EP3114099B1 - Pyrotechnische rauchzusammensetzungen mit geringer toxizität zur breitbandigen verdeckung - Google Patents

Pyrotechnische rauchzusammensetzungen mit geringer toxizität zur breitbandigen verdeckung Download PDF

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Publication number
EP3114099B1
EP3114099B1 EP15707643.1A EP15707643A EP3114099B1 EP 3114099 B1 EP3114099 B1 EP 3114099B1 EP 15707643 A EP15707643 A EP 15707643A EP 3114099 B1 EP3114099 B1 EP 3114099B1
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EP
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Prior art keywords
composition
weight
polyaromatic
pyrotechnic
binder
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EP15707643.1A
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English (en)
French (fr)
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EP3114099A1 (de
Inventor
Alexandrine Maraval
Loic BORDERIEUX
Dominique Medus
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Etienne LaCroix Tous Artifices SA
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Etienne LaCroix Tous Artifices 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)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
    • F42B12/02—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect
    • F42B12/36—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information
    • F42B12/46—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information for dispensing gases, vapours, powders or chemically-reactive substances
    • F42B12/48—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the warhead or the intended effect for dispensing materials; for producing chemical or physical reaction; for signalling ; for transmitting information for dispensing gases, vapours, powders or chemically-reactive substances smoke-producing, e.g. infrared clouds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B27/00—Hand grenades

