a blast and/or bubble effect
FR2678262B1 (en) * 1991-06-26 1993-12-10 Poudres Explosifs Ste Nale LITTLE VULNERABLE ELEMENT OF EXPLOSIVE AMMUNITION COMPRISING A BI-COMPOSITION EXPLOSIVE LOADING AND METHOD FOR OBTAINING A SHARD EFFECT.
FR2688498B1 (en) * 1992-03-11 1994-05-06 Poudres Explosifs Ste Nale PROPULSIVE POWDER WITH LOW VULNERABILITY SENSITIVE TO IGNITION.
GB2466236B (en) * 1992-06-05 2010-11-17 Poudres & Explosifs Ste Nale Dual-composition plastic bonded explosive
US5417161A (en) * 1993-02-23 1995-05-23 Sri International Fabrication of molded block of dilute high explosive foamed polyurethane
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FR2741437B1 (en) * 1995-11-16 1997-12-19 Poudres & Explosifs Ste Nale METHOD OF MANUFACTURING EXPLOSIVE ELEMENT WITH CONTROLLED FRAGMENTATION
DE102010022982B3 (en) * 2010-06-08 2013-09-26 Rheinmetall Waffe Munition Gmbh Pressure-increasing explosive charge and ammunition containing this charge

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FR2577919B1 (en) * 1985-02-27 1987-02-20 Poudres & Explosifs Ste Nale PROCESS FOR THE MANUFACTURE WITHOUT SOLVENT OF COMPOSITE PYROTECHNIC PRODUCTS WITH THERMOSETTING BINDER AND PRODUCTS THUS OBTAINED, IN PARTICULAR COMPOSITE PROPULSIVE POWDERS
US4952254A (en) * 1989-08-07 1990-08-28 The United States Of America As Represented By The Secretary Of The Army High impulse, non-detonable propellant
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US5085725A (en) * 1990-08-06 1992-02-04 The United States Of America As Represented By The Secretary Of The Army Method of chemical bonding of solid propellant grains to the internal insulation of an interceptor motor

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FR2668146B1 (en) 1993-10-22
CA2053501A1 (en) 1992-04-18
JP3004779B2 (en) 2000-01-31
NO174664C (en) 1994-06-15
FR2668146A1 (en) 1992-04-24
FI105473B (en) 2000-08-31
NO174664B (en) 1994-03-07
IL99021A (en) 1994-12-29
DE69108507T2 (en) 1995-08-17
AU8346391A (en) 1992-04-30
NO913285D0 (en) 1991-08-22
US5189247A (en) 1993-02-23
DK0481838T3 (en) 1995-07-03
AU645120B2 (en) 1994-01-06
JPH04244599A (en) 1992-09-01
FI914872A0 (en) 1991-10-16
FI914872A (en) 1992-04-18
EP0481838A1 (en) 1992-04-22
ES2071258T3 (en) 1995-06-16
ATE120442T1 (en) 1995-04-15
CA2053501C (en) 1999-09-07
IL99021A0 (en) 1992-07-15
NO913285L (en) 1992-04-21
DE69108507D1 (en) 1995-05-04

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