EP0814069B1 - Meltable/castable explosive composition with reduced sensitivity - Google Patents

Meltable/castable explosive composition with reduced sensitivity Download PDF

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Publication number
EP0814069B1
EP0814069B1 EP97401425A EP97401425A EP0814069B1 EP 0814069 B1 EP0814069 B1 EP 0814069B1 EP 97401425 A EP97401425 A EP 97401425A EP 97401425 A EP97401425 A EP 97401425A EP 0814069 B1 EP0814069 B1 EP 0814069B1
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Prior art keywords
mass
meltable
trinitro
composition according
explosive
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German (de)
French (fr)
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EP0814069A1 (en
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André Espagnaco
Philippe Morand
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Giat Industries SA
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Giat Industries SA
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/005—By a process involving melting at least part of the ingredients
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/04—Compositions containing a nitrated organic compound the nitrated compound being an aromatic

Definitions

  • the technical field of the invention is that of explosive fusable / flowable compositions.
  • TNT trinitrotoluene
  • TNT is most often used in admixture with a other more energetic solid explosive, for example hexogen or octogen.
  • a other more energetic solid explosive for example hexogen or octogen.
  • MURAT ammunition mitigated risks
  • These composite explosives are used by casting explosive mixed with the binder and an additive polymerization. Solidification is obtained by loading of the load.
  • the cooking is long (several days). It therefore consumes a lot of energy and therefore cannot be implemented for quantities of ammunition important.
  • ammunition with an explosive charge composite are difficult to demilitarize. Indeed, it it is not possible to melt the load for the come out of its envelope.
  • the only possible solutions are chemical destruction or the detonation, costly solutions harmful to the environment.
  • this composition can be implemented by casting. She also has the interesting property of being very not very sensitive to the main vulnerability tests as defined for example by the operating modes described by AFNOR NFT standards 70510 to 70515 or UN tests 7d) i, 7e), 7g), 7h), 7j) and 7k).
  • TNT melting temperature
  • US-A-5,431,756 and DE-A-2,310,217 describe explosive compositions liquid at 90 ° C or 100 ° C.
  • the first composition being based on TNT and the second at base of pentryl and tetryl.
  • US-A-3,994,756 proposes a composition explosive flowable at 121 ° C and whose fusible matrix is formed from a mixture of trinitrobenzene and 2,4,6 trinitro-m-xylene.
  • Patent FR-A-1,535,427 finally describes a composition explosive based on Trinitromethylaniline.
  • composition proposed by the invention has sensitivity to heating (slow or fast), impact and detonation by influence which is at least equal to that of known composite explosives. But she can be implemented industrially simple and economical by casting / melting.
  • the subject of the invention is a composition explosive fusible / flowable and with reduced vulnerability, as claimed in claim 1 and comprising on the one hand a fusible part formed of at least at least one fusible explosive, at least one phlegmatizer, and at least one phlegmatizer emulsifier in the fusible explosive chosen from the group defined in claim 1 and on the other hand a solid part comprising at least one solid explosive with vulnerability reduced, composition characterized in that the explosive fusable is a nitro-aromatic whose temperature of melting is greater than 100 ° C, the phlegmatizer having a melting temperature substantially equal to that of the fusible explosive and the proportion of phlegmatizer being at least equal to 3% of the total mass of the composition, the whole having a reaction temperature higher than 185 ° C.
  • the inventors' merit was to discover that it was possible to design an explosive fusable / flowable using explosives other than the TNT.
  • These explosives will be chosen with a melting point higher than 100 ° C, which will ensure the best performance of the thermal stress composition.
  • the invention proposes different criteria for choosing explosives which ensure that a composition with reduced vulnerability allowing to undergo successfully the main standardized tests.
  • this family of explosives presents a chemical stability analogous to that of TNT, allowing to guarantee behavior during detonation tests by influence and impact of projectiles which is close to that of TNT.
  • the phlegmatizer will incorporate an emulsifier which will chosen to ensure the best explosive interface Fade / phlegmatizer.
  • the phlegmatizer will both favor the dispersion of the powdery constituents and stabilize the emulsion obtained.
  • We will choose a phlegmatizer and an inert emulsifier (in particular, avoid nitrocellulose-based emulsifiers).
  • TNMA 2,4,6-trinitro-N-Methylaniline
  • Nitrated aromatic explosives have a structure of base consisting of at least one aromatic nucleus comprising at least three NO2 radicals and three other radicals designated for example R, R 'and R ".
  • radicals R, R 'and R may be chosen from the radicals: -H, -CH3, -NHCH3, -OH, -NH2 and their combinations.
  • the inventors studied the molecular and electronic structures of the different nitro aromatic explosives and chose a certain number of explosives having both a temperature of high melting and good behavior in the above tests bullet impact, slow or rapid heating and detonation by influence.
  • the structure of this body is as follows:
  • the mergeable part will advantageously constitute between 20% and 40% by mass of the composition.
  • the phlegmatizing agent may be a polyolefin wax and the emulsifier a vinyl pyrrolidone copolymer.
  • the solid explosive with reduced vulnerability could be chosen from the following explosives: oxynitrotriazol (ONTA), triaminotrinitrobenzene (TATB), Nitroguanidine (NGU).
  • ONTA oxynitrotriazol
  • TATB triaminotrinitrobenzene
  • NGU Nitroguanidine
  • the composition will advantageously be formulated so that its thermal diffusivity is at least 3.5 ⁇ 10 -7 m 2 / s between 30 and 47 ° C., thus improving the behavior of the composition during heating tests.
  • This thermal diffusivity can be obtained at by means of a dispersion of aluminum powder.
  • composition comprising:
  • the emulsifier is mixed with the phlegmatizer.
  • the proportion of emulsifier is chosen between 2 and 3% of the total mass of phlegmatizer used.
  • TNMA 2,4,6-trinitro-N-Methyl Aniline or TNMA is a known explosive, although not used industrially. he is described in particular by patent FR1535427. It is easy to be produced and has a melting point of 113 ° C to 119 ° C according to its degree of purity.
  • the phlegmatizer selected is a polyethylene wax (particular type of polyolefin) which is produced under the reference PED121 by the company Hoechst Wachs. Its temperature melting point is around 115 ° C (drop point from 113 to 118 ° C), which corresponds substantially to the temperature of TNMA merger.
  • This wax is commonly used in the field food for coating citrus fruits.
  • the emulsifier used for this wax is a copolymer of vinyl pyrrolidone, which is sold under the name Antaron WP660 by the company International Specialty Products.
  • This wax allows the production of an emulsion homogeneous and stable with TNMA and the emulsifier.
  • composition was carried out according to the process next:
  • ONTA is then incorporated in the form of a mixture of two different particle sizes and in proportions in equal mass.
  • a class grading 2 for which the size of. grains is between 200 and 800 micrometers, and a class 3 particle size for which the average grain diameter is 50 micrometers.
  • This combination of particle sizes ensures optimal loading of the composition while retaining good flowability properties.
  • the mixture is poured into an ammunition envelope maintained at the temperature of 120 ° C.
  • the ammunition envelope containing the composition according to the invention a certain number of tests described by AFNOR standards 70513 and 70515 and the tests UN 7d) i, 7f) and 7j).
  • the ammunition envelopes tested are models conform to those defined by the GEMO 3L1 operating mode (3 liter envelope containing 5 kg of explosive, wall in 10mm thick steel, explosive block diameter approximately 123mm, length of the explosive block approximately 239mm).
  • the tests provided by the UN tests 7d) i, 7e) and 7f) and which have been selected for the tests of the different compositions include the following steps:
  • a shot is made with a 12.7 mm caliber bullet.
  • the impact on the model envelope is located in the axis of this one and halfway up.
  • the test is carried out at room temperature (20 ° C) and for an impact speed of 850m / s.
  • the acceptance criterion is the absence of detonation or of violent reaction.
  • a model as defined above is placed above a fuel tank, its lower generator being 250 mm from this one.
  • the fuel used is kerosene.
  • the average flame temperature being higher or equal to 800 ° C.
  • the acceptance criterion is the absence of detonation or of violent reaction.
  • the model is placed in the center of an electric oven ensuring a temperature rise of 3.3 ° C per hour.
  • Acceptance criterion is lack of reaction violent with projection of shards.
  • composition according to the invention has a level of non-vulnerability as good as that of the known composition.
  • the detonic characteristics of the composition according to the invention have a performance level at least equivalent to that of the known composition.
  • composition according to the invention has very low vulnerability while retaining interesting detonic properties.
  • the phlegmatizer used is a consumer product mass produced quantities and for which supply problems do not arise.
  • a other solid explosive than ONTA for example from octogen. But we will preferably leave a proportion low vulnerability explosive which will be greater than 20% in mass in order to maintain low qualities interesting vulnerability.
  • CS sensitivity criterion
  • Vulnerability tests conducted were able to show a composition whose CS was greater than or equal to 100 could not meet all of the vulnerability tests.
  • One of the essential criteria for defining a composition capable of satisfying aggression tests thermal and mechanical is therefore the choice of a percentage phlegmatizer (wax) greater than or equal to 3%.
  • compositions in which the phlegmatizer is each time the previously described wax to which is incorporated the emulsifier:
  • compositions following:

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  • Compositions Of Macromolecular Compounds (AREA)
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  • Heat Sensitive Colour Forming Recording (AREA)
  • Fire-Extinguishing Compositions (AREA)

Abstract

A melt/flow explosive composition with a reduced sensitivity comprises a fusible explosive, a binding agent and an emulsifier of the binder with the explosive, and a solid explosive of low sensitivity.The fusible explosive is a nitro-aromatic compound with a m.pt. higher than 100 degrees C and the binder has a similar m.pt., the proportion of the latter being at least 3% of the total composition mass. The overall composition has a reaction temperature greater than 185 degrees C.

Description

Le domaine technique de l'invention est celui des compositions explosives fusionnables/coulables.The technical field of the invention is that of explosive fusable / flowable compositions.

On sait réaliser des compositions explosives fusionnables mettant en oeuvre le trinitrotoluène (TNT). Cet explosif a un point de fusion qui se situe aux environs de 80°C, il peut donc être facilement mis en place sous forme liquide dans une enveloppe de munition (par exemple dans un corps d'obus).We know how to make explosive compositions fusable using trinitrotoluene (TNT). This explosive has a melting point in the vicinity 80 ° C, so it can be easily installed under liquid form in an ammunition shell (e.g. in a shell body).

Le TNT est utilisé le plus souvent en mélange avec un autre explosif solide plus énergétique, par exemple l'hexogène ou l'octogène. On peut également lui adjoindre un ou plusieurs adjuvants (flegmatisant, sensibilisant...).TNT is most often used in admixture with a other more energetic solid explosive, for example hexogen or octogen. We can also add it one or more adjuvants (phlegmatizing, sensitizing ...).

On cherche aujourd'hui à réaliser des munitions dites à risques atténués (MURAT) c'est à dire dont la vulnérabilité aux agressions extérieures, par exemple un échauffement lent ou rapide (feu de fuel), ou un impact de projectile ou encore un choc provoqué par la détonation d'une munition voisine est fortement atténuée voire nulle.We are now looking to produce so-called ammunition mitigated risks (MURAT), i.e. the vulnerability external aggressions, for example overheating slow or fast (fuel fire), or a projectile impact or another shock caused by the detonation of a munition neighbor is strongly attenuated or even zero.

A ce jour seuls les explosifs à base de polymères organiques réticulables dits explosifs composites (ou PBX en anglais Plastic Bonded Explosives) étaient réputés conférer la propriété MURAT aux munitions.To date only explosives based on polymers crosslinkable organic materials known as composite explosives (or PBX Plastic Bonded Explosives) give the MURAT property to the munitions.

Ces explosifs composites sont mis en oeuvre par coulée de l'explosif mélangé avec le liant et un additif de polymérisation. La solidification est obtenue par la cuisson du chargement.These composite explosives are used by casting explosive mixed with the binder and an additive polymerization. Solidification is obtained by loading of the load.

Un tel type de chargement explosif présente de nombreux inconvénients.Such a type of explosive charge presents numerous disadvantages.

Tout d'abord, la cuisson est longue (plusieurs jours). Elle consomme donc beaucoup d'énergie et ne peut donc pas être mise en oeuvre pour des quantités de munitions importantes.First, the cooking is long (several days). It therefore consumes a lot of energy and therefore cannot be implemented for quantities of ammunition important.

Il est donc exclu, pour des raisons de coût, d'utiliser un tel chargement dans les munitions produites en grandes séries, comme les obus de gros calibre ou les autres projectiles et il serait pratiquement impossible en temps de guerre de satisfaire des demandes de production massive de munitions.It is therefore excluded, for cost reasons, to use such a load in ammunition produced in large series, like large caliber shells or others projectiles and it would be practically impossible in time of war to meet demands for massive production ammunition.

De plus la plupart des liants utilisés sont spécifiques à cet emploi munitionnaire, il en résulte un risque du point de vue des commodités d'approvisionnement et des quantités et qualités qu'il est possible d'acquérir.In addition, most of the binders used are specific this munition use results in a risk of from the point of view of convenience of supply and quantities and qualities that can be acquired.

Enfin les munitions dotées d'un chargement en explosif composite sont difficiles à démilitariser. En effet, il n'est pas possible de faire fondre le chargement pour le sortir de son enveloppe. Les seules solutions possibles sont la destruction par voie chimique ou encore la détonation, solutions coûteuses et nuisibles à l'environnement.Finally, ammunition with an explosive charge composite are difficult to demilitarize. Indeed, it it is not possible to melt the load for the come out of its envelope. The only possible solutions are chemical destruction or the detonation, costly solutions harmful to the environment.

Des travaux ont été conduits en France et aux Etats Unis qui ont débouché sur la définition d'une composition explosive fusionnable/coulable qui associe du TNT (trinitrotoluène), de l'oxynitrotriazole (ONTA), de l'aluminium et de la cire.Works have been carried out in France and in the States States which led to the definition of a composition explosive fusable / flowable which combines TNT (trinitrotoluene), oxynitrotriazole (ONTA), aluminum and wax.

Du fait de la présence du TNT et de la cire, cette composition peut être mise en oeuvre par coulée. Elle présente également la propriété intéressante d'être très peu sensible aux principales épreuves de vulnérabilité telles que définies par exemple par les modes opératoires décrits par les normes AFNOR NFT 70510 à 70515 ou les épreuves ONU 7d)i, 7e), 7g), 7h), 7j) et 7k).Due to the presence of TNT and wax, this composition can be implemented by casting. She also has the interesting property of being very not very sensitive to the main vulnerability tests as defined for example by the operating modes described by AFNOR NFT standards 70510 to 70515 or UN tests 7d) i, 7e), 7g), 7h), 7j) and 7k).

Cette composition a ainsi été déjà testée aux épreuves ONU 7d)i (impact de balle), ONU 7e) (tenue à l'incendie) et ONU 7f) (échauffement lent).This composition has thus already been tested in the tests UN 7d) i (bullet impact), UN 7e) (fire resistance) and UN 7f) (slow heating).

Cette relative insensibilité est due principalement à la présence de l'ONTAThis relative insensitivity is mainly due to the presence of ONTA

Cependant, cette composition présente encore des inconvénients.However, this composition still presents disadvantages.

La température de fusion du TNT étant trop basse (80,6°C), il en résulte une mauvaise tenue des munitions aux stockages sous contraintes thermiques sévères. Ainsi, le TNT peut refusionner et exsuder hors de la munition et ce d'autant plus qu'il contient des impuretés (dinitrotoluène...) impliquant la formation d'eutectiques en combinaison avec le TNT (le point de fusion des eutectiques est bien inférieur à 80°C). L'homogénéité du chargement n'est plus alors assurée, et ses caractéristiques détoniques, notamment sa faible vulnérabilité, ne sont plus garanties.The melting temperature of TNT is too low (80.6 ° C), this results in poor ammunition performance storage under severe thermal constraints. So, TNT can refuse and exude out of ammunition and especially since it contains impurities (dinitrotoluene ...) involving the formation of eutectics in combination with TNT (the melting point of eutectics is well below 80 ° C). The homogeneity of the loading is no longer ensured, and its detonic characteristics, in particular its low vulnerability, are no longer guaranteed.