Definitions

  • the present invention relates to pyrotechnic compositions of low toxicity advantageously intended for the protection of land platforms (such as vehicles or armored vehicles), in particular against infrared guided threats. Said compositions make it possible to produce an effective camouflage cloud in the visible and infrared range.
  • the masking compositions currently used generally comprise an oxidizing / reducing couple, and a compound serving as fuel (fuel oil). During combustion, the fuel makes it possible to generate particles of shape and size adapted to ensure effective masking in the visible and infrared, in particular for the spectral window of between 3 and 14 ⁇ m.
  • These compositions include chlorinated compounds, such as CLONACIRE® (composition comprising a mixture of chlorinated naphthalenes with a degree of substitution greater than 3) or hexachloroethane. These play the role of either an oxidizer or a particle generator product.
  • the threshold for the first lethal effects and the threshold for irreversible effects associated with gaseous HCl for 10 minutes of exposure are 1300 ppm (threshold for first lethal effects, or 1937 mg / m 3 ), and 240 ppm (threshold for irreversible effects, or 358 mg / m 3 ).
  • brominated compounds in pyrotechnic compositions is already known, in particular for applications as a decoy for the protection of aerial targets against infrared-guided threats, without however addressing the problem of the toxicity of said compositions.
  • the effects sought in this case are generally not masking fumes but infra-red radiation imitating the radiation from the engine of aerial platforms.
  • patents US 3,498,925 and US 3,400,082 teach the use of metallic or organometallic compounds but not halogenated to reduce the toxicity of pyrotechnic compositions for masking in the visible.
  • Requirement US 2012/0267016 which relates to smoke-producing compositions for masking in the visible, for its part recommends the use of a mixture comprising melamine and polymethylated methylgallate.
  • these compositions comprise sucrose as fuel, and a chlorate as oxidant.
  • the patent US 4,238,254 describes pyrotechnic compositions for visible masking, including guanidine nitrate, which produces basic compounds capable of neutralizing hydrogen chloride (HCl) or phosphorus pentoxide produced in fumes.
  • Requirement EP 1 876 161 teaches a pyrotechnic charge for the production of infrared radiation containing a brominated compound as fuel and / or as an oxidizing agent.
  • a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as fuel in a pyrotechnic composition, preferably a fumigant, makes it possible to significantly reduce the toxicity of the pyrotechnic compositions. compared to those of the prior art, while retaining their masking performance both in the visible and in the infrared.
  • spectral window is understood to mean a wavelength domain.
  • polyaromatic compound is understood to mean a C10 to C14 hydrocarbon-based compound, consisting of 2 to 3 adjoining aromatic rings.
  • polyaromatic compounds mention may be made in particular of naphthalene, anthracene and phenanthrene.
  • it is naphthalene and anthracene, more preferably naphthalene.
  • polyheteroaromatic compound means a compound consisting of 2 to 3 aromatic or heteroaromatic rings joined together and comprising at least one nitrogenous heteroaromatic ring.
  • polyheteroaromatic compounds mention may be made in particular of quinoline, isoquinoline and naphthyridine. Preferably, it is quinoline.
  • chlorinated compound means an organic compound comprising at least one chlorine atom, in particular a compound comprising at least one chlorine carbon bond (C-Cl).
  • the present invention relates exclusively to chemically stable compounds.
  • the polyaromatic or polyheteroaromatic compounds substituted with 1 to 3 bromine atoms according to the invention do not contain chlorinated substituents.
  • the polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms does not contain other substituents.
  • the potentially toxic species emitted during the combustion of the fumigant are determined.
  • the quantities emitted during combustion are evaluated by thermodynamic calculation codes.
  • the literature is searched for the thresholds for the first lethal effects and the thresholds for irreversible effects. These two thresholds are evaluated as a function of the duration of exposure of the subject to the toxic substance, in this case gaseous HBr.
  • the threshold for the first lethal effects and the threshold for the associated irreversible effects to gaseous HBr for 10 minutes of exposure are 3290 ppm (threshold for first lethal effects, or 11 054 mg / m 3 ), and 366 ppm (threshold for irreversible effects, or 1228 mg / m 3 ).
  • the present invention relates to the subject of the claims.
  • the present application firstly describes the use of a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as fuel in a pyrotechnic composition, preferably a fumigant, so that, during the combustion of said composition, the content of toxic substance in the gases emitted, such as hydrobromic acid, is less than 350 ppm, preferably less than 300 ppm.
  • the present invention further relates to a pyrotechnic device comprising said composition.
  • the present invention also relates to a method of masking a target comprising the production of a smoke screen preventing the transmission of infrared radiation between the target and the threat using a pyrotechnic composition, preferably smoke, comprising a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as fuel, in which the pyrotechnic composition is a composition according to the invention.
  • a pyrotechnic composition preferably smoke, comprising a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as fuel, in which the pyrotechnic composition is a composition according to the invention.
  • the present application describes the use of a polyaromatic or polyheteroaromatic compound substituted with 1 to 3 bromine atoms as defined above as fuel in a pyrotechnic composition, preferably a fumigant, in which, during the combustion of said composition, the content of toxic substance, in particular hydrobromic acid, of the gases emitted is less than 350 ppm, preferably less than 300 ppm.
  • the combustion of said composition offers a camouflage coefficient in the spectral window 8 to 12 ⁇ m greater than 50%, preferably greater than 60%, typically for 15 seconds, preferably for 20 seconds.
  • the combustion of said composition offers a camouflage coefficient in the spectral window 3 to 5 ⁇ m greater than 60%, preferably greater than 70%, typically for 15 seconds, preferably for 20 seconds.
  • the smoke-producing composition does not contain a chlorinated compound.
  • the polyaromatic or polyheteroaromatic compound is substituted by 2 bromine atoms, even more advantageously, it is a dibromonaphthalene or a dibromoquinoline, even more advantageously 1,4-dibromonapthalene, 1,8-dibromoquinoline or 4,7-dibromoquinoline.
  • composition not containing a chlorinated compound.
  • the weight of the binder is adjusted, if necessary, so that the percentages of the various elements added are equal to 100%.
  • the percentage of binder is adjusted relative to the mass percentages of reducing agent, fuel, optionally oxidant and additives, to obtain 100%.
  • the composition is devoid of chlorine compound.
  • the polyaromatic or polyheteroaromatic compound is substituted with 2 bromine atoms.
  • the polyaromatic or polyheteroaromatic compound is substituted by 2 bromine atoms, even more advantageously, it is a dibromonaphthalene or a dibromoquinoline, even more advantageously 1,4-dibromonapthalene, 1,8-dibromoquinoline or 4,7-dibromoquinoline.
  • the reducing agent is chosen from magnesium, aluminum, zirconium, titanium, silicon and boron or their mixtures, for example in the form of metal powder.
  • the reducing agent consists essentially of powder of magnesium or of a mixture of zirconium and magnesium.
  • the binder is then chosen from fluoroelastomers or their mixtures, advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF, in English polycarbon mono fluoride) or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or tetrafluoroethylene (such as VITON®) or their mixtures.
  • fluoroelastomers or their mixtures advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF, in English polycarbon mono fluoride) or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinylether and / or tetrafluoroethylene (such as VITON®) or their mixtures.
  • the binder does not act as an oxidant.
  • the compositions according to the invention comprise between 5% and 15% by weight of oxidant, advantageously chosen from potassium chlorate, ammonium chlorate, potassium perchlorate, ammonium perchlorate, potassium nitrate or ammonium nitrate, or mixtures thereof.
  • the oxidant can also be chosen from fluoroelastomers or their mixtures, advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF, in English polycarbon mono fluoride) or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinyl ether and / or tetrafluoroethylene or their mixtures.
  • fluoroelastomers or their mixtures advantageously polytetrafluoroethylene, poly (carbon monofluoride) (PMF, in English polycarbon mono fluoride) or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethylvinyl ether and / or tetrafluoroethylene or their mixtures.
  • the binder is then chosen from phenolic polymers, epoxy resins and polybutadiene.
  • the oxidant is advantageously chosen from polytetrafluoroethylene, poly (carbon monofluoride) (PMF, in English polycarbon mono fluoride) or a copolymer of vinylidene fluoride, hexafluoropropylene, perfluoromethyl vinyl ether and / or tetrafluoroethylene or their mixtures.
  • compositions according to the invention can also comprise additives, such as hardