EP3737657B1 - Use of a halogenated salt of tetraphenylphosphonium as a smoke-producing agent and smoke-producing pyrotechnic composition incorporating such material - Google Patents

Use of a halogenated salt of tetraphenylphosphonium as a smoke-producing agent and smoke-producing pyrotechnic composition incorporating such material Download PDF

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EP3737657B1
EP3737657B1 EP18833334.8A EP18833334A EP3737657B1 EP 3737657 B1 EP3737657 B1 EP 3737657B1 EP 18833334 A EP18833334 A EP 18833334A EP 3737657 B1 EP3737657 B1 EP 3737657B1
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weight
composition according
smoke
agent
tetraphenylphosphonium
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EP3737657C0 (en
EP3737657A1 (en
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Nicolas Perrot
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Mecar SA
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D3/00—Generation of smoke or mist (chemical part)
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

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  • the technical field of the invention is that of pyrotechnic smoke-producing compositions and more particularly smoke-producing compositions capable of masking an objective with respect to electromagnetic radiation in a given range of wavelengths.
  • compositions combining an oxidant, a reducing agent and a material capable of generating masking particles which is constituted by a chlorinated aromatic compound.
  • the masking particles generated are essentially carbon particles whose average particle size is close to the wavelengths of the radiation to be masked.
  • compositions are very effective from a masking point of view, both for the visible spectrum and for the infrared domains: range of 3 to 5 micrometers and range of 8 to 12 micrometers.
  • they have the disadvantage of using a substance, chlorinated naphthalene, which is currently banned from manufacturing and use by the European Union.
  • the material generating masking particles consists of a polyaromatic compound substituted with 1 to 3 bromine atoms, such as a dibromonaphthalene or a dibromoquinoline, and more particularly 1,4-dibromonaphthalene, 1,8 -dibromoquinoline or 4,7-dibromoquinoline.
  • This composition thus makes it possible, by replacing chlorine with bromine, to produce a smoke-producing composition having substantially the performance of that known based on chlorinated naphthalene while having less toxicity than the latter.
  • the subject of the invention is the use of at least one halogenated salt of tetraphenyl phosphonium as a smoke agent in a pyrotechnic composition intended to ensure the masking of an objective with respect to electromagnetic radiation in a range of wavelengths. given.
  • This phosphonic acid is much less toxic than phosphoric acid and it leads to the production of masking clouds with reduced toxicity.
  • a halogenated tetraphenyl phosphonium salt has the following structural formula in which X - denotes the halogen ion (Chlorine, Bromine, Iodine or fluorine).
  • This molecule has four aromatic rings which ensure, during combustion, the production of the carbon particles desired for masking.
  • Combustion will lead to the recombination of halogen atoms with other species: carbon or hydrogen, giving hydrogen halides or halogenated carbon derivatives.
  • Phosphorus recombines in the form of phosphonic acid.
  • the tetraphenyl phosphonium salt used is tetraphenyl phosphonium bromide.
  • This salt is low cost and, as described in the patent WO2015/132266 , the use of bromine makes it possible to avoid the formation of hydrogen chloride during combustion, which reduces the toxicity of the fumes.
  • tetraphenyl phosphonium bromide or tetraphenyl phosphonium iodide will be preferred to reduce the toxicity of the cloud generated.
  • the invention also relates to a pyrotechnic smoke composition intended to ensure the masking of an objective with respect to electromagnetic radiation in a given range of wavelengths and comprising at least one energetic material, such as an oxido-couple. reducing agent, as well as at least one smoke agent generating masking particles, composition characterized in that it comprises as a smoke-producing agent, at least one halogenated tetraphenyl phosphonium salt.
  • An energetic material is a material or composition which can be initiated and which provides sufficient energy to burn the smoke agent and thus cause the emission of the masking particles, mainly carbon particles. Combustion will be carried out at a sufficient speed to avoid extinction of the smoke mass.
  • an oxido-reducing couple for example a couple combining, as reducer, a metal powder, and as oxidant, a fluoropolymer having in its molecular structure a fluorine percentage greater than 60%.
  • the reducer can be chosen from the following bodies: aluminum, zirconium, magnesium, titanium, calcium silicide, boron.
  • the oxidant may be chosen from the following bodies: di-polymer of vinylidene fluoride and hexafluoro-propylene (for example the product sold by the company 3M under the brand Dyneon FC2230), polytetra-fluoroethylene, tetrafluoroethylene or their mixture.
  • the composition may comprise: at least one organochlorinated compound in a proportion less than 10% by mass. This chlorinated compound allows the smoke generated to be further pressed to the ground.
  • This chlorinated compound will be added in small proportions so that the toxicity of the cloud is not increased excessively.
  • the binder makes it possible to improve the mechanical strength of the composition block which will for example be implemented by compression.
  • the binder may consist of at least one epoxy type resin added in a proportion of approximately 5% of the overall mass of the block (for a 100 gram block, 5 grams of binder are added).
  • compositions in accordance with the invention proportions of the constituents given relative to the total mass of the composition
  • This composition is put in the form of a block without binder.
  • the block is made by compression with the compression rate specified previously (17 Mega Pascals for a diameter of 125 mm). Such a compression rate is sufficient to ensure the cohesion of the block.
  • This block was positioned in an optronic tunnel at a distance of 6 meters from the optical measurement line.
  • the block burns like a “cigarette”. That is to say that the initiation is carried out at the level of the free upper surface of the block which is gradually consumed from its upper surface to its lower surface (supporting surface).
  • the cloud of smoke generated was moved using a fan at a controlled speed of 3m/s so as to make it pass in front of the measuring means.
  • Masking is evaluated by comparing the effect of passing smoke past thermal sources (cold and hot) on the temperature seen by the thermal camera.
  • the masking performances are very similar for the different compositions, which indicates a certain stability of operation even with a few % formulation differences.
  • the combustion speed depends on the magnesium content.
  • the combustion rate increases when the magnesium level increases. For example, a magnesium content of 15% will provide a block combustion time of nearly 52 seconds while a magnesium content of 12% will provide a combustion time of 88 seconds.