En effet les changements de phases de l'explosif peuvent conduire à la formation de micro cavités ou de porosités qui diminuent la résistance du chargement aux contraintes thermiques ou aux chocs.Indeed the changes of phases of the explosive can lead to the formation of micro cavities or porosity which reduces the resistance of the load to thermal or shock stresses.

Les brevets US-A-5 431 756 et DE-A-2 310 217 décrivent des compositions explosives liquides à 90°C ou 100°C. La première composition étant à base de TNT et la deuxième à base de pentryl et de tétryl.US-A-5,431,756 and DE-A-2,310,217 describe explosive compositions liquid at 90 ° C or 100 ° C. The first composition being based on TNT and the second at base of pentryl and tetryl.

Le brevet US-A-3 994 756 propose une composition explosive coulable à 121°C et dont la matrice fusible est formée d'un mélange de trinitrobenzène et de 2,4,6 trinitro-m-xylène.US-A-3,994,756 proposes a composition explosive flowable at 121 ° C and whose fusible matrix is formed from a mixture of trinitrobenzene and 2,4,6 trinitro-m-xylene.

Le brevet FR-A-1 535 427 décrit enfin une composition explosive à base de Trinitrométhylaniline.Patent FR-A-1,535,427 finally describes a composition explosive based on Trinitromethylaniline.

Aucune des compositions ainsi décrites ne présente une vulnérabilité réduite.None of the compositions thus described exhibits a reduced vulnerability.

C'est le but de l'invention que de proposer une composition explosive n'ayant pas de tels inconvénients.It is the object of the invention to propose a explosive composition having no such drawbacks.

Ainsi, la composition proposée par l'invention présente une sensibilité à l'échauffement (lent ou rapide), à l'impact et à la détonation par influence qui est au moins égale à celle des explosifs composites connus. Mais elle peut être mise en oeuvre de façon industrielle simple et économique par coulée/fusion.Thus, the composition proposed by the invention has sensitivity to heating (slow or fast), impact and detonation by influence which is at least equal to that of known composite explosives. But she can be implemented industrially simple and economical by casting / melting.

De plus, sa tenue au stockage et aux contraintes thermiques est meilleure que celle de la composition associant TNT et ONTA.In addition, its resistance to storage and constraints is better than that of the composition combining TNT and ONTA.

Ainsi, l'invention a pour objet une composition explosive fusionnable/coulable et à vulnérabilité réduite, telle que revendiquée dans la revendication 1 et comportant d'une part une partie fusionnable formée d'au moins un explosif fusionnable, d'au moins un flegmatisant, et d'au moins un émulsifiant du flegmatisant dans l'explosif fusionnable choisi dans le groupe défini dans la revendication 1 et d'autre part une partie solide comportant au moins un explosif solide à vulnérabilité réduite, composition caractérisée en ce que l'explosif fusionnable est un aromatique nitré dont la température de fusion est supérieure à 100°C, le flegmatisant ayant une température de fusion sensiblement égale à celle de l'explosif fusionnable et la proportion de flegmatisant étant au moins égale à 3% de la masse totale de la composition, l'ensemble ayant une température de réaction supérieure à 185°C.Thus, the subject of the invention is a composition explosive fusible / flowable and with reduced vulnerability, as claimed in claim 1 and comprising on the one hand a fusible part formed of at least at least one fusible explosive, at least one phlegmatizer, and at least one phlegmatizer emulsifier in the fusible explosive chosen from the group defined in claim 1 and on the other hand a solid part comprising at least one solid explosive with vulnerability reduced, composition characterized in that the explosive fusable is a nitro-aromatic whose temperature of melting is greater than 100 ° C, the phlegmatizer having a melting temperature substantially equal to that of the fusible explosive and the proportion of phlegmatizer being at least equal to 3% of the total mass of the composition, the whole having a reaction temperature higher than 185 ° C.

Le mérite des inventeurs a été de découvrir, qu'il était possible de concevoir un explosif fusionnable/coulable en utilisant d'autres explosifs que le TNT.The inventors' merit was to discover that it was possible to design an explosive fusable / flowable using explosives other than the TNT.

Ces explosifs seront choisis avec un point de fusion supérieur à 100°C, ce qui assurera la meilleure tenue de la composition aux contraintes thermiques.These explosives will be chosen with a melting point higher than 100 ° C, which will ensure the best performance of the thermal stress composition.

Bien que des explosifs ayant un point de fusion supérieur à 100°C étaient déjà connus, il n'était pas évident de pouvoir réaliser avec ces derniers des compositions explosives ayant une vulnérabilité réduite.Although explosives with a melting point higher than 100 ° C were already known, it was not obvious to be able to achieve with these explosive compositions with reduced vulnerability.

L'invention propose différents critères de choix des explosifs qui permettent d'assurer l'obtention d'une composition à vulnérabilité réduite permettant de subir avec succès les principaux tests normalisés.The invention proposes different criteria for choosing explosives which ensure that a composition with reduced vulnerability allowing to undergo successfully the main standardized tests.

Un tel résultat est obtenu en ne considérant, pour la partie fusionnable de la composition, que les explosifs dont la structure moléculaire et électronique est proche de celle du TNT (aromatiques nitrés).Such a result is obtained by not considering, for the fusable part of the composition, that explosives whose molecular and electronic structure is close to that of TNT (nitro aromatics).

En effet, cette famille d'explosifs présente une stabilité chimique analogue à celle du TNT, ce qui permet de garantir un comportement aux essais de détonation par influence et d'impact de projectiles qui est proche de celui du TNT.Indeed, this family of explosives presents a chemical stability analogous to that of TNT, allowing to guarantee behavior during detonation tests by influence and impact of projectiles which is close to that of TNT.

On notera ainsi que parmi les familles d'explosifs classiques connues (aromatiques nitrés, esters nitriques et nitramines), les explosifs ayant les valeurs les plus faibles du point de vue des coefficients de sensibilités à l'impact et à l'échauffement sont ceux appartenant à la famille des aromatiques nitrés.It should be noted that among the families of explosives known classics (nitro aromatics, nitric esters and nitramines), the explosives with the highest values low in terms of sensitivity coefficients to impact and warming are those belonging to the family of nitro aromatics.

On combinera à un tel aromatique nitré un flegmatisant approprié dont la température de fusion sera sensiblement égale à celle de l'explosif (à plus ou moins 2°C près), la proportion de flegmatisant étant choisie supérieure à 3%.We will combine with such a nitro-aromatic phlegmatizer suitable whose melting temperature will be appreciably equal to that of the explosive (within plus or minus 2 ° C), the proportion of phlegmatizer being chosen greater than 3%.

Un tel choix permet d'assurer que cet additif, uniformément réparti, a effectivement une fonction concourant à la désensibilisation de la composition en augmentant son homogénéité et non simplement d'additif facilitant la coulée.Such a choice ensures that this additive, uniformly distributed, effectively has a function contributing to the desensitization of the composition in increasing its homogeneity and not simply an additive facilitating the casting.

Le flegmatisant incorporera un émulsifiant qui sera choisi de façon à assurer le meilleur interface explosif fondu/flegmatisant. Le flegmatisant permettra à la fois de favoriser la dispersion des constituants pulvérulents et de stabiliser l'émulsion obtenue. On choisira un flegmatisant et un émulsifiant inertes (on évitera notamment les émulsifiants à base de nitrocellulose).The phlegmatizer will incorporate an emulsifier which will chosen to ensure the best explosive interface Fade / phlegmatizer. The phlegmatizer will both favor the dispersion of the powdery constituents and stabilize the emulsion obtained. We will choose a phlegmatizer and an inert emulsifier (in particular, avoid nitrocellulose-based emulsifiers).

Il en résulte une homogénéité de la composition qui concourt à obtenir une composition moins sensible à l'échauffement.This results in a homogeneity of the composition which contributes to obtaining a composition less sensitive to heating.

Enfin, on formulera l'ensemble de la composition de telle sorte que sa température de réaction soit supérieure à 185°C.Finally, we will formulate the entire composition of so that its reaction temperature is higher at 185 ° C.

Une telle disposition permet de garantir la bonne tenue de la composition aux tests d'échauffement.Such an arrangement ensures good performance of the composition in the heating tests.

Parmi les explosifs fusibles connus, on pourra notamment utiliser comme matériau de base le 2,4,6-trinitro-N-Méthylaniline (TNMA) (matériau peu connu et jamais utilisé industriellement comme explosif de chargement), cela en ayant recours à un flegmatisant inhabituel dans le domaine des explosifs (une cire de polyoléfine) et à un additif assurant l'émulsification de cet explosif et de cette cire.Among the known fusible explosives, we can in particular use as base material 2,4,6-trinitro-N-Methylaniline (TNMA) (little known material and never used industrially as an explosive of loading), this by using a phlegmatizer unusual in the field of explosives (a wax of polyolefin) and an additive ensuring the emulsification of this explosive and this wax.

Les explosifs aromatiques nitrés ont une structure de base constituée d'au moins un noyau aromatique comportant au moins trois radicaux NO2 et trois autres radicaux désignés par exemple R, R' et R".Nitrated aromatic explosives have a structure of base consisting of at least one aromatic nucleus comprising at least three NO2 radicals and three other radicals designated for example R, R 'and R ".

On peut schématiser une telle molécule par la structure suivante:

Figure 00060001
We can schematize such a molecule by the following structure:
Figure 00060001

Les radicaux R, R' et R" pourront être choisis parmi les radicaux : -H, -CH3, -NHCH3, -OH, -NH2 et leurs combinaisons.The radicals R, R 'and R "may be chosen from the radicals: -H, -CH3, -NHCH3, -OH, -NH2 and their combinations.

Ainsi le 2,4,6-trinitro-N-Méthyl Aniline a une structure dans laquelle R et R' sont des radicaux -H et R'' est un radical -NHCH3.Thus 2,4,6-trinitro-N-Methyl Aniline has a structure in which R and R 'are radicals -H and R' ' is a radical -NHCH3.

D'une façon plus précise, les inventeurs ont étudié les structures moléculaires et électroniques des différents explosifs aromatiques nitrés et ont choisi un certain nombre d'explosifs ayant à la fois une température de fusion élevée et un bon comportement aux essais précités d'impact par balle, de chauffage lent ou rapide et de détonation par influence.More specifically, the inventors studied the molecular and electronic structures of the different nitro aromatic explosives and chose a certain number of explosives having both a temperature of high melting and good behavior in the above tests bullet impact, slow or rapid heating and detonation by influence.

Les explosifs retenus par les inventeurs comme ayant une faible vulnérabilité sont (outre le 2,4,6-trinitro-N-Méthyl Aniline ou TNMA) :

  • Deux explosifs ayant une structure proche de celle du TNT:
    • le TNC ou 2,4,6-Trinitro-3-Méthylphénol (C7H5N3O7) qui présente une structure TNT sur laquelle une fonction-OH est rajoutée en 4. Sa structure est la suivante:
      Figure 00060002
    • l'ATNT ou 3-Amino-Trinitrotoluène (C7H6N406) présente une structure TNT sur laquelle une fonction -NH2 est rajoutée en 2. Sa structure est la suivante:
      Figure 00070001
         la TNA ou 2,4,6-Trinitro-Aniline (C6H4N4O6) a une structure proche de celle de la TNMA, une fonction CH3 étant substituée à un des hydrogènes de NH2.
    • The explosives selected by the inventors as having a low vulnerability are (in addition to 2,4,6-trinitro-N-Methyl Aniline or TNMA):
  • Two explosives with a structure close to that of TNT:
    • TNC or 2,4,6-Trinitro-3-Methylphenol (C7H5N3O7) which has a TNT structure on which an OH-function is added in 4. Its structure is as follows:
      Figure 00060002
    • ATNT or 3-Amino-Trinitrotoluene (C7H6N406) has a TNT structure on which an -NH2 function is added at 2. Its structure is as follows:
      Figure 00070001
      TNA or 2,4,6-Trinitro-Aniline (C6H4N4O6) has a structure close to that of TNMA, a CH3 function being substituted for one of the hydrogens of NH2.

    • Sa structure est la suivante:

    Figure 00070002
    Its structure is as follows:
    Figure 00070002

    On pourra enfin utiliser un composé de structure atypique dérivée du naphtalène, le TNN ou isomère 1,3,8-Trinitronaphtalène (C10H6N4O6). On utilisera de préférence le mélange d'isomères qui a une température de fusion de 115°C.We can finally use a structural compound atypical derivative of naphthalene, TNN or isomer 1,3,8-Trinitronaphthalene (C10H6N4O6). We will preferably use the mixture of isomers which has a melting point of 115 ° C.

    La structure de ce corps est la suivante:

    Figure 00070003
    The structure of this body is as follows:
    Figure 00070003

    La partie fusionnable constituera avantageusement entre 20% et 40% en masse de la composition.The mergeable part will advantageously constitute between 20% and 40% by mass of the composition.

    Suivant un mode particulier de réalisation, le flegmatisant pourra être une cire de polyoléfine et l'émulsifiant un copolymère de vinyl pyrrolidone.According to a particular embodiment, the phlegmatizing agent may be a polyolefin wax and the emulsifier a vinyl pyrrolidone copolymer.

    L'explosif solide à vulnérabilité réduite pourra être choisi parmi les explosifs suivants: oxynitrotriazol (ONTA), triaminotrinitrobenzène (TATB), Nitroguanidine (NGu).The solid explosive with reduced vulnerability could be chosen from the following explosives: oxynitrotriazol (ONTA), triaminotrinitrobenzene (TATB), Nitroguanidine (NGU).

    On formulera avantageusement la composition de telle sorte que sa diffusivité thermique soit d'au moins 3,5 10-7 m2/s entre 30 et 47°C, on améliore ainsi le comportement de la composition aux tests d'échauffement.The composition will advantageously be formulated so that its thermal diffusivity is at least 3.5 × 10 -7 m 2 / s between 30 and 47 ° C., thus improving the behavior of the composition during heating tests.

    Cette diffusivité thermique pourra être obtenue au moyen d'une dispersion de poudre d'aluminium.This thermal diffusivity can be obtained at by means of a dispersion of aluminum powder.

    La composition pourra comprendre un mélange de :

    • 20% à 40% en masse de 2,4,6-trinitro-N-Méthyl Aniline,
    • 25% à 60% en masse d'au moins un explosif solide en grains de vulnérabilité réduite,
    • 0% à 30% en masse d'un explosif solide complémentaire en grains,
    • 0% à 25% en masse de poudre d'aluminium,
    • 3% à 12% en masse d'un flegmatisant,
    • 0,1% à 1% en masse d'un additif assurant l'emulsification de l'explosif fusible et du flegmatisant.
    The composition may include a mixture of:
    • 20% to 40% by mass of 2,4,6-trinitro-N-Methyl Aniline,
    • 25% to 60% by mass of at least one solid explosive in grains of reduced vulnerability,
    • 0% to 30% by mass of an additional solid explosive in grains,
    • 0% to 25% by mass of aluminum powder,
    • 3% to 12% by mass of a phlegmatizer,
    • 0.1% to 1% by mass of an additive ensuring the emulsification of the fusible explosive and of the phlegmatizer.

    La composition pourra comprendre :

    • 20% à 40% en masse de 2,4,6-trinitro-N-Méthyl Aniline,
    • 25% à 60% en masse d'oxynitrotriazole,
    • 0% à 20% en masse d'octogène,
    • 0% à 25% en masse de poudre d'aluminium,
    • 3% à 12% en masse de cire de polyoléfine,
    • 0,1% à 1% en masse d'un copolymère de vinyl pyrrolidone.
    The composition may include:
    • 20% to 40% by mass of 2,4,6-trinitro-N-Methyl Aniline,
    • 25% to 60% by mass of oxynitrotriazole,
    • 0% to 20% by mass of octogen,
    • 0% to 25% by mass of aluminum powder,
    • 3% to 12% by mass of polyolefin wax,
    • 0.1% to 1% by mass of a vinyl pyrrolidone copolymer.

    L'invention sera mieux comprise à la lecture de la description qui va suivre de modes particuliers de réalisation.The invention will be better understood on reading the description which follows of particular modes of production.

