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EP0880006A1 - Non-toxic composite projectile with biodegradable polymer matrix for ammunition cartridges - Google Patents

Non-toxic composite projectile with biodegradable polymer matrix for ammunition cartridges Download PDF

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Publication number
EP0880006A1
EP0880006A1 EP98401174A EP98401174A EP0880006A1 EP 0880006 A1 EP0880006 A1 EP 0880006A1 EP 98401174 A EP98401174 A EP 98401174A EP 98401174 A EP98401174 A EP 98401174A EP 0880006 A1 EP0880006 A1 EP 0880006A1
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EP
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Prior art keywords
weight
polymer matrix
projectile according
projectiles
tungsten
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Granted
Application number
EP98401174A
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German (de)
French (fr)
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EP0880006B1 (en
Inventor
Jacques Maucourt
Claude Combette
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Safran Ceramics SA
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Societe Nationale des Poudres et Explosifs
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B7/00—Shotgun ammunition
    • F42B7/02—Cartridges, i.e. cases with propellant charge and missile
    • F42B7/04—Cartridges, i.e. cases with propellant charge and missile of pellet type
    • F42B7/046—Pellets or shot therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0094—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with organic materials as the main non-metallic constituent, e.g. resin

Definitions

  • the present invention relates to the field of hunting and rifle shooting, specifically that of generally spherical projectiles, also called "pellets”, contained in hunting cartridges or shoot.
  • Lead projectiles have been used for a very long time. a long time, but due to the toxicity of this metal its use is becoming more and more regulated, and it has proposed to replace lead with other metals dense non-toxic, or less toxic than lead, like for example iron and tungsten, but these metal projectiles are too hard, which results, on the one hand, rapid erosion of the rifle barrel, and on the other hand unwanted injuries and bleeding game which, not being killed instantly, suffers unnecessarily and sometimes even flee despite his injuries.
  • patents GB 2 149 067 and GB 2 200 976 describe for example spherical composite projectiles for cartridges, obtained by extrusion or injection molding, and made up of particles rich in tungsten in a polyethylene plastic or rubber silicone.
  • EP 641 836 describes compositions for cartridge projectiles made of particles dense, preferably tungsten powder, in a polymer matrix comprising a rigid polymer thermoplastic such as polypropylene or polystyrene associated with a thermoplastic elastomeric polymer, such as copolymers based on polystyrene.
  • PCT patent WO 94/24511 describes projectiles composites for cartridges made of particles finely divided metals, based in particular on tungsten and / or molybdenum, dispersed in a polymer matrix which can be either thermoplastic polystyrene, chlorosulfonated polyethylene or copolymer of ethylene and vinyl acetate, i.e. thermosetting in epoxy resin or formaldehyde-based.
  • the polymer matrix of these projectiles is not biodegradable, which leads to pollution undesirable from nature, especially fields and meadows, or the environment of shooting ranges.
  • the object of the present invention is precisely to offer such composite projectiles for cartridges hunting or shooting.
  • solid polymeric matrix means a solid matrix under normal conditions use of cartridges, i.e. at a pressure close to normal atmosphere pressure and at a temperature between approximately - 20 ° C and approximately + 50 ° C.
  • the titanium oxide is in anatase form.
  • the rutile form is also usable, but we have unexpectedly found that the use of the anatase form made it possible to obtain the biodegradation of the polymer matrix.
  • the hydrocarbon binder also comprises, in addition to the ester functional groups, urethane functional groups and / or amide functional groups
  • the molar ratio between the urethane groups and ester groups is less than 0.05.
  • the polymer matrix also comprises at least one additive chosen from the group consisting of alkaline stearates, alkaline earth stearates, alkali carbonates, alkaline earth carbonates, alkali sulfates and alkaline earth sulfates.
  • this additive consists of a mixture of calcium stearate and carbonate calcium.
  • the polymer matrix also includes a plasticizer.
  • a plasticizer In addition to its plasticizing function, hydrocarbon binder allowing or promoting a setting work according to the usual techniques of shaping thermoplastic materials such as injection or extrusion, it was found that the presence of this plasticizer also promoted the biodegradation of polymer matrix.
  • plasticizers are trialkyl acetylcitrates, especially those whose alkyl radicals each have from 2 to 4 atoms of carbon, such as triethyl acetyl citrate and tributyl acetyl citrate.
  • the composite projectiles according to the invention have a density of between 7.5 g / cm 3 and 10.5 g / cm 3 .
  • the particles are made of tungsten or a alloy comprising tungsten, but it is possible to use, in the context of the invention, many other metals such as tin, molybdenum, titanium, bismuth, iron and copper.
  • Alloys containing tungsten are particularly preferred, especially those with iron, especially those for which the content tungsten weight is between 30% and 70%, from preferably between 40% by weight and 60% by weight.
  • tungsten-iron alloys can also understand other metals, like nickel and cobalt.
  • the particles metal are in powder form, the diameter of which median is preferably between 10 ⁇ m and 300 ⁇ m.
  • the composite projectiles according to the invention may also include, at low content, various additives well known to those skilled in the art for this type projectiles, for example a lubricant mold release like calcium stearate.
  • the composition corresponding to the polymer matrix is first prepared, preferably in the form of thermoplastic granules, from thermoplastic hydrocarbon binders comprising functional ester groups associated C 1 - C 20 aliphatic hydrocarbon chains, some of which are commercial products, and which can for example be obtained by reaction of an aliphatic diol such as 1,4-butane diol with an aliphatic diacid such as succinic acid or adipic acid.
  • thermoplastic hydrocarbon binders comprising functional ester groups associated C 1 - C 20 aliphatic hydrocarbon chains, some of which are commercial products, and which can for example be obtained by reaction of an aliphatic diol such as 1,4-butane diol with an aliphatic diacid such as succinic acid or adipic acid.
  • the formulation of this binder may contain some aliphatic diisocyanate or cycloaliphatic to introduce some functions urethanes, or even contain a diamine aliphatic or a lactam to introduce functions amides, for example of the polycaprolactam type.
  • the binder is introduced in the form of granules and the other constituents of the matrix polymer in a heated mixer, for example a "BUSS" co-kneader well known to those skilled in the art loom, so as to form a homogeneous paste.
  • a heated mixer for example a "BUSS" co-kneader well known to those skilled in the art loom, so as to form a homogeneous paste.
  • the composition in the form of granules thermoplastics, for example cylindrical, the length is close to the diameter, of the order of mm or a few mm.
  • thermoplastic granules and particles metallic we can then make a molding powder based of these thermoplastic granules and particles metallic, either “dry” by agitation in a mixer after grinding the granules, either by “solvent”, by dissolving the thermoplastic granules in a solvent such as chloroform in the presence of metal particles, then evaporation of the solvent under stirring of the mixture.
  • solvent such as chloroform
  • the composite projectiles according to the invention can then be obtained by pelletizing this molding powder, for example at room temperature (Approximately 20 ° C), in molds containing imprints to the desired shape.
  • granules can be produced cylindrical, for example with a diameter of 3 mm and length 3 mm, by co-mixing then extrusion and cutting. These cylindrical granules are then injected into molds to the desired shape using a press injection for thermoplastic materials.
  • Example 1 Production of non-toxic spherical composite projectiles (diameter 3 mm) according to the invention, with a biodegradable polyester-urethane polymer matrix, with a density of 7.9 g / cm 3 .
  • Example 2 Production of non-toxic spherical composite projectiles (diameter 3 mm) according to the invention, with a biodegradable polyester-amide polymer matrix, with a density of 7.8 g / cm 3

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Non-toxic composite projectiles, used for cartridges in hunting or shooting galleries, consist of metallic particles dispersed in solid polymer matrix, which is biodegradable and comprises hydrocarbon binder containing (i) functional ester groups attached to 1-20 C saturated or unsaturated chains; (ii) starch; and (iii) titanium dioxide.

Description

La présente invention concerne le domaine de la chasse et du tir au fusil, plus précisément celui des projectiles en général sphériques, encore appelés "plombs", contenus dans les cartouches de chasse ou de tir.The present invention relates to the field of hunting and rifle shooting, specifically that of generally spherical projectiles, also called "pellets", contained in hunting cartridges or shoot.

Les projectiles en plomb sont utilisés depuis très longtemps, mais du fait de la toxicité de ce métal son utilisation devient de plus en plus réglementée, et il a été proposé de remplacer le plomb par d'autres métaux denses non toxiques, ou moins toxiques que le plomb, comme par exemple le fer et le tungstène, mais ces projectiles métalliques sont trop durs, ce qui entraíne, d'une part une érosion rapide du canon du fusil, et d'autre part des blessures et saignements indésirables du gibier qui, n'étant pas tué sur le coup, souffre inutilement et, parfois même, peut prendre la fuite malgré ses blessures.Lead projectiles have been used for a very long time. a long time, but due to the toxicity of this metal its use is becoming more and more regulated, and it has proposed to replace lead with other metals dense non-toxic, or less toxic than lead, like for example iron and tungsten, but these metal projectiles are too hard, which results, on the one hand, rapid erosion of the rifle barrel, and on the other hand unwanted injuries and bleeding game which, not being killed instantly, suffers unnecessarily and sometimes even flee despite his injuries.

Pour notamment remédier à ce problème de dureté, il est maintenant connu de réaliser des projectiles composites non toxiques constitués de fines particules métalliques non toxiques dispersées dans une matrice solide polymérique.To remedy this hardness problem in particular, it is now known to make projectiles non-toxic composites made up of fine particles non-toxic metals dispersed in a matrix polymeric solid.

Les brevets GB 2 149 067 et GB 2 200 976 décrivent par exemple des projectiles composites sphériques pour cartouches, obtenus par extrusion ou injection-moulage, et constituées de particules riches en tungstène dans une matière plastique en polyéthylène ou en gomme de silicone.The patents GB 2 149 067 and GB 2 200 976 describe for example spherical composite projectiles for cartridges, obtained by extrusion or injection molding, and made up of particles rich in tungsten in a polyethylene plastic or rubber silicone.

Le brevet EP 641 836 décrit des compositions pour projectiles de cartouches constituées de particules denses, de préférence du tungstène en poudre, dans une matrice polymérique comprenant un polymère rigide thermoplastique comme le polypropylène ou le polystyrène associé à un polymère élastomère thermoplastique, comme les copolymères à base de polystyrène. EP 641 836 describes compositions for cartridge projectiles made of particles dense, preferably tungsten powder, in a polymer matrix comprising a rigid polymer thermoplastic such as polypropylene or polystyrene associated with a thermoplastic elastomeric polymer, such as copolymers based on polystyrene.

Le brevet PCT WO 94/24511 décrit des projectiles composites pour cartouches constitués de particules métalliques finement divisées, à base notamment de tungstène et/ou de molybdène, dispersées dans une matrice polymérique qui peut être, soit thermoplastique en polystyrène, polyéthylène chlorosulfoné ou en copolymère d'éthylène et d'acétate de vinyle, soit thermodurcissable en résine époxy ou à base de formol.PCT patent WO 94/24511 describes projectiles composites for cartridges made of particles finely divided metals, based in particular on tungsten and / or molybdenum, dispersed in a polymer matrix which can be either thermoplastic polystyrene, chlorosulfonated polyethylene or copolymer of ethylene and vinyl acetate, i.e. thermosetting in epoxy resin or formaldehyde-based.

Ces divers projectiles composites non toxiques représentant l'état de la technique sont toutefois très onéreux, du fait des matières premières utilisées ou des procédés de mise en oeuvre et de mise en forme, et/ou du fait qu'ils présentent des propriétés balistiques nettement insuffisantes comparées à celles des projectiles classiques en plomb.These various non-toxic composite projectiles representing the state of the art are however very expensive, due to the raw materials used or implementation and shaping methods, and / or fact that they have ballistic properties clearly insufficient compared to those of conventional lead projectiles.

De plus, la matrice polymérique de ces projectiles n'est pas biodégradable, ce qui entraíne une pollution indésirable de la nature, notamment des champs et prairies, ou de l'environnement des stands de tir.In addition, the polymer matrix of these projectiles is not biodegradable, which leads to pollution undesirable from nature, especially fields and meadows, or the environment of shooting ranges.

Le brevet EP 641 836 précité mentionne bien l'utilisation possible de certains polymères ou copolymères insaturés dans la matrice polymérique pour favoriser après tir sa dégradation oxydante par l'oxygène de l'air, mais ce document ne décrit pas de projectile composite à matrice biodégradable, c'est à dire dégradable beaucoup plus rapidement selon des mécanismes biologiques faisant intervenir des microorganismes.The aforementioned patent EP 641 836 mentions well the possible use of certain polymers or unsaturated copolymers in the polymer matrix for promote after oxidative degradation by oxygen in the air, but this document does not describe composite projectile with a biodegradable matrix, say degradable much faster according to biological mechanisms involving microorganisms.

De façon générale, lors de la dégradation oxydante des matrices polymériques jusqu'alors utilisées dans les projectiles composites pour cartouches de chasse ou de tir, le liant se décompose très lentement, durant plusieurs dizaines d'années sous l'action de l'oxygène de l'air, en petits fragments macromoléculaires totalement imputrescibles qui peuvent, même s'ils ne sont pas visibles, endommager gravement le système digestif des animaux qui viennent à les avaler avec l'herbe qu'ils broutent. De tels fragments subsistent en général bien au delà de 100 ans, comme c'est le cas pour le polyéthylène.Generally, during oxidative degradation polymer matrices hitherto used in composite projectiles for hunting cartridges or shot, the binder decomposes very slowly, during several decades under the action of oxygen air, in small macromolecular fragments totally rot-proof which can, even if they do not are not visible, seriously damage the system digestive of animals that come to swallow them with the grass they graze on. Such fragments remain in generally well beyond 100 years, as is the case for polyethylene.

L'homme du métier est donc à la recherche de projectiles composites pour cartouches de chasse ou de tir, non toxiques, à matrice polymérique biodégradable dans de brefs délais, dont le prix n'est pas prohibitif et dont les performances balistiques sont voisines de celles des projectiles classiques en plomb.Those skilled in the art are therefore looking for composite projectiles for hunting cartridges or shot, non-toxic, with biodegradable polymer matrix at short notice, the price of which is not prohibitive and whose ballistic performances are close to those of conventional lead projectiles.

L'objet de la présente invention est précisément de proposer de tels projectiles composites pour cartouches de chasse ou de tir.The object of the present invention is precisely to offer such composite projectiles for cartridges hunting or shooting.

Selon l'invention, ces projectiles composites, de préférence sphériques et qui sont constitués de particules métalliques, de préférence finement divisées sous forme de poudre, dispersées dans une matrice polymérique solide, sont caractérisées en ce que la matrice polymérique solide est biodégradable et comprend :

  • un liant hydrocarboné comportant des groupes fonctionnels esters
    Figure 00030001
    associés à des chaínes hydrocarbonées choisies dans le groupe constitué par les chaínes aliphatiques saturées ou insaturées comportant de 1 à 20 atomes de carbone, de préférence de 2 à 12 atomes de carbone,
  • de l'amidon,
  • du dioxyde de titane.
According to the invention, these composite projectiles, preferably spherical and which consist of metallic particles, preferably finely divided in powder form, dispersed in a solid polymer matrix, are characterized in that the solid polymer matrix is biodegradable and comprises:
  • a hydrocarbon binder comprising ester functional groups
    Figure 00030001
    associated with hydrocarbon chains chosen from the group consisting of saturated or unsaturated aliphatic chains containing from 1 to 20 carbon atoms, preferably from 2 to 12 carbon atoms,
  • starch,
  • titanium dioxide.

On entend par matrice polymérique "solide", une matrice solide dans les conditions normales d'utilisation des cartouches, c'est-à-dire à une pression proche de la pression atmosphère normale et à une température comprise entre environ - 20°C et environ + 50°C.The term "solid" polymeric matrix means a solid matrix under normal conditions use of cartridges, i.e. at a pressure close to normal atmosphere pressure and at a temperature between approximately - 20 ° C and approximately + 50 ° C.

On a constaté, de façon inattendue, que ces projectiles composites non toxiques selon l'invention présentaient simultanément tout un ensemble de propriétés rendant leur utilisation particulièrement attractive :

  • tous les constituants organiques sont totalement biodégradables. Ils ne laissent subsister, après exposition à la lumière et à la pluie, dans des délais pouvant être aussi brefs que 1 à 2 ans, aucune particule susceptible de nuire à un animal,
  • le comportement balistique est proche de celui des projectiles en plomb,
  • le coût de fabrication n'est plus prohibitif et est très nettement inférieur à celui des projectiles composites connus, notamment du fait de la nature de la matrice polymérique et de la simplicité du procédé de mise en oeuvre et de mise en forme, qui peut très facilement être extrapolable au stade industriel,
  • la masse volumique des projectiles est supérieure ou égale à celle de l'acier,
  • les projectiles sont particulièrement non érosifs. Ils ne détériorent pas le canon des fusils et ne nécessitent pas d'aménagements particuliers des armes ou des munitions,
  • l'aptitude aux ricochets sur tout obstacle est faible et la pénétration dans l'écorce des arbres est aussi réduite qu'avec des projectiles en plomb,
  • l'aptitude particulièrement élevée du liant selon l'invention à apporter la cohésion des particules métalliques, ce qui permet des taux de charges élevés, pouvant être supérieurs à 95% en poids environ.
It was found, unexpectedly, that these non-toxic composite projectiles according to the invention simultaneously exhibited a whole set of properties making their use particularly attractive:
  • all organic constituents are completely biodegradable. They do not allow to remain, after exposure to light and rain, in periods which can be as short as 1 to 2 years, no particle liable to harm an animal,
  • ballistic behavior is close to that of lead projectiles,
  • the manufacturing cost is no longer prohibitive and is very much lower than that of known composite projectiles, in particular due to the nature of the polymer matrix and the simplicity of the process of implementation and shaping, which can very easily be extrapolated to the industrial stage,
  • the density of the projectiles is greater than or equal to that of steel,
  • projectiles are particularly non-erosive. They do not deteriorate the barrel of the rifles and do not require special arrangements of weapons or ammunition,
  • the ability to ricochet on any obstacle is low and penetration into the bark of trees is as reduced as with lead projectiles,
  • the particularly high ability of the binder according to the invention to bring the cohesion of the metal particles, which allows high loading rates, which can be greater than 95% by weight approximately.

Selon une première variante préférée de l'invention, l'oxyde de titane est sous forme anatase. According to a first preferred variant of the invention, the titanium oxide is in anatase form.

La forme rutile est également utilisable, mais on a constaté, de façon inattendue, que l'utilisation de la forme anatase permettait d'obtenir plus rapidement la biodégradation de la matrice polymérique.The rutile form is also usable, but we have unexpectedly found that the use of the anatase form made it possible to obtain the biodegradation of the polymer matrix.

Selon une seconde variante préférée de l'invention, le liant hydrocarboné comporte également, en plus des groupes fonctionnels esters, des groupes fonctionnels uréthannes

Figure 00050001
et/ou des groupes fonctionnels amides
Figure 00050002
According to a second preferred variant of the invention, the hydrocarbon binder also comprises, in addition to the ester functional groups, urethane functional groups
Figure 00050001
and / or amide functional groups
Figure 00050002

On a constaté, avec surprise, que notamment les fonctions uréthannes, en association avec les fonctions esters, permettaient d'obtenir une biodégradation plus rapide de la matrice polymérique.It was noted, with surprise, that in particular the urethane functions, in combination with the functions esters, provided more biodegradation rapid polymer matrix.

Avantageusement, le rapport molaire entre les groupes uréthannes et les groupes esters est inférieur à 0,05.Advantageously, the molar ratio between the urethane groups and ester groups is less than 0.05.

Selon une troisième variante préférée de l'invention, la matrice polymérique comprend également au moins un additif choisi dans le groupe constitué par les stéarates alcalins, les stéarates alcalino-terreux, les carbonates alcalins, les carbonates alcalino-terreux, les sulfates alcalins et les sulfates alcalino-terreux.According to a third preferred variant of the invention, the polymer matrix also comprises at least one additive chosen from the group consisting of alkaline stearates, alkaline earth stearates, alkali carbonates, alkaline earth carbonates, alkali sulfates and alkaline earth sulfates.

On a constaté, sans explication, que la présence d'un tel additif favorisait également la biodégradation de la matrice polymérique.It was found, without explanation, that the presence of such an additive also promoted biodegradation of the polymer matrix.

Avantageusement, cet additif est constitué par un mélange de stéarate de calcium et de carbonate de calcium.Advantageously, this additive consists of a mixture of calcium stearate and carbonate calcium.

Selon une autre variante préférée de l'invention, la matrice polymérique comprend également un plastifiant. En plus de sa fonction de plastification du liant hydrocarboné permettant ou favorisant une mise en oeuvre selon les techniques usuelles de mise en forme des matériaux thermoplastiques comme l'injection ou l'extrusion, on a constaté que la présence de ce plastifiant favorisait également la biodégradation de la matrice polymérique.According to another preferred variant of the invention, the polymer matrix also includes a plasticizer. In addition to its plasticizing function, hydrocarbon binder allowing or promoting a setting work according to the usual techniques of shaping thermoplastic materials such as injection or extrusion, it was found that the presence of this plasticizer also promoted the biodegradation of polymer matrix.

Les plastifiants particulièrement préférés sont les acétylcitrates de trialkyle, notamment ceux dont les radicaux alkyles comportent chacun de 2 à 4 atomes de carbone, comme par exemple l'acétylcitrate de triéthyle et l'acétylcitrate de tributyle.Particularly preferred plasticizers are trialkyl acetylcitrates, especially those whose alkyl radicals each have from 2 to 4 atoms of carbon, such as triethyl acetyl citrate and tributyl acetyl citrate.

Les matrices polymériques préférées selon l'invention comprennent :

  • au moins 75% en poids de liant, de préférence entre 75% en poids et 90% en poids,
  • au moins 2,5% en poids d'amidon, de préférence entre 2,5% en poids et 20% en poids,
  • au moins 0,5% en poids d'oxyde de titane sous forme anatase, de préférence entre 0,5% en poids et 5% en poids,
  • au moins 0,5% en poids de carbonate de calcium, de préférence entre 0,5% en poids et 2,5% en poids,
  • au moins 0,5% en poids de stéarate de calcium, de préférence entre 0,5% en poids et 1% en poids,
  • au moins 1% en poids d'un acétylcitrate de trialkyle, de préférence entre 1% en poids et 10% en poids.
The preferred polymeric matrices according to the invention comprise:
  • at least 75% by weight of binder, preferably between 75% by weight and 90% by weight,
  • at least 2.5% by weight of starch, preferably between 2.5% by weight and 20% by weight,
  • at least 0.5% by weight of titanium oxide in anatase form, preferably between 0.5% by weight and 5% by weight,
  • at least 0.5% by weight of calcium carbonate, preferably between 0.5% by weight and 2.5% by weight,
  • at least 0.5% by weight of calcium stearate, preferably between 0.5% by weight and 1% by weight,
  • at least 1% by weight of a trialkyl acetyl citrate, preferably between 1% by weight and 10% by weight.

Selon une autre variante préférée, les projectiles composites selon l'invention ont une masse volumique comprise entre 7,5 g/cm3 et 10,5 g/cm3.According to another preferred variant, the composite projectiles according to the invention have a density of between 7.5 g / cm 3 and 10.5 g / cm 3 .

Selon une autre variante préférée, les particules métalliques sont constituées de tungstène ou d'un alliage comportant du tungstène, mais on peut utiliser, dans le cadre de l'invention, de nombreux autres métaux tels que l'étain, le molybdène, le titane, le bismuth, le fer et le cuivre.According to another preferred variant, the particles are made of tungsten or a alloy comprising tungsten, but it is possible to use, in the context of the invention, many other metals such as tin, molybdenum, titanium, bismuth, iron and copper.

Les alliages comportant du tungstène sont particulièrement préférés, notamment ceux avec le fer, plus particulièrement ceux pour lesquels la teneur pondérale en tungstène est comprise entre 30% et 70%, de préférence entre 40% en poids et 60% en poids.Alloys containing tungsten are particularly preferred, especially those with iron, especially those for which the content tungsten weight is between 30% and 70%, from preferably between 40% by weight and 60% by weight.

Ces alliages tungstène-fer peuvent également comprendre d'autres métaux, comme le nickel et le cobalt.These tungsten-iron alloys can also understand other metals, like nickel and cobalt.

Selon une autre variante préférée, les particules métalliques sont sous forme de poudre, dont le diamètre médian est de préférence compris entre 10µm et 300µm.According to another preferred variant, the particles metal are in powder form, the diameter of which median is preferably between 10 μm and 300 μm.

De façon générale, dans le cadre de la présente invention, les projectiles composites comprennent :

  • entre 90% et 97% en poids de particules métalliques, de préférence entre 94% et 97% en poids, mieux encore entre 95% et 97% en poids,
  • entre 3% et 10% en poids de matrice polymérique, de préférence entre 3% et 7% en poids, mieux encore entre 3% et 5% en poids.
In general, in the context of the present invention, the composite projectiles comprise:
  • between 90% and 97% by weight of metallic particles, preferably between 94% and 97% by weight, better still between 95% and 97% by weight,
  • between 3% and 10% by weight of polymeric matrix, preferably between 3% and 7% by weight, better still between 3% and 5% by weight.

Les projectiles composites selon l'invention peuvent également comprendre, à faible teneur, divers additifs bien connus de l'homme du métier pour ce type de projectiles, par exemple un agent lubrifiant de démoulage comme le stéarate de calcium.The composite projectiles according to the invention may also include, at low content, various additives well known to those skilled in the art for this type projectiles, for example a lubricant mold release like calcium stearate.

En ce qui concerne l'obtention des projectiles composites précités selon l'invention, on prépare tout d'abord la composition correspondant à la matrice polymérique, de préférence sous forme de granulés thermoplastiques, à partir de liants hydrocarbonés thermoplastiques comportant des groupes fonctionnels esters associés à des chaínes hydrocarbonées aliphatiques C1 - C20, dont certains sont des produits commerciaux, et qui peuvent par exemple être obtenus par réaction d'un diol aliphatique comme le butane diol-1,4 avec un diacide aliphatique comme l'acide succinique ou l'acide adipique.With regard to obtaining the aforementioned composite projectiles according to the invention, the composition corresponding to the polymer matrix is first prepared, preferably in the form of thermoplastic granules, from thermoplastic hydrocarbon binders comprising functional ester groups associated C 1 - C 20 aliphatic hydrocarbon chains, some of which are commercial products, and which can for example be obtained by reaction of an aliphatic diol such as 1,4-butane diol with an aliphatic diacid such as succinic acid or adipic acid.

Afin d'allonger les chaínes du liant thermoplastique polyester, la formulation de ce liant pourra contenir un peu d'un diisocyanate aliphatique ou cycloaliphatique pour introduire quelques fonctions uréthannes, ou bien encore contenir une diamine aliphatique ou une lactame pour introduire des fonctions amides, par exemple de type polycaprolactame.In order to lengthen the chains of the binder thermoplastic polyester, the formulation of this binder may contain some aliphatic diisocyanate or cycloaliphatic to introduce some functions urethanes, or even contain a diamine aliphatic or a lactam to introduce functions amides, for example of the polycaprolactam type.

De façon préférée, on introduit le liant sous forme de granulés et les autres constituants de la matrice polymérique dans un mélangeur chauffé, par exemple un co-malaxeur de type "BUSS" bien connu de l'homme du métier, de manière à former une pâte homogène.Preferably, the binder is introduced in the form of granules and the other constituents of the matrix polymer in a heated mixer, for example a "BUSS" co-kneader well known to those skilled in the art loom, so as to form a homogeneous paste.

A l'aide d'une filière, puis d'une granulatrice, on peut récupérer la composition, sous forme de granulés thermoplastiques, par exemple cylindriques, dont la longueur est voisine du diamètre, de l'ordre du mm ou de quelques mm.Using a die, then a granulator, we can recover the composition, in the form of granules thermoplastics, for example cylindrical, the length is close to the diameter, of the order of mm or a few mm.

On peut ensuite réaliser une poudre à mouler à base de ces granulés thermoplastiques et des particules métalliques, soit par voie "sèche" par agitation dans un mélangeur après broyage des granulés, soit par voie "solvant", par dissolution des granulés thermoplastiques dans un solvant comme le chloroforme en présence des particules métalliques, puis évaporation du solvant sous agitation du mélange.We can then make a molding powder based of these thermoplastic granules and particles metallic, either "dry" by agitation in a mixer after grinding the granules, either by "solvent", by dissolving the thermoplastic granules in a solvent such as chloroform in the presence of metal particles, then evaporation of the solvent under stirring of the mixture.

Les projectiles composites selon l'invention peuvent ensuite être obtenus par pastillage de cette poudre à mouler, par exemple à la température ambiante (20°C environ), dans des moules contenant des empreintes à la forme désirée.The composite projectiles according to the invention can then be obtained by pelletizing this molding powder, for example at room temperature (Approximately 20 ° C), in molds containing imprints to the desired shape.

Selon une autre variante, en remplacement de la poudre à mouler, on peut réaliser des granulés cylindriques, par exemple de diamètre 3 mm et de longueur 3 mm, par comalaxage puis extrusion et découpe. Ces granulés cylindriques sont ensuite injectés dans des moules à la forme désirée à l'aide d'une presse à injection pour matériaux thermoplastiques.According to another variant, replacing the molding powder, granules can be produced cylindrical, for example with a diameter of 3 mm and length 3 mm, by co-mixing then extrusion and cutting. These cylindrical granules are then injected into molds to the desired shape using a press injection for thermoplastic materials.

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

Exemple 1 : Réalisation de projectiles composites sphériques (diamètre 3 mm) selon l'invention, non toxiques, à matrice polymérique biodégradable polyester-uréthanne, de masse volumique 7,9 g/cm3. Example 1 : Production of non-toxic spherical composite projectiles (diameter 3 mm) according to the invention, with a biodegradable polyester-urethane polymer matrix, with a density of 7.9 g / cm 3 .

  • a) Préparation de granulés thermoplastiques (composition pour la matrice polymérique des projectiles) Dans un co-malaxeur "BUSS" chauffé à 175°C environ, on introduit le liant polyester-uréthanne commercialisé sous forme de granulés par la Société SHOWA DENKO sous la marque de commerce BIONOLLE® 3001, qui est un copolymère de butane diol-1,4, d'acide adipique, d'acide succinique et d'un diisocyanate cycloaliphatique, ainsi que les constituants suivants en quantité telle qu'on obtienne la composition suivante :
    - liant BIONOLLE® 3001
    : 87,5% en poids
    - amidon de blé
    : 8,0% en poids
    - acétylcitrate de tributyle
    : 3,0% en poids
    - TiO2 sous forme anatase
    : 0,5% en poids
    - carbonate de calcium
    : 0,5% en poids
    - stéarate de calcium
    : 0,5% en poids
    Après formation d'une pâte homogène, et à l'aide d'une vis de transfert, la pâte est amenée au travers d'une filière de diamètre environ 2 mm.En sortie de filière, les brins sont amenés à l'entrée d'une granulatrice sous eau.On obtient finalement des granulés thermoplastiques cylindriques de diamètre environ 2 mm, de longueur environ 2 mm et de masse volumique 1,24 g/cm3.    a) Preparation of thermoplastic granules (composition for the polymer matrix of projectiles) In a "BUSS" co-kneader heated to approximately 175 ° C., the polyester-urethane binder sold in the form of granules is introduced by the company SHOWA DENKO under the brand BIONOLLE® 3001, which is a copolymer of 1,4-butane diol, adipic acid, succinic acid and a cycloaliphatic diisocyanate, as well as the following constituents in an amount such that the following composition is obtained:
    - BIONOLLE® 3001 binder
    : 87.5% by weight
    - wheat starch
    : 8.0% by weight
    - tributyl acetyl citrate
    : 3.0% by weight
    - TiO 2 in anatase form
    : 0.5% by weight
    - calcium carbonate
    : 0.5% by weight
    - calcium stearate
    : 0.5% by weight
    After forming a homogeneous paste, and using a transfer screw, the paste is brought through a die with a diameter of about 2 mm. At the end of the die, the strands are brought to the entry of granulator under water. Finally, we obtain cylindrical thermoplastic granules with a diameter of about 2 mm, a length of about 2 mm and a density of 1.24 g / cm 3 .
  • b) Préparation d'une poudre à mouler par voie "sèche" Après broyage cryogénique des granulés thermoplastiques obtenus selon a), de façon à obtenir une poudre ayant un diamètre médian de 150µm, on homogénéise, à la température ambiante, par agitation dans un mélangeur :
    • 4,5 parties en poids de la poudre précitée de diamètre médian 150µm,
    • 95 parties en poids d'une poudre de diamètre médian 90µm en alliage fer-tungstène de masse volumique 10,7 g/cm3, et dont les proportions pondérales Fe/W sont respectivement 45/55,
    • 0,5 partie en poids de stéarate de calcium (agent de démoulage).
    On obtient ainsi une poudre à mouler.    b) Preparation of a “dry” powder for molding After cryogenic grinding of the thermoplastic granules obtained according to a), so as to obtain a powder having a median diameter of 150 μm, it is homogenized, at ambient temperature, by stirring in a mixer:
    • 4.5 parts by weight of the above-mentioned powder with a median diameter of 150 μm,
    • 95 parts by weight of a powder with a median diameter of 90 μm of an iron-tungsten alloy with a density of 10.7 g / cm 3 , and whose weight proportions Fe / W are respectively 45/55,
    • 0.5 part by weight of calcium stearate (release agent).
    A powder for molding is thus obtained.
  • c) Réalisation et évaluation des projectiles composites A l'aide d'une pastilleuse, on effectue, à la température ambiante et sous une pression de plusieurs centaines de bars, un compactage de la poudre à mouler obtenue selon b) dans un moule multi-empreintes, chaque empreinte étant constituée de 2 cavités hémisphériques de diamètre intérieur 3 mm.
    Après démoulage, les projectiles composites sphériques obtenus ont une masse volumique de 7,9 g/cm3.On a observé un comportement balistique satisfaisant en tir de cartouche de chasse contenant 32 g de ces projectiles, aussi bien à - 20°C, qu'à + 20°C et + 50°C, avec une malléabilité et une intégrité comparables à celles d'un projectile en plomb.Ces projectiles, laissés au contact d'un sol en terre battue dans un environnement naturel à la température ambiante, se désintègrent très rapidement sous l'effet de la lumière et des microorganismes, notamment des bactéries.
    On observe l'apparition de craquelures après quelques semaines, suivie d'une désintégration du projectile.
    Après 6 mois, puis un an, il ne reste que respectivement 60% en poids environ et 30% en poids environ de la matrice polymérique.
    On note la disparition complète de cette matrice dans un délai de 2 ans environ.On a également réalisé un test de biodégradation selon la norme ASTM D 5988-96 à partir d'un projectile réduit en poudre puis mélangé avec de la terre. La biodégradation de la matrice est totale après 95 jours. Par ailleurs, un test comparatif, effectué rigoureusement dans les mêmes conditions selon la norme ASTM D 5988-96 à partir de cellulose, montre une disparition complète de la cellulose dans approximativement le même délai.On a ainsi observé, de façon surprenante, que la matrice polymérique des projectiles selon l'invention se biodégradait aussi rapidement que de la cellulose.    c) Production and evaluation of composite projectiles Using a pelletizer, compaction of the molding powder obtained according to b) is carried out at room temperature and under a pressure of several hundred bars in a multi- impressions, each impression consisting of 2 hemispherical cavities with an internal diameter of 3 mm.
    After demoulding, the spherical composite projectiles obtained have a density of 7.9 g / cm 3. We observed satisfactory ballistic behavior when firing a hunting cartridge containing 32 g of these projectiles, both at - 20 ° C, '' at + 20 ° C and + 50 ° C, with malleability and integrity comparable to that of a lead projectile. These projectiles, left in contact with a clay floor in a natural environment at room temperature, disintegrate very quickly under the effect of light and microorganisms, especially bacteria.
    The appearance of cracks is observed after a few weeks, followed by disintegration of the projectile.
    After 6 months, then one year, there remains only approximately 60% by weight approximately and 30% by weight approximately of the polymer matrix.
    We note the complete disappearance of this matrix in about 2 years. We also carried out a biodegradation test according to standard ASTM D 5988-96 from a projectile reduced to powder and then mixed with earth. The biodegradation of the matrix is complete after 95 days. In addition, a comparative test, carried out rigorously under the same conditions according to standard ASTM D 5988-96 from cellulose, shows a complete disappearance of the cellulose in approximately the same time period. It was thus observed, surprisingly, that the polymer matrix of projectiles according to the invention biodegraded as quickly as cellulose.

    • Exemple 2 : Réalisation de projectiles composites sphériques (diamètre 3 mm) selon l'invention, non toxiques, à matrice polymérique biodégradable polyester-amide, de masse volumique 7,8 g/cm3 Example 2 : Production of non-toxic spherical composite projectiles (diameter 3 mm) according to the invention, with a biodegradable polyester-amide polymer matrix, with a density of 7.8 g / cm 3

  • a) Préparation de granulés thermoplastiques (composition pour la matrice polymérique des projectiles) on opère rigoureusement comme selon l'exemple 1, mais en utilisant, à la place du liant polyester-uréthanne BIONOLLE®, le liant polyester-amide commercialisé sous forme de granulés par la Société BAYER sous la marque de commerce BAK® 1095, qui est un copolymère de butane diol-1,4, d'acide adipique et de caprolactame.On obtient des granulés cylindriques thermoplastiques de diamètre 2 mm, de longueur 2 mm et de masse volumique 1,17 g/cm3.a) Preparation of thermoplastic granules (composition for the polymeric matrix of projectiles), the procedure is rigorously carried out as according to Example 1, but using, in place of the polyester-urethane bion BIONOLLE®, the polyester-amide binder sold in the form of granules by the company BAYER under the trademark BAK® 1095, which is a copolymer of 1,4-butane diol, adipic acid and caprolactam. Thermoplastic cylindrical granules with a diameter of 2 mm, a length of 2 mm and density 1.17 g / cm 3 .
  • b) Préparation d'une poudre à mouler par voie "solvant" Dans un mélangeur avec pales en Z, on introduit :
    • 4,5 parties en poids de granulés thermoplastiques obtenus selon a),
    • 95 parties en poids d'une poudre de diamètre médian 90µm en alliage fer-tungstène de masse volumique 10,7 g/cm3, et dont les proportions pondérales sont respectivement 45/55,
    • 0,5 partie en poids de stéarate de calcium (agent de démoulage),
    • 50 parties en poids de chloroforme (solvant).
    Après dissolution des granulés et homogénéisation du mélange par agitation lente à la température ambiante durant 1/2 h environ, on évapore lentement, par léger chauffage, le solvant, tout en poursuivant l'agitation.On obtient ainsi une poudre à mouler constituée de grains de poudre métallique enrobés par un film polymérique.    b) Preparation of a molding powder by the "solvent" route In a mixer with Z-shaped blades, the following are introduced:
    • 4.5 parts by weight of thermoplastic granules obtained according to a),
    • 95 parts by weight of a powder with a median diameter of 90 μm of an iron-tungsten alloy with a density of 10.7 g / cm 3 , and whose weight proportions are 45/55 respectively,
    • 0.5 parts by weight of calcium stearate (release agent),
    • 50 parts by weight of chloroform (solvent).
    After dissolving the granules and homogenizing the mixture by slow stirring at room temperature for about 1/2 h, the solvent is evaporated slowly, with slight heating, while continuing the stirring. This gives a molding powder consisting of grains metallic powder coated with a polymer film.
  • c) Réalisation et évaluation des projectiles composites On opère rigoureusement comme selon l'exemple 1 avec la poudre à mouler obtenue selon b).On obtient des projectiles composites sphériques de diamètre 3 mm et de masse volumique 7,8 g/cm3.On a observé un comportement balistique satisfaisant en tir de cartouche de chasse contenant 32 g de ces projectiles, aussi bien à - 20°C, qu'à + 20°C et + 50°C, avec une malléabilité comparable à celle d'un projectile en plomb.Ces projectiles, laissés au contact d'un sol en terre battue dans un environnement naturel, présentent rapidement, au bout de quelques semaines, des craquelures, puis le projectile se désintègre après quelques mois.La matrice polymérique disparaít complètement après quelques années.c) Production and evaluation of composite projectiles The procedure is rigorous as in Example 1 with the molding powder obtained according to b). We obtain spherical composite projectiles with a diameter of 3 mm and a density of 7.8 g / cm 3 . observed satisfactory ballistic behavior when firing a hunting cartridge containing 32 g of these projectiles, both at - 20 ° C, and at + 20 ° C and + 50 ° C, with a malleability comparable to that of a projectile These projectiles, left in contact with a clay floor in a natural environment, quickly present, after a few weeks, cracks, then the projectile disintegrates after a few months.The polymer matrix disappears completely after a few years .

    • Claims (10)

    Projectile composite non toxique pour cartouches de chasse ou de tir au fusil, constitué de particules métalliques dispersées dans une matrice solide polymérique, caractérisé en ce que la matrice solide polymérique est biodégradable et comprend : un liant hydrocarboné comportant des groupes fonctionnels esters associés à des chaínes hydrocarbonées choisies dans le groupe constitué par les chaínes aliphatiques, saturées ou insaturées, comportant de 1 à 20 atomes de carbone, de l'amidon, du dioxyde de titane. Non-toxic composite projectile for hunting or rifle cartridges, consisting of metal particles dispersed in a solid polymer matrix, characterized in that the solid polymer matrix is biodegradable and comprises: a hydrocarbon binder comprising ester functional groups associated with hydrocarbon chains chosen from the group consisting of aliphatic chains, saturated or unsaturated, comprising from 1 to 20 carbon atoms, starch, titanium dioxide. Projectile selon la revendication 1, caractérisé en ce que sa masse volumique est comprise entre 7,5 g/cm3 et 10,5 g/cm3.Projectile according to claim 1, characterized in that its density is between 7.5 g / cm 3 and 10.5 g / cm 3 . Projectile selon la revendication 2, caractérisé en ce que les particules métalliques sont constituées de tungstène ou d'un alliage comportant du tungstène.Projectile according to claim 2, characterized in what metal particles are made up of tungsten or an alloy comprising tungsten. Projectile selon la revendication 3, caractérisé en ce que l'alliage comportant du tungstène est un alliage tungstène-fer.Projectile according to claim 3, characterized in what the alloy comprising tungsten is an alloy tungsten-iron. Projectile selon la revendication 1, caractérisé en ce que le dioxyde de titane est sous forme anatase.Projectile according to claim 1, characterized in what titanium dioxide is in anatase form. Projectile selon la revendication 1, caractérisé en ce que les chaínes hydrocarbonées aliphatiques comportent de 2 à 12 atomes de carbone. Projectile according to claim 1, characterized in what aliphatic hydrocarbon chains have 2 to 12 carbon atoms. Projectile selon la revendication 1, caractérisé en ce que le liant comporte également des groupes fonctionnels uréthannes et/ou amides.Projectile according to claim 1, characterized in what the binder also has groups functional urethanes and / or amides. Projectile selon la revendication 1, caractérisé en ce que la matrice polymérique comprend également au moins un additif choisi dans le groupe constitué par les stéarates alcalins, les stéarates alcalino-terreux, les carbonates alcalins, les carbonates alcalino-terreux, les sulfates alcalins et les sulfates alcalino-terreux.Projectile according to claim 1, characterized in which the polymer matrix also includes minus one additive chosen from the group consisting of alkaline stearates, alkaline earth stearates, alkaline carbonates, alkaline earth carbonates, alkali sulfates and alkaline earth sulfates. Projectile selon la revendication 1, caractérisé en ce que la matrice polymérique comprend également un plastifiant.Projectile according to claim 1, characterized in what the polymer matrix also includes a plasticizer. Projectile selon la revendication 1, caractérisé en ce que la matrice polymérique comprend : au moins 75% en poids de liant, au moins 2,5% en poids d'amidon, au moins 0,5% en poids d'oxyde de titane sous forme anatase, au moins 0,5% en poids de carbonate de calcium,
    au moins 0,5% en poids de stéarate de calcium,     au moins 1% en poids d'un acétylcitrate de trialkyle.     Projectile according to claim 1, characterized in that the polymer matrix comprises: at least 75% by weight of binder, at least 2.5% by weight of starch, at least 0.5% by weight of titanium oxide in anatase form, at least 0.5% by weight of calcium carbonate,
    at least 0.5% by weight of calcium stearate,     at least 1% by weight of a trialkyl acetyl citrate.
    EP98401174A 1997-05-23 1998-05-15 Non-toxic composite projectile with biodegradable polymer matrix for ammunition cartridges Expired - Lifetime EP0880006B1 (en)

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    DE19924747A1 (en) * 1999-05-31 2000-12-07 Dynamit Nobel Ag Lead-free projectile for hand-held weapons comprises a core of biodegradable molded material containing a biodegradable polymer and a mineral and/or metallic filler(s) and a (non)metallic coat.
    DE19924747B4 (en) * 1999-05-31 2014-07-17 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Lead-free projectile with density that can be set as required
    WO2001018483A1 (en) * 1999-09-08 2001-03-15 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Lead-reduced or lead-free hunting rifle projectile having an improved retention force of the core in the case
    WO2002012820A1 (en) * 2000-08-09 2002-02-14 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Projectile for short trajectory training ammunition
    EP4477987A1 (en) * 2023-06-15 2024-12-18 Decathlon Wad for shot or bullet cartridge, shot or bullet cartridge comprising such a wad, and methods for producing said wad and bullet cartridge
    FR3149966A1 (en) * 2023-06-15 2024-12-20 Decathlon Wad for shot or bullet cartridge, shot or bullet cartridge comprising such a wad, and methods of manufacturing said wad and said cartridge

    Also Published As

    Publication number Publication date
    FR2763675A1 (en) 1998-11-27
    DE69802230T2 (en) 2002-07-11
    FR2763675B1 (en) 1999-06-18
    CA2237848C (en) 2005-09-20
    CA2237848A1 (en) 1998-11-23
    DE69802230D1 (en) 2001-12-06
    US6101949A (en) 2000-08-15
    PT880006E (en) 2002-04-29
    DK0880006T3 (en) 2002-02-25
    EP0880006B1 (en) 2001-10-31
    ES2165133T3 (en) 2002-03-01

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