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Description

Le domaine technique de l'invention est celui des compositions pyrotechniques fumigènes et plus particulièrement des compositions fumigènes pouvant assurer un masquage d'un objectif vis à vis des rayonnements électromagnétiques dans une gamme de longueurs d'ondes donnée.The technical field of the invention is that of pyrotechnic smoke-producing compositions and more particularly smoke-producing compositions capable of masking an objective with respect to electromagnetic radiation in a given range of wavelengths.

On recherche aujourd'hui. des fumigènes pouvant couvrir un large spectre de longueur d'ondes, allant du visible jusqu'à l'infrarouge lointain, soit des longueurs d'onde de 0,7 micromètres à 14 micromètres.We are looking today. smoke bombs that can cover a wide spectrum of wavelengths, ranging from visible to far infrared, i.e. wavelengths from 0.7 micrometers to 14 micrometers.

On connaît par les brevets FR2583037 et FR2560186 des compositions associant un oxydant, un réducteur et un matériau pouvant engendrer des particules de masquage qui est constitué par un composé aromatique chloré. Les particules de masquage engendrées sont pour l'essentiel des particules de carbone dont la granulométrie moyenne est voisine des longueurs d'onde des rayonnements à occulter.We know from patents FR2583037 And FR2560186 compositions combining an oxidant, a reducing agent and a material capable of generating masking particles which is constituted by a chlorinated aromatic compound. The masking particles generated are essentially carbon particles whose average particle size is close to the wavelengths of the radiation to be masked.

Ces compositions sont très efficaces du point de vue du masquage, tant pour le spectre visible que pour les domaines infrarouges : gamme de 3 à 5 micromètres et gamme de 8 à 12 micromètres. Elles présentent cependant l'inconvénient de mettre en oeuvre une substance, le naphtalène chloré, qui est aujourd'hui interdite de fabrication et d'emploi par l'Union Européenne.These compositions are very effective from a masking point of view, both for the visible spectrum and for the infrared domains: range of 3 to 5 micrometers and range of 8 to 12 micrometers. However, they have the disadvantage of using a substance, chlorinated naphthalene, which is currently banned from manufacturing and use by the European Union.

Il existe ainsi un besoin de définir, pour la protection des forces terrestres et navales, de nouvelles compositions pyrotechniques de masquage pouvant assurer un masquage dans un domaine spectral large tout en mettant en œuvre des composants peu toxiques.There is thus a need to define, for the protection of land and naval forces, new compositions masking pyrotechnics capable of providing masking in a wide spectral range while using low-toxic components.

On connaît également par le brevet WO2015/132266 une composition fumigène dans laquelle le matériau engendrant des particules de masquage est constitué par un composé polyaromatique substitué par 1 à 3 atomes de brome, tel qu'un dibromonaphtalène ou une dibromoquinoline, et plus particulièrement le 1,4-dibromonaphtalène, la 1,8-dibromoquinoline ou la 4,7- dibromoquinoline.We also know from the patent WO2015/132266 a smoke-producing composition in which the material generating masking particles consists of a polyaromatic compound substituted with 1 to 3 bromine atoms, such as a dibromonaphthalene or a dibromoquinoline, and more particularly 1,4-dibromonaphthalene, 1,8 -dibromoquinoline or 4,7-dibromoquinoline.

Cette composition permet ainsi, en remplaçant le chlore par le brome, de réaliser une composition fumigène ayant sensiblement les performances de celle connue à base de naphtalène chloré tout en ayant une toxicité moindre que cette dernière.This composition thus makes it possible, by replacing chlorine with bromine, to produce a smoke-producing composition having substantially the performance of that known based on chlorinated naphthalene while having less toxicity than the latter.

C'est le but de l'invention que de proposer une nouvelle composition pyrotechnique qui présente une toxicité réduite mais qui a une certaine efficacité de masquage, tant dans le domaine visible qu'infrarouge.It is the aim of the invention to propose a new pyrotechnic composition which has reduced toxicity but which has a certain masking effectiveness, both in the visible and infrared range.

Ainsi l'invention a pour objet l'utilisation d'au moins un sel halogéné de tetraphenyl phosphonium comme agent fumigène dans une composition pyrotechnique destinée à assurer le masquage d'un objectif vis à vis des rayonnements électromagnétiques dans une gamme de longueurs d'ondes donnée.Thus the subject of the invention is the use of at least one halogenated salt of tetraphenyl phosphonium as a smoke agent in a pyrotechnic composition intended to ensure the masking of an objective with respect to electromagnetic radiation in a range of wavelengths. given.

Ces sels halogénés sont disponibles dans le commerce et répertoriés sous les numéros internationaux CAS :

  • 2751 90 8 pour le bromure de tetraphenyl phosphonium ;
  • 2001 45 8 pour le chlorure de tetraphenyl phosphonium :
  • 2065 67 0 pour le iodure de tetraphenyl phosphonium :
  • 3587 05 1 pour le fluorure de tetraphenyl phosphonium.
These halogenated salts are commercially available and listed under international CAS numbers:
  • 2751 90 8 for tetraphenyl phosphonium bromide;
  • 2001 45 8 for tetraphenyl phosphonium chloride:
  • 2065 67 0 for tetraphenyl phosphonium iodide:
  • 3587 05 1 for tetraphenyl phosphonium fluoride.

Ils n'ont à ce jour jamais été utilisés dans des compositions pyrotechniques, qu'elles soient fumigènes ou non.To date, they have never been used in pyrotechnic compositions, whether smoke-producing or not.

Ils sont le plus souvent mis en œuvre comme produits précurseurs ou intermédiaires dans la synthèse d'autres composés, en particulier dans le domaine pharmaceutique. Leur structure facilite en effet la précipitation de molécules organiques.They are most often used as precursor products or intermediates in the synthesis of other compounds, particularly in the pharmaceutical field. Their structure facilitates the precipitation of organic molecules.

La demanderesse a découvert que la combustion de ces sels conduisait à la formation principalement d'acide phosphonique et non d'acide phosphorique comme pour la plupart des organophosphorés connus.The Applicant discovered that the combustion of these salts led to the formation mainly of phosphonic acid and not of phosphoric acid as for most known organophosphorus compounds.

Cet acide phosphonique est bien moins toxique que l'acide phosphorique et il conduit à la réalisation de nuages de masquage à toxicité réduite.This phosphonic acid is much less toxic than phosphoric acid and it leads to the production of masking clouds with reduced toxicity.

Par ailleurs cette combustion d'organophosphorés conduit à la réalisation de nuages de masquage ayant une efficacité importante vis-à-vis des rayonnements infrarouges.Furthermore, this combustion of organophosphorus compounds leads to the production of masking clouds having significant effectiveness with respect to infrared radiation.

Un sel halogéné de tétraphényl phosphonium a la formule développée suivante dans laquelle X- désigne l'ion halogène (Chlore, Brome, Iode ou fluor).

Figure imgb0001
A halogenated tetraphenyl phosphonium salt has the following structural formula in which X - denotes the halogen ion (Chlorine, Bromine, Iodine or fluorine).
Figure imgb0001

Cette molécule comporte quatre cycles aromatiques qui assurent lors de la combustion la production des particules de carbone souhaitées pour le masquage.This molecule has four aromatic rings which ensure, during combustion, the production of the carbon particles desired for masking.

La combustion conduira à la recombinaison des atomes d'halogène avec les autres espèces : carbone ou hydrogène, donnant des halogénures d'hydrogène ou des dérivés carbonés halogénés.Combustion will lead to the recombination of halogen atoms with other species: carbon or hydrogen, giving hydrogen halides or halogenated carbon derivatives.

Le phosphore se recombine sous la forme d'acide phosphonique.Phosphorus recombines in the form of phosphonic acid.

D'une façon préférée, le sel de tetraphenyl phosphonium mis en oeuvre est le bromure de tetraphenyl phosphonium.Preferably, the tetraphenyl phosphonium salt used is tetraphenyl phosphonium bromide.

Ce sel est de coût réduit et, comme le décrit le brevet WO2015/132266 , l'utilisation du brome permet d'éviter la formation de chlorure d'hydrogène lors de la combustion, ce qui réduit, la toxicité des fumées.This salt is low cost and, as described in the patent WO2015/132266 , the use of bromine makes it possible to avoid the formation of hydrogen chloride during combustion, which reduces the toxicity of the fumes.

Il serait aussi possible de mettre en oeuvre les autres sels halogénés qui assureront des performances de masquage comparables. On préférera cependant le bromure de tetraphenyl phosphonium ou le iodure de tetraphenyl phosphonium pour réduire la toxicité du nuage engendré.It would also be possible to use other halogenated salts which will ensure comparable masking performance. However, tetraphenyl phosphonium bromide or tetraphenyl phosphonium iodide will be preferred to reduce the toxicity of the cloud generated.

L'invention a également pour objet une composition pyrotechnique fumigène destinée à assurer le masquage d'un objectif vis à vis des rayonnements électromagnétiques dans une gamme de longueurs d'ondes donnée et comprenant au moins un matériau énergétique, tel qu'un couple oxydo-réducteur, ainsi qu'au moins un agent fumigène générateur de particules de masquage, composition caractérisée en ce qu'elle comprend comme agent fumigène au moins un sel halogéné de tetraphenyl phosphonium.The invention also relates to a pyrotechnic smoke composition intended to ensure the masking of an objective with respect to electromagnetic radiation in a given range of wavelengths and comprising at least one energetic material, such as an oxido-couple. reducing agent, as well as at least one smoke agent generating masking particles, composition characterized in that it comprises as a smoke-producing agent, at least one halogenated tetraphenyl phosphonium salt.

Un matériau énergétique est un matériau ou une composition qui peut être initiée et qui fournit une énergie suffisante pour brûler l'agent fumigène et provoquer ainsi l'émission des particules de masquage, essentiellement des particules de carbone. La combustion sera conduite avec un régime suffisant pour éviter l'extinction de la masse fumigène.An energetic material is a material or composition which can be initiated and which provides sufficient energy to burn the smoke agent and thus cause the emission of the masking particles, mainly carbon particles. Combustion will be carried out at a sufficient speed to avoid extinction of the smoke mass.

Comme matériau énergétique on pourra mettre en oeuvre un couple oxydo réducteur, par exemple un couple associant, comme réducteur une poudre métallique, et comme oxydant un polymère fluoré possédant dans sa structure moléculaire un pourcentage en fluor supérieur à 60%.As an energetic material, it is possible to use an oxido-reducing couple, for example a couple combining, as reducer, a metal powder, and as oxidant, a fluoropolymer having in its molecular structure a fluorine percentage greater than 60%.

Le réducteur pourra être choisi parmi les corps suivants : aluminium, zirconium, magnésium, titane, siliciure de calcium, bore.The reducer can be chosen from the following bodies: aluminum, zirconium, magnesium, titanium, calcium silicide, boron.

L'oxydant pourra être choisi parmi les corps suivants : di-polymère de fluorure de vinylidène et d'hexafluoro-propylène (par exemple le produit commercialisé par la société 3M sous la marque Dyneon FC2230), polytetra-fluoroéthylène, tétrafluoroéthylène ou leur mélange.The oxidant may be chosen from the following bodies: di-polymer of vinylidene fluoride and hexafluoro-propylene (for example the product sold by the company 3M under the brand Dyneon FC2230), polytetra-fluoroethylene, tetrafluoroethylene or their mixture.

Selon un mode particulier de réalisation, la composition pourra comprendre : au moins un composé organo chloré dans une proportion inférieure à 10% en masse. Ce composé chloré permet de plaquer davantage la fumée engendrée au sol.According to a particular embodiment, the composition may comprise: at least one organochlorinated compound in a proportion less than 10% by mass. This chlorinated compound allows the smoke generated to be further pressed to the ground.

En effet, le chlore va se combiner lors de la combustion aux espèces carbonées du nuage, formant des molécules de masse molaire relativement importante, cette recombinaison aura un effet mécanique d'alourdissement du nuage.Indeed, chlorine will combine during combustion with the carbon species in the cloud, forming molecules of mass relatively large molar, this recombination will have a mechanical effect of weighing down the cloud.

Il a pour avantage d'augmenter la durée du masquage en extérieur pour une masse de composition donnée en évitant une dispersion trop rapide de la fumée.It has the advantage of increasing the duration of outdoor masking for a given mass of composition by avoiding too rapid dispersion of the smoke.

Ce composé chloré sera ajouté en faible proportion pour que la toxicité du nuage ne soit pas augmentée de façon excessive. On choisira un corps incorporant un grand nombre d'atomes de chlore (taux de chloration supérieur à 60%) pour que, malgré la masse réduite, la recombinaison du chlore ait un effet notable.This chlorinated compound will be added in small proportions so that the toxicity of the cloud is not increased excessively. We will choose a body incorporating a large number of chlorine atoms (chlorination rate greater than 60%) so that, despite the reduced mass, the recombination of chlorine has a notable effect.

On pourra par exemple mettre en oeuvre le composé commercialisé sous la marque Dechlorane plus par la société américaine Oxychem. Ce composé est un polyhetéroaromatique utilisé comme retardateur de flamme bien connu et il est répertorié sous le numéro CAS 13560-89-9 . Il comporte dans sa structure moléculaire 12 atomes de chlore.For example, we could use the compound marketed under the brand Dechlorane plus by the American company Oxychem. This compound is a polyheteroaromatic used as a well-known flame retardant and is listed under the number CAS 13560-89-9 . It contains 12 chlorine atoms in its molecular structure.

Plus précisément, la composition de masquage selon l'invention pourra associer :

  • de 10 à 40% en masse de matériau énergétique et de préférence 20% à 30%,
  • de 90% à 60% en masse d'agent fumigène et de préférence 60% à 70%,
  • de 0% à 10% en masse d'agent chloré et de préférence 0 à 7%,
  • de 0% à 8% en masse de liant et de préférence 0 à 5%.
More precisely, the masking composition according to the invention may combine:
  • from 10 to 40% by mass of energetic material and preferably 20% to 30%,
  • from 90% to 60% by weight of fumigant and preferably 60% to 70%,
  • from 0% to 10% by weight of chlorinated agent and preferably 0 to 7%,
  • from 0% to 8% by weight of binder and preferably 0 to 5%.

Le liant permet d'améliorer la tenue mécanique du bloc de composition qui sera par exemple mis en oeuvre par compression.The binder makes it possible to improve the mechanical strength of the composition block which will for example be implemented by compression.

Le liant pourra être constitué par au moins une résine de type époxy ajoutée dans une proportion d'environ 5% de la masse globale du bloc (pour un bloc de 100 grammes, 5 grammes de liant sont ajoutés).The binder may consist of at least one epoxy type resin added in a proportion of approximately 5% of the overall mass of the block (for a 100 gram block, 5 grams of binder are added).

Dans tous les cas la mise en œuvre par compression se fera avec un taux de compression relativement important (17 Méga Pascals pour un diamètre de 125 mm par exemple).In all cases, the implementation by compression will be done with a relatively high compression rate (17 Mega Pascals for a diameter of 125 mm for example).

Pour plus de clarté, quelques exemples de compositions selon l'invention et de leurs utilisation sont décrits ci-après à titre illustratif et non restrictif, référence étant faite aux dessins annexés dans lesquels :

  • La figure 1 est une courbe montrant l'évolution au cours du temps du coefficient de camouflage Cm pour une composition selon l'exemple 2 donné ci-après;
  • La figure 2 montre l'évolution au cours du temps du coefficient de camouflage Cm pour une composition selon l'exemple 3 donné ci-après;
  • La figure 3 montre l'évolution au cours du temps du coefficient de camouflage Cm pour une composition selon l'exemple 4 donné ci-après.
For greater clarity, some examples of compositions according to the invention and their use are described below by way of illustration and not limitation, reference being made to the appended drawings in which:
  • There figure 1 is a curve showing the evolution over time of the camouflage coefficient Cm for a composition according to Example 2 given below;
  • There figure 2 shows the evolution over time of the camouflage coefficient Cm for a composition according to Example 3 given below;
  • There Figure 3 shows the evolution over time of the camouflage coefficient Cm for a composition according to Example 4 given below.

La demanderesse a réalisé un certain nombre de compositions conformes à l'invention (proportions des constituants données par rapport à la masse totale de la composition) et a procédé à l'évaluation de leurs performances de masquage.The applicant has produced a certain number of compositions in accordance with the invention (proportions of the constituents given relative to the total mass of the composition) and has carried out an evaluation of their masking performance.

Exemple 1Example 1

  • 12% en masse de poudre de magnésium,12% by mass of magnesium powder,
  • 18% en masse de di-polymère de fluorure de vinylidène et d'hexafluoropropylène,18% by mass of di-polymer of vinylidene fluoride and hexafluoropropylene,
  • 63% en masse de sel de tetraphenyl phosphonium,63% by mass of tetraphenyl phosphonium salt,
  • 7% en masse d'agent chloré.7% by weight of chlorinated agent.

Cette composition est mise sous la forme d'un bloc sans liant. Le bloc est réalisé par compression avec le taux de compression précisé précédemment (17 Méga Pascals pour un diamètre de 125 mm). Un tel taux de compression suffit à assurer la cohésion du bloc.This composition is put in the form of a block without binder. The block is made by compression with the compression rate specified previously (17 Mega Pascals for a diameter of 125 mm). Such a compression rate is sufficient to ensure the cohesion of the block.

Exemple 2Example 2

  • 12% en masse de poudre de magnésium,12% by mass of magnesium powder,
  • 12% en masse de di-polymère de fluorure de vinylidène et d'hexafluoropropylène,12% by mass of di-polymer of vinylidene fluoride and hexafluoropropylene,
  • 69% en masse de sel de tetraphenyl phosphonium,69% by mass of tetraphenyl phosphonium salt,
  • 7% en masse d'agent chloré,7% by mass of chlorinated agent,
  • 5% en masse de résine époxy.5% by mass of epoxy resin.
Exemple 3Example 3

  • 15% en masse de poudre de magnésium,15% by mass of magnesium powder,
  • 15% en masse de di-polymère de fluorure de vinylidène et d'hexafluoropropylène,15% by mass of di-polymer of vinylidene fluoride and hexafluoropropylene,
  • 69% en masse de sel de tetraphenyl phosphonium,69% by mass of tetraphenyl phosphonium salt,
  • 5% en masse de résine époxy.5% by mass of epoxy resin.
Exemple 4Example 4

  • 15% en masse de poudre de magnésium,15% by mass of magnesium powder,
  • 15% en masse de di-polymère de fluorure de vinylidène et d'hexafluoropropylène,15% by mass of di-polymer of vinylidene fluoride and hexafluoropropylene,
  • 62% en masse de sel de tetraphenyl phosphonium,62% by mass of tetraphenyl phosphonium salt,
  • 7% en masse d'agent chloré,7% by mass of chlorinated agent,
  • 5% en masse de résine époxy.5% by mass of epoxy resin.

Pour chaque composition on a réalisé un bloc fumigène d'environ 800 grammes.For each composition we made a smoke block of approximately 800 grams.

Ce bloc a été positionné dans un tunnel optronique à une distance de 6 mètres de la ligne de mesure optique.This block was positioned in an optronic tunnel at a distance of 6 meters from the optical measurement line.

La combustion du bloc se fait à la façon d'une « cigarette ». C'est-à-dire que l'initiation est réalisée au niveau de la surface supérieure libre du bloc qui se consume progressivement de sa surface supérieure à sa surface inférieure (surface d'appui).The block burns like a “cigarette”. That is to say that the initiation is carried out at the level of the free upper surface of the block which is gradually consumed from its upper surface to its lower surface (supporting surface).

On a déplacé le nuage de fumée engendré à l'aide d'un ventilateur à une vitesse contrôlée de 3m/s de façon à le faire passer devant les moyens de mesures.The cloud of smoke generated was moved using a fan at a controlled speed of 3m/s so as to make it pass in front of the measuring means.

Les moyens de mesure comprennent :

  • une source chaude qui présente une température régulée autour de 160°C ;
  • une source froide (constituée par la paroi en acier du tunnel optronique) :
  • une caméra thermique observant en bande 3 (fenêtre spectrale de 8 à 12um).
Means of measurement include:
  • a hot spring which has a regulated temperature around 160°C;
  • a cold source (consisting of the steel wall of the optronic tunnel):
  • a thermal camera observing in band 3 (spectral window from 8 to 12um).

Le masquage est évalué en comparant l'effet du passage de la fumée devant les sources thermiques (froide et chaude) sur la température vue par la caméra thermique.Masking is evaluated by comparing the effect of passing smoke past thermal sources (cold and hot) on the temperature seen by the thermal camera.

Pour chaque pot testé, les coefficients de camouflage Cm (en pourcentage) sont calculés en appliquant la formule suivante : C m t = 100 × 1 − Nb t − Nn t Nb ′ − Nn ′

Figure imgb0002
For each pot tested, the camouflage coefficients Cm (in percentage) are calculated by applying the following formula: VS m t = 100 × 1 − No. t − Nn t No. ′ − Nn ′
Figure imgb0002

Formule dans laquelle :

  • Nb (t) et Nb' sont les niveaux numériques mesurés par la caméra au niveau de la source chaude, en présence de la fumée (Nb(t)) et en l'absence de fumée (Nb') ;
  • Nn(t) et Nn' sont les niveaux numériques mesurés par la caméra au niveau de la source froide, en présence de la fumée (Nn(t)) et en l'absence de fumée (Nn').
Formula in which:
  • Nb (t) and Nb' are the digital levels measured by the camera at the hot source, in the presence of smoke (Nb(t)) and in the absence of smoke (Nb');
  • Nn(t) and Nn' are the digital levels measured by the camera at the cold source, in the presence of smoke (Nn(t)) and in the absence of smoke (Nn').

Comme précisé précédemment, les figures annexées montrent l'évolution au cours du temps en abscisse du coefficient de camouflage Cm en ordonnée pour différents exemples de composition.As previously specified, the appended figures show the evolution over time on the abscissa of the camouflage coefficient Cm on the ordinate for different examples of composition.

La figure 1 correspond à la composition selon l'exemple 2, la figure 2 correspond à la composition selon l'exemple 3 et la figure 3 correspond à la composition selon l'exemple 4.There figure 1 corresponds to the composition according to Example 2, the figure 2 corresponds to the composition according to Example 3 and the Figure 3 corresponds to the composition according to Example 4.

On remarque en considérant toutes les figures que les compositions de masquage selon l'invention permettent d'obtenir un coefficient de camouflage supérieur à 45% pendant une durée d'au moins 90 secondes ce qui est particulièrement avantageux.We note by considering all the figures that the masking compositions according to the invention make it possible to obtain a camouflage coefficient greater than 45% for a duration of at least 90 seconds which is particularly advantageous.

Par ailleurs, les performances de masquage sont très similaires pour les différentes compositions, ce qui dénote une certaine stabilité du fonctionnement même avec quelques % d'écarts de formulation.Furthermore, the masking performances are very similar for the different compositions, which indicates a certain stability of operation even with a few % formulation differences.

On remarque également que la mise en place du rideau de fumée est rapide. Elle est comprise entre 3 secondes et 10 secondes.We also notice that the installation of the smoke curtain is rapid. It is between 3 seconds and 10 seconds.

On a pu remarquer par ailleurs, dans le cadre d'autres essais, que la vitesse de combustion est fonction du taux de magnésium. Ainsi, la vitesse de combustion augmente lorsque le taux de magnésium augmente. Par exemple, un taux de magnésium de 15% procurera une durée de combustion du bloc de près de 52 secondes tandis qu'un taux de magnésium de 12% procurera un temps de combustion de 88 secondes.It was also noted, in the context of other tests, that the combustion speed depends on the magnesium content. Thus, the combustion rate increases when the magnesium level increases. For example, a magnesium content of 15% will provide a block combustion time of nearly 52 seconds while a magnesium content of 12% will provide a combustion time of 88 seconds.

Ceci n'est pas particulièrement visible sur les figures qui montrent les résultats d'essais en tunnel de tir.This is not particularly visible in the figures which show the results of firing tunnel tests.

On a pu observer par ailleurs que l'ajout de Dechlorane permettait d'augmenter la durée du masquage lors d'une combustion en extérieur.It was also observed that the addition of Dechlorane made it possible to increase the duration of masking during outdoor combustion.

Il est évident que l'invention n'est nullement limitée aux exemples décrits ci-avant mais que de nombreuses modifications peuvent être apportées à la composition pyrotechnique fumigène et son utilisation décrites ci-avant sans sortir du cadre de l'invention telle que définie dans les revendications suivantes.It is obvious that the invention is in no way limited to the examples described above but that numerous modifications can be made to the pyrotechnic smoke composition and its use described above without departing from the scope of the invention as defined in the following claims.

Claims (16)

  1. Use of at least one tetraphenylphosphonium halogenated salt as smoke-producing agent in a pyrotechnic composition for masking a target relating to electromagnetic radiation in a given wavelengths range.
  2. Use according to claim 1, characterised in that the tetraphenylphosphonium halogenated salt used is tetraphenylphosphonium bromide.
  3. Smoke-producing pyrotechnic composition for masking a target relating to electromagnetic radiation in a given wavelengths range and comprising at least one energetic material, such as a redox couple, and also at least one smoke-producing generating masking particle agent, said composition being characterised in that it comprises at least one tetraphenylphosphonium halogenated salt as smoke-producing agent.
  4. Composition according to claim 3, characterised in that it comprises bromide or iodide tetraphenylphosphonium as smoke-producing agent.
  5. Composition according to claim 4, characterised in that it comprises a redox couple which combines, by way of reducing agent, a metal powder, and by way of oxidant, a fluorinated polymer as energetic material.
  6. Composition according to claim 5, characterised in that the fluorinated polymer is a fluorinated polymer having a fluorine percentage greater than 60% in its molecular structure.
  7. Composition according to claim 5 or 6, characterised in that it comprises at least one reducing agent chosen from the following substances or compounds: magnesium, aluminium, zirconium, titanium, calcium silicide, boron.
  8. Composition according to any one of the claims 5 to 7, characterised in that it comprises at least one oxidant chosen from the following substances or compounds: di-polymer of vinylidene fluoride and hexafluoropropylene, polytetrafluoroethylene, tetrafluoroethylene or mixtures thereof.
  9. Composition according to any one of the claims 5 to 8, characterised in that it comprises at least one chlorine compound in a proportion of less than 10% by weight.
  10. Composition according to claim 9, characterised in that it comprises at least one organochlorine compound with a chlorine level greater than 60%.
  11. Composition according to one of the claims 3 to 10, characterised in that it comprises:
    - 10% to 40% by weight of energetic material and preferably 20% to 30%,
    - 90% to 60% by weight of smoke-producing agent and preferably 60% to 70%,
    - 0% to 10% by weight of chlorine agent and preferably 0 to 7%,
    - 0% to 8% by weight of binding agent and preferably 0 to 5%.
  12. Composition according to claim 11, characterised in that said binding agent consists of at least an epoxy resin added in a proportion of about 5% of the overall mass of the block.
  13. Composition according to claim 11, characterised in that it comprises:
    - 12% by weight of magnesium powder,
    - 18% by weight of di-polymer of vinylidene fluoride and hexafluoropropylene,
    - 63% by weight of tetraphenylphosphonium salt,
    - 7% by weight of chorine agent.
  14. Composition according to claim 11, characterised in that it comprises:
    - 12% by weight of magnesium powder,
    - 12% by weight of di-polymer of vinylidene fluoride and hexafluoropropylene,
    - 69% by weight of tetraphenylphosphonium salt,
    - 7% by weight of chorine agent,
    - 5% by weight of epoxy resin.
  15. Composition according to claim 11, characterised in that it comprises:
    - 15% by weight of magnesium powder,
    - 15% by weight of di-polymer of vinylidene fluoride and hexafluoropropylene,
    - 69% by weight of tetraphenylphosphonium salt,
    - 5% by weight of epoxy resin.
  16. Composition according to claim 11, characterised in that it comprises:
    - 15% by weight of magnesium powder,
    - 15% by weight of di-polymer of vinylidene fluoride and hexafluoropropylene,
    - 62% by weight of tetraphenylphosphonium salt,
    - 7% by weight of chlorine agent,
    - 5% by weight of epoxy resin.
EP18833334.8A 2018-01-08 2018-12-21 Use of a halogenated salt of tetraphenylphosphonium as a smoke-producing agent and smoke-producing pyrotechnic composition incorporating such material Active EP3737657B1 (en)

Applications Claiming Priority (2)

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BE2018/5007A BE1025879B1 (en) 2018-01-08 2018-01-08 Use of a halogenated salt of tetraphenyl phosphonium as a fumigant and fumigant pyrotechnic composition incorporating such material
PCT/IB2018/060502 WO2019135144A1 (en) 2018-01-08 2018-12-21 Use of a halogenated salt of tetraphenylphosphonium as a smoke-producing agent and smoke-producing pyrotechnic composition incorporating such material

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US (1) US20200331822A1 (en)
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CA (1) CA3085839A1 (en)
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WO (1) WO2019135144A1 (en)

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Publication number Priority date Publication date Assignee Title
FR2560186B1 (en) * 1982-07-27 1987-06-05 France Etat Armement PYROTECHNIC COMPOSITION GENERATING OPAQUE SMOKE WITH INFRARED RADIATION AND FUMIGENE AMMUNITION OBTAINED
TW318861B (en) * 1994-08-16 1997-11-01 Mitsui Toatsu Chemicals
JPH08217587A (en) * 1995-02-08 1996-08-27 Otsuka Chem Co Ltd Gas generating agent for air bag
FR3018073B1 (en) * 2014-03-03 2016-04-01 Etienne Lacroix Tous Artifices S A WET-BAND LOW-BAND SMOKING MASK FUNGICY PYROTECHNIC COMPOSITIONS WITH LOW TOXICITY

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US20200331822A1 (en) 2020-10-22
WO2019135144A1 (en) 2019-07-11
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BE1025879B1 (en) 2019-08-06
CA3085839A1 (en) 2019-07-11
PL3737657T3 (en) 2024-07-08
EP3737657A1 (en) 2020-11-18

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