    Selon un premier mode de réalisation de l'invention on a fabriqué une composition comprenant :According to a first embodiment of the invention, manufactured a composition comprising:

    Example 1Example 1

  • 30% en masse de 2,4,6-trinitro-N-Méthyl Aniline (TNMA),30% by mass of 2,4,6-trinitro-N-Methyl Aniline (TNMA),
  • 40% en masse d'Oxynitrotriazole (ONTA),40% by mass of Oxynitrotriazole (ONTA),
  • 20% en masse de poudre d'aluminium,20% by mass of aluminum powder,
  • 9,5% en masse d'un flegmatisant,9.5% by mass of a phlegmatizer,
  • 0,5% en masse d'un émulsifiant.0.5% by mass of an emulsifier.

    • L'émulsifiant est mélangé au flegmatisant. La proportion d'émulsifiant est choisie comprise entre 2 et 3% de la masse totale de flegmatisant utilisée.The emulsifier is mixed with the phlegmatizer. The proportion of emulsifier is chosen between 2 and 3% of the total mass of phlegmatizer used.

    Le 2,4,6-trinitro-N-Méthyl Aniline ou TNMA est un explosif connu, bien que non utilisé industriellement. Il est décrit notamment par le brevet FR1535427. Il est facile à fabriquer et présente un point de fusion de 113°C à 119°C suivant son degré de pureté.2,4,6-trinitro-N-Methyl Aniline or TNMA is a known explosive, although not used industrially. he is described in particular by patent FR1535427. It is easy to be produced and has a melting point of 113 ° C to 119 ° C according to its degree of purity.

    Le flegmatisant retenu est une cire de polyéthylène (type particulier de polyoléfine) qui est produite sous la référence PED121 par la firme Hoechst Wachs. Sa température de fusion est voisine de 115°C (point de goutte de 113 à 118°C), ce qui correspond sensiblement à la température de fusion du TNMA.The phlegmatizer selected is a polyethylene wax (particular type of polyolefin) which is produced under the reference PED121 by the company Hoechst Wachs. Its temperature melting point is around 115 ° C (drop point from 113 to 118 ° C), which corresponds substantially to the temperature of TNMA merger.

    Cette cire est utilisée habituellement dans le domaine agro alimentaire pour l'enrobage des agrumes.This wax is commonly used in the field food for coating citrus fruits.

    D'une façon surprenante elle se mélange au TNMA assurant la flegmatisation de celui ci et contribuant à la diminution de la vulnérabilité de la composition.Surprisingly it mixes with TNMA ensuring the phlegmatization of this one and contributing to the decrease in the vulnerability of the composition.

    L'émulsifiant retenu pour cette cire est un copolymère de vinyl pyrrolidone, qui est vendu sous la dénomination Antaron WP660 par la société International Specialty Products.The emulsifier used for this wax is a copolymer of vinyl pyrrolidone, which is sold under the name Antaron WP660 by the company International Specialty Products.

    Cette cire permet la réalisation d'une émulsion homogène et stable avec la TNMA et l'émulsifiant.This wax allows the production of an emulsion homogeneous and stable with TNMA and the emulsifier.

    La composition a été réalisée conformément au procédé suivant:The composition was carried out according to the process next:

    On réalise tout d'abord la fusion du TNMA dans un malaxeur, à la température de 125°C, sous la pression atmosphérique. On mélange au TNMA, le flegmatisant et l'émulsifiant tout en agitant.We first carry out the merger of TNMA in a mixer, at a temperature of 125 ° C, under pressure atmospheric. We mix TNMA, the phlegmatizer and the emulsifier while stirring.

    On incorpore ensuite l'ONTA sous forme d'un mélange de deux granulométries différentes et dans des proportions en masse égales. On utilise ainsi une granulométrie de classe 2 pour laquelle la taille des. grains est comprise entre 200 et 800 micromètres, et une granulométrie de classe 3 pour laquelle le diamètre moyen des grains est de 50 micromètres.ONTA is then incorporated in the form of a mixture of two different particle sizes and in proportions in equal mass. We thus use a class grading 2 for which the size of. grains is between 200 and 800 micrometers, and a class 3 particle size for which the average grain diameter is 50 micrometers.

    Cette association de granulométries permet de garantir un chargement optimal de la composition tout en conservant de bonnes propriétés de coulabilité. This combination of particle sizes ensures optimal loading of the composition while retaining good flowability properties.

    On incorpore la poudre d'aluminium d'une granulométrie moyenne égale à 10 micromètres.We incorporate the aluminum powder with a grain size average equal to 10 micrometers.

    Le mélange est versé dans une enveloppe de munition maintenue à la température de 120°C.The mixture is poured into an ammunition envelope maintained at the temperature of 120 ° C.

    L'ensemble est refroidi ensuite progressivement afin d'éviter porosités et retassures. Le temps de refroidissement est de l'ordre d'une quinzaine d'heures.The whole is then gradually cooled in order to to avoid porosity and shrinkage. Time to cooling is around fifteen hours.

    On a fait subir à l'enveloppe de munition contenant la composition selon l'invention un certain nombre des tests décrits par les normes AFNOR 70513 et 70515 et les épreuves ONU 7d)i, 7f) et 7j).The ammunition envelope containing the composition according to the invention a certain number of tests described by AFNOR standards 70513 and 70515 and the tests UN 7d) i, 7f) and 7j).

    Les résultats obtenus sont consignés dans le tableau suivant qui met en parallèle les performances de la composition selon l'invention et celles de la composition coulée connue utilisant le TNT.The results obtained are recorded in the table next which parallels the performance of the composition according to the invention and those of the composition known casting using TNT.

    Les enveloppes de munition testées sont des maquettes conformes à celles définies par le mode opératoire GEMO 3L1 (enveloppe de 3 litres contenant 5 kg d'explosif, paroi en acier de 10mm d'épaisseur, diamètre du bloc d'explosif environ 123mm, longueur du bloc d'explosif environ 239 mm).The ammunition envelopes tested are models conform to those defined by the GEMO 3L1 operating mode (3 liter envelope containing 5 kg of explosive, wall in 10mm thick steel, explosive block diameter approximately 123mm, length of the explosive block approximately 239mm).

    Les tests prévus par les épreuves ONU 7d)i, 7e) et 7f) et qui ont été retenus pour les essais des différentes compositions comprennent les étapes suivantes:The tests provided by the UN tests 7d) i, 7e) and 7f) and which have been selected for the tests of the different compositions include the following steps:

    Epreuve ONU 7d)i (impact de balle)UN test 7d) i (bullet impact)

    On effectue un tir avec une balle de calibre 12,7 mm. L'impact sur l'enveloppe de maquette est situé dans l'axe de celle ci et à mi hauteur.A shot is made with a 12.7 mm caliber bullet. The impact on the model envelope is located in the axis of this one and halfway up.

    Le test est conduit à température ambiante (20°C) et pour une vitesse d'impact de 850m/s.The test is carried out at room temperature (20 ° C) and for an impact speed of 850m / s.

    Le critère d'acceptation est l'absence de détonation ou de réaction violente.The acceptance criterion is the absence of detonation or of violent reaction.

    Epreuve ONU 7e) (tenue à l'incendie)UN test 7e) (fire resistance)

    Une maquette telle que définie précédemment est placée au dessus d'un bac à combustible, sa génératrice inférieure étant à 250 mm de celui ci. Le combustible utilisé est du kérosène. La température moyenne de flamme étant supérieure ou égale à 800°C. A model as defined above is placed above a fuel tank, its lower generator being 250 mm from this one. The fuel used is kerosene. The average flame temperature being higher or equal to 800 ° C.

    Le critère d'acceptation est l'absence de détonation ou de réaction violente.The acceptance criterion is the absence of detonation or of violent reaction.

    Epreuve ONU 7f) (échauffement lent)UN test 7f) (slow heating)

    La maquette est disposée au centre d'un four électrique assurant une montée en température de 3,3°C par heure.The model is placed in the center of an electric oven ensuring a temperature rise of 3.3 ° C per hour.

    On note le type de réaction obtenu et la température à laquelle elle intervient.The type of reaction obtained and the temperature at which it intervenes.

    Le critère d'acceptation est l'absence de réaction violente avec projection d'éclats.Acceptance criterion is lack of reaction violent with projection of shards.

    Les essais ont été conduits pour une composition selon l'invention (exemple 1) et pour une composition connue à base de TNT et dont la formulation est la suivante :

  • Trinitrotoluène (TNT) 30% en masse
  • ONTA 40% en masse
  • Aluminium 20% en masse
  • Cire 10% en masse
    • The tests were conducted for a composition according to the invention (Example 1) and for a known composition based on TNT and the formulation of which is as follows:
  • Trinitrotoluene (TNT) 30% by mass
  • ONTA 40% by mass
  • Aluminum 20% by mass
  • Wax 10% by mass

    • Les résultats sont consignés dans le tableau suivant. Epreuves de vulnérabilité Composition connue utilisant le TNT Composition selon l'invention utilisant le TNMA    Tenue à l'impact de balle (ONU 7d)i) Non détonation Non détonation    Tenue à l'incendie (AFNOR NFT 70513, ONU 7e)) Non détonation Non détonation    Tenue à l'échauffement lent (3,3°C/heure)
       (AFNOR NFT 70515, ONU 7f))     Non détonation Non détonation     The results are recorded in the following table. Vulnerability tests Known composition using TNT Composition according to the invention using TNMA Resistance to bullet impact (UN 7d) i) No detonation No detonation Fire behavior (AFNOR NFT 70513, UN 7e)) No detonation No detonation Resistance to slow heating (3.3 ° C / hour)
    (AFNOR NFT 70515, ONU 7f))     No detonation No detonation

    On constate que la composition selon l'invention a un niveau de non vulnérabilité aussi bon que celui de la composition connue.It can be seen that the composition according to the invention has a level of non-vulnerability as good as that of the known composition.

    Par ailleurs les caractéristiques détoniques de la composition selon l'invention ont un niveau de performance au moins équivalent à celui de la composition connue. On a ainsi mesuré une vitesse de détonation de 6830 m/s avec la composition selon l'invention, la composition connue à base de TNT ayant une vitesse de 6770 m/s.Furthermore, the detonic characteristics of the composition according to the invention have a performance level at least equivalent to that of the known composition. We have thus measured a detonation speed of 6830 m / s with the composition according to the invention, the known composition based of TNT having a speed of 6770 m / s.

    Sa diffusivité thermique est de 3,5 10-7 m2/s.Its thermal diffusivity is 3.5 10-7 m 2 / s.

    On constate donc que la composition selon l'invention a une vulnérabilité très faible tout en conservant des propriétés détoniques intéressantes.It can therefore be seen that the composition according to the invention has very low vulnerability while retaining interesting detonic properties.

    Mais elle présente par rapport à la composition connue à base de TNT l'énorme avantage de ne pas fusionner avant 113°C, ce qui garantit une bonne tenue des munitions aux stockages sous contraintes thermiques.But it presents compared to the known composition based on TNT the huge advantage of not merging before 113 ° C, which guarantees good resistance of the ammunition to storage under thermal constraints.

    Aucune exsudation n'est donc à craindre, l'homogénéité du chargement et les caractéristiques à la fois de détonique et de vulnérabilité ne sont pas modifiées par le stockage.No exudation is therefore to be feared, homogeneity of loading and the characteristics of both detonation and vulnerability are not modified by the storage.

    On notera également que le flegmatisant utilisé est un produit de consommation courante produit en grande quantités et pour lequel les problèmes d'approvisionnement ne se posent pas.It will also be noted that the phlegmatizer used is a consumer product mass produced quantities and for which supply problems do not arise.

    Il n'apparaissait pas évident à priori que l'emploi d'un explosif à point de fusion supérieur permettrait d'obtenir une nouvelle composition explosive à vulnérabilité réduite.It did not appear obvious a priori that employment of a higher melting point explosive would to obtain a new explosive composition at reduced vulnerability.

    Ce résultat a pu être obtenu grâce aux critères de choix des explosifs proposés par la présente invention. C'est à dire par un choix judicieux d'un explosif fusionnable ayant une structure d'aromatique nitré comparable électroniquement au TNT et par l'association de cet explosif avec une masse suffisante d'un flegmatisant ayant une température de fusion du même ordre de grandeur. L'ensemble de la composition étant formulé pour avoir une température de réaction supérieure à 185°C.This result could be obtained thanks to the criteria of choice of explosives proposed by the present invention. Ie by a judicious choice of an explosive fusable with a structure of nitro aromatic electronically comparable to TNT and by the association of this explosive with a sufficient mass of a phlegmatizer having a melting temperature of the same order of magnitude. The entire composition being formulated to have a reaction temperature above 185 ° C.

    En fonction des performances recherchées il est possible de faire varier les proportions relatives des différents composants. Depending on the desired performance it is possible to vary the relative proportions of different components.

    La poudre d'aluminium a pour fonction principale d'améliorer l'effet de souffle de la composition. Elle permet également d'améliorer la conductivité thermique de la composition. Une augmentation de la masse d'aluminium permet donc aussi d'accroítre la tenue de la composition à l'échauffement (lent ou rapide).The main function of aluminum powder to improve the blast effect of the composition. She also improves the thermal conductivity of the composition. An increase in the mass of aluminum therefore also allows to increase the hold of the composition to warming up (slow or fast).

    Un accroissement de la proportion d'ONTA permet d'augmenter l'effet détonant tout en diminuant la vulnérabilité de la composition.An increase in the proportion of ONTA allows increase the detonating effect while decreasing the vulnerability of the composition.

    On pourra par ailleurs ajouter à la composition un autre explosif solide que l'ONTA, par exemple de l'octogène. Mais on laissera de préférence une proportion d'explosif peu vulnérable qui sera supérieure à 20% en masse afin de maintenir des qualités de faible vulnérabilité intéressantes.We can also add to the composition a other solid explosive than ONTA, for example from octogen. But we will preferably leave a proportion low vulnerability explosive which will be greater than 20% in mass in order to maintain low qualities interesting vulnerability.

    Pour définir précisément les limites de formulation, les inventeurs ont mis au point un critère de sensibilité (CS) spécifique qui est dérivé des travaux conduits dans l'industrie chimique (Code CHETAH ASTM chemical Thermodynamic Energy Release Evaluation Program publié en novembre 1974 - Auteurs: MM Scaton, Freedman et Treweek). Ce critère s'appuie sur le calcul des propriétés thermochimiques des différents constituants d'une composition et notamment l'enthalpie et le nombre d'atome gramme. Il permet d'exprimer avec un bon degré de fiabilité le risque potentiel d'explosion thermique.To precisely define the formulation limits, the inventors have developed a sensitivity criterion (CS) specific which is derived from the work carried out in the chemical industry (Code CHETAH ASTM chemical Thermodynamic Energy Release Evaluation Program published in November 1974 - Authors: MM Scaton, Freedman and Treweek). This criterion is based on the calculation of properties thermochemicals of the different constituents of a composition and in particular the enthalpy and the number of atoms gram. It allows to express with a good degree of reliability the potential risk of thermal explosion.

    Ce critère n'avait jusqu'à présent jamais été utilisé dans le domaine de l'armement et des explosifs.This criterion had never been used until now in the field of armaments and explosives.

    Pour qu'une composition explosive soit considérée comme non vulnérable aux principaux tests précités, les essais de sensibilité à l'impact (mouton BAM) et de vulnérabilité conduits par les inventeurs ont permis de vérifier que son CS calculé devait être inférieur à 100. Ce qui ne peut s'obtenir qu'avec des formulations contenant au moins 3% de cire.For an explosive composition to be considered not vulnerable to the main aforementioned tests, the tests of impact sensitivity (BAM sheep) and vulnerability conducted by the inventors have made it possible to verify that its Calculated CS had to be less than 100. Which cannot be obtained with formulations containing at least 3% of wax.

    Les tableaux ci-dessous donnent les valeurs de ces coefficients de sensibilité CS pour différentes compositions et matériaux explosifs: Compositions explosives Critère CS TNMA 30%/ ONTA 40%/ Al 20% / cire 10% 73 TNT 30%/ ONTA 40%/ Al 20%/ cire 10% 75 TNMA 36%/ ONTA 40%/ Al 20%/ cire 4% 92 TNMA 37%/ ONTA 40%/ Al 20%/ cire 3% 96 TNMA 38%/ ONTA 40%/ Al 20%/ cire 2% 100 Matériaux explosifs Critère CS TATB 125 ONTA 133 TNMA 165 TNT 181 Hexogène 233 The tables below give the values of these sensitivity coefficients CS for different explosive compositions and materials: Explosive compositions CS criterion TNMA 30% / ONTA 40% / Al 20% / wax 10% 73 TNT 30% / ONTA 40% / Al 20% / wax 10% 75 TNMA 36% / ONTA 40% / Al 20% / wax 4% 92 TNMA 37% / ONTA 40% / Al 20% / wax 3% 96 TNMA 38% / ONTA 40% / Al 20% / wax 2% 100 Explosive materials CS criterion TATB 125 HAVE A 133 TNMA 165 TNT 181 hexogen 233

    Les essais de vulnérabilité conduits ont pu montrer qu'une composition dont le CS était supérieur ou égal à 100 ne pouvait pas satisfaire tous les tests de vulnérabilité.Vulnerability tests conducted were able to show a composition whose CS was greater than or equal to 100 could not meet all of the vulnerability tests.

    Un des critères essentiels permettant de définir une composition pouvant satisfaire les essais d'agression thermique et mécanique est donc le choix d'un pourcentage de flegmatisant (cire) supérieur ou égal à 3%.One of the essential criteria for defining a composition capable of satisfying aggression tests thermal and mechanical is therefore the choice of a percentage phlegmatizer (wax) greater than or equal to 3%.

    Pratiquement on ne choisira pas un pourcentage de cire supérieur à 12%, les caractéristiques détoniques d'une composition trop chargée en cire n'étant pas intéressantes.In practice, we will not choose a percentage of wax greater than 12%, the detonic characteristics of a composition too loaded with wax not being interesting.

    A titre de variantes on pourra également réaliser les compositions suivantes, dans lesquelles le flegmatisant est à chaque fois la cire décrite précédemment à laquelle est incorporé l'émulsifiant : By way of variants, it is also possible to carry out the following compositions, in which the phlegmatizer is each time the previously described wax to which is incorporated the emulsifier:

    Exemple 2Example 2

  • 36% en masse de 2,4,6-trinitro-N-Méthyl Aniline (TNMA),
  • 52% en masse d'Oxynitrotriazole (ONTA),
  • 8% en masse de poudre d'aluminium,
  • 4% en masse de cire.
    •    Vitesse de détonation: 7390 m/s.
  • 36% by mass of 2,4,6-trinitro-N-Methyl Aniline (TNMA),
  • 52% by mass of Oxynitrotriazole (ONTA),
  • 8% by mass of aluminum powder,
  • 4% by mass of wax.
    • Detonation speed: 7390 m / s.

    Exemple 3Example 3

  • 30% en masse de 2,4,6-trinitro-N-Méthyl Aniline (TNMA),
  • 47% en masse d'Oxynitrotriazole (ONTA),
  • 13% en masse de poudre d'aluminium,
  • 10% en masse de cire.
    •    Vitesse de détonation: 7190 m/s.
  • 30% by mass of 2,4,6-trinitro-N-Methyl Aniline (TNMA),
  • 47% by mass of Oxynitrotriazole (ONTA),
  • 13% by mass of aluminum powder,
  • 10% by mass of wax.
    • Detonation speed: 7190 m / s.

    Exemple 4Example 4

  • 37% en masse de 2,4,6-trinitro-N-Méthyl Aniline (TNMA),
  • 45% en masse d'Oxynitrotriazole (ONTA),
  • 15% en masse de poudre d'aluminium,
  • 3% en masse de cire.
    •    Vitesse de détonation : 7773 m/s
  • 37% by mass of 2,4,6-trinitro-N-Methyl Aniline (TNMA),
  • 45% by mass of Oxynitrotriazole (ONTA),
  • 15% by mass of aluminum powder,
  • 3% by mass of wax.
    • Detonation speed: 7773 m / s

    Exemple 5Example 5

  • 37% en masse de 2,4,6-trinitro-N-Méthyl Aniline (TNMA),
  • 40% en masse d'Oxynitrotriazole (ONTA),
  • 20% en masse de poudre d'aluminium,
  • 3% en masse de cire.
    •    Vitesse de détonation : 7666 m/s
  • 37% by mass of 2,4,6-trinitro-N-Methyl Aniline (TNMA),
  • 40% by mass of Oxynitrotriazole (ONTA),
  • 20% by mass of aluminum powder,
  • 3% by mass of wax.
    • Detonation speed: 7666 m / s

    Example 6Example 6

  • 30% en masse de 2,4,6-trinitro-N-Méthyl Aniline (TNMA),
  • 41,6% en masse d'Oxynitrotriazole (ONTA),
  • 10,4% en masse d'Octogène,
  • 8% en masse de poudre d'aluminium,
  • 10% en masse de cire.
    •    Vitesse de détonation: 7510 m/s.
  • 30% by mass of 2,4,6-trinitro-N-Methyl Aniline (TNMA),
  • 41.6% by mass of Oxynitrotriazole (ONTA),
  • 10.4% by mass of Octogen,
  • 8% by mass of aluminum powder,
  • 10% by mass of wax.
    • Detonation speed: 7510 m / s.

    Example 7Example 7

  • 28% en masse de 2,4,6-trinitro-N-Méthyl Aniline (TNMA),
  • 38% en masse d'Oxynitrotriazole (ONTA),
  • 18% en masse d'Octogène,
  • 6% en masse de poudre d'aluminium,
  • 10% en masse de cire.
    •    Vitesse de détonation: 7600 m/s.
  • 28% by mass of 2,4,6-trinitro-N-Methyl Aniline (TNMA),
  • 38% by mass of Oxynitrotriazole (ONTA),
  • 18% by mass of Octogen,
  • 6% by mass of aluminum powder,
  • 10% by mass of wax.
    • Detonation speed: 7600 m / s.

    On voit donc qu'il est possible de faire varier les caractéristiques détoniques de ces compositions peu vulnérables en jouant sur la proportion de l'explosif solide en grains qui est ajouté à l'Onta. Cet explosif est ici de l'Octogène (ou tétramethylène-tetranitramine). Vitesse de détonation : 9100 m/s. La masse d'explosif complémentaire (octogène) sera au plus égale à celle de l'explosif à vulnérabilité réduite (ONTA).We therefore see that it is possible to vary the detonic characteristics of these compositions little vulnerable by playing on the proportion of the explosive grain solid which is added to Onta. This explosive is here Octogen (or tetramethylene-tetranitramine). Detonation speed: 9100 m / s. The mass of explosive complementary (octogenous) will be at most equal to that of explosives with reduced vulnerability (ONTA).

    On pourrait également utiliser l'hexogène comme explosif énergétique complémentaire.We could also use hexogen as additional energy explosive.

    On pourra également remplacer l'ONTA par un autre explosif en grains peu sensible.We can also replace ONTA with another explosive in insensitive grains.

    On pourra par exemple réaliser les compositions suivantes:We can for example make the compositions following:

    Exemple 8Example 8

  • 30% en masse de 2,4,6-trinitro-N-Méthyl Aniline,30% by mass of 2,4,6-trinitro-N-Methyl Aniline,
  • 40% en masse de nitroguanidine,40% by mass of nitroguanidine,
  • 20% en masse de poudre d'aluminium,20% by mass of aluminum powder,
  • 10% en masse de cire10% by mass of wax

    • Exemple 9Example 9

  • 30% en masse de 2,4,6-trinitro-N-Méthyl Aniline (TNMA),30% by mass of 2,4,6-trinitro-N-Methyl Aniline (TNMA),
  • 40% en masse de triaminotrinitrobenzène (TATB),40% by mass of triaminotrinitrobenzene (TATB),
  • 20% en masse de poudre d'aluminium,20% by mass of aluminum powder,
  • 10% en masse de cire.10% by mass of wax.

    • Claims (18)

    1. A low vulnerability meltable/castable explosive composition incorporating at least one meltable part formed of at least one meltable explosive, at least one desensitiser, at least one desensitiser emulsifier in the meltable explosive and additionally a solid part incorporating at least one low vulnerability solid explosive, composition characterised in that the meltable explosive is a nitrated aromatic whose melting point is greater than 100°C, selected from among the following compounds: 2,4,6-Trinitro-N-Methyl Aniline, 2,4,6-Trinitro-3-Methyphenol, 3-Amino-Trinitrotoluene, 2,4,6-Trinitro-Aniline, 1,3,8-Trinitro-Naphthalene and its mixture of isomers meltable at 115°C, the desensitiser having a melting temperature that is substantially equal to that of the meltable explosive and the proportion of desensitiser being at least equal to 3% of the total mass of the composition, the assembly having a reaction temperature of greater than 185°C.
    2. A low vulnerability meltable/castable explosive composition according to Claim 1, wherein the meltable part constitutes between 20% and 40% in mass of the composition.
    3. A low vulnerability meltable/castable explosive composition according to one of Claims 1 or 2, wherein the desensitiser is a polyolefin wax.
    4. A low vulnerability meltable/castable explosive composition according to Claim 2, wherein the emulsifier is constituted by a pyrrolidone vinyl copolymer.
    5. A low vulnerability meltable/castable explosive composition according to one of Claims 1 to 3, wherein the low vulnerability solid explosive is selected from among the following explosives: oxynitrotriazole (ONTA), triaminotrinitrobenzene (TATB), Nitroguanidine (NGu).
    6. A low vulnerability meltable/castable explosive composition according to one of Claims 1 to 5, wherein its thermal diffusivity is at least 3.5.10-7 m2/s between 30 and 47°C.
    7. A low vulnerability meltable/castable explosive composition according to Claim 6, wherein the thermal diffusivity is obtained by means of the dispersion of aluminium powder.
    8. A low vulnerability meltable/castable explosive composition according to one of Claims 1 to 7, wherein it comprises a mixture of:
      20% to 40% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      25% to 60% in mass of at least one granulated low sensitivity solid explosive,
      0% to 30% in mass of a complementary granulated solid explosive,
      0% to 25% in mass of aluminium powder,
      3% to 12% in mass of a desensitiser,
      0.1% to 1% in mass of an additive ensuring the emulsification of the meltable explosive and the desensitiser.
    9. A low vulnerability meltable/castable explosive composition according to Claim 8, wherein it comprises a mixture of:
      20% to 40% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      25% to 60% in mass of oxynitrotriazol,
      0% to 20% in mass of octogen,
      0% to 25% in mass of aluminium powder,
      3% to 12% in mass of polyolefin wax,
      0.1% to 1% in mass of a pyrrolidone vinyl copolymer.
    10. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      30% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      40% in mass of oxynitrotriazol,
      20% in mass of aluminium powder,
      10% in mass of polyolefin wax mixed with emulsifier.
    11. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      36% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      52% in mass of oxynitrotriazol,
      8% in mass of aluminium powder,
      4% in mass of polyolefin wax mixed with emulsifier.
    12. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      30% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      47% in mass of oxynitrotriazol,
      13% in mass of aluminium powder,
      10% in mass of polyolefin wax mixed with emulsifier.
    13. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      37% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      45% in mass of oxynitrotriazol,
      15% in mass of aluminium powder,
      3% in mass of polyolefin wax mixed with emulsifier.
    14. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      37% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      40% in mass of oxynitrotriazol,
      20% in mass of aluminium powder,
      3% in mass of polyolefin wax mixed with emulsifier.
    15. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      30% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      41.6% in mass of oxynitrotriazol,
      10.4% in mass of octogen,
      8% in mass of aluminium powder,
      10% in mass of polyolefin wax mixed with emulsifier.
    16. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      28% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      38% in mass of oxynitrotriazol,
      18% in mass of octogen,
      6% in mass of aluminium powder,
      10% in mass of polyolefin wax mixed with emulsifier.
    17. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      30% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      40% in mass of nitroguanidine,
      20% in mass of aluminium powder,
      10% in mass of polyolefin wax mixed with emulsifier.
    18. A low vulnerability meltable/castable explosive composition according to Claim 9, wherein it comprises:
      30% in mass of 2,4,6-trinitro-N-Methyl Aniline,
      40% in mass of triaminotrinitrobenzene,
      20% in mass of aluminium powder,
      10% in mass of polyolefin wax mixed with emulsifier.
    EP97401425A 1996-06-19 1997-06-19 Meltable/castable explosive composition with reduced sensitivity Expired - Lifetime EP0814069B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    FR9607643 1996-06-19
    FR9607643A FR2750131B1 (en) 1996-06-19 1996-06-19 EXPLOSIVE COMPOSITION MELT / CASTABLE AND WITH REDUCED VULNERABILITY

    Publications (2)

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    EP0814069A1 EP0814069A1 (en) 1997-12-29
    EP0814069B1 true EP0814069B1 (en) 2002-03-27

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    AT (1) ATE215058T1 (en)
    DE (1) DE69711268T2 (en)
    FR (1) FR2750131B1 (en)
    NO (1) NO308595B1 (en)

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    FR2801883B1 (en) * 1999-12-06 2002-01-18 Giat Ind Sa COMPLIMENTABLE EXPLOSIVE COMPOSITION WITH REDUCED VULNERABILITY AND PROCESS FOR PREPARING SUCH A COMPOSITION
    FR2934260B1 (en) * 2008-07-28 2010-08-27 Nexter Munitions METHOD FOR CASTING AN EXPLOSIVE MATERIAL WITH REDUCED VULNERABILITY AND MATERIALS IMPLEMENTED IN SUCH A METHOD
    FR2940683B1 (en) 2008-12-31 2011-03-18 Nexter Munitions MILITARY HEAD PROJECTING BARS.
    FR2954308B1 (en) 2009-12-23 2012-02-24 Nexter Munitions FUSIBLE / COULABLE EXPLOSIVE COMPOSITION WITH REDUCED VULNERABILITY
    FR2984885B1 (en) * 2011-12-21 2014-07-04 Nexter Munitions METHOD FOR MANUFACTURING PELLETS OF A COMPRESSABLE EXPLOSIVE COMPOSITION AND ESPLOSIVE MATERIAL OBTAINED WITH SUCH A METHOD
    FR3123649A1 (en) 2021-06-03 2022-12-09 Thales FUSIBLE/FLOWABLE EXPLOSIVE COMPOSITION AND METHOD FOR MAKING IT
    FR3141172A1 (en) 2022-10-20 2024-04-26 Thales Process for manufacturing a meltable/castable explosive composition.

    Family Cites Families (8)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US2353147A (en) * 1941-06-05 1944-07-11 Du Pont High-density explosive charge
    FR1535427A (en) * 1965-03-01 1968-08-09 France Etat Explosive composition
    DE2310217A1 (en) * 1973-03-01 1974-09-05 Dynamit Nobel Ag Castable explosive compsn. - which melts at below 100 deg C and has increased explosive force and shattering power
    US3994756A (en) * 1975-11-26 1976-11-30 The United States Of America As Represented By The Secretary Of The Army Castable composite explosive compositions containing a mixture of trinitrobenzene and trinitroxylene
    FR2499976A1 (en) * 1981-02-13 1982-08-20 France Etat Castable explosive compsn. comprising solid explosive - fusible explosive and vinyl! polymer coating
    DE3838084A1 (en) * 1988-11-10 1990-05-17 Rheinmetall Gmbh METHOD FOR PRODUCING EXPLOSIVE CHARGES FROM NON-FOOD MIXTURES
    US5431756A (en) * 1993-02-25 1995-07-11 Mach I, Inc. Method and composition for melt cast explosives, propellants and pyrotechnics
    FR2738562B1 (en) * 1995-09-08 1997-10-03 Poudres & Explosifs Ste Nale EXPLOSIVE MELTED COMPOSITIONS

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    NO972873L (en) 1997-12-22
    NO972873D0 (en) 1997-06-20
    FR2750131B1 (en) 1998-07-17
    EP0814069A1 (en) 1997-12-29
    DE69711268T2 (en) 2002-09-05
    ATE215058T1 (en) 2002-04-15
    DE69711268D1 (en) 2002-05-02
    FR2750131A1 (en) 1997-12-26
    NO308595B1 (en) 2000-10-02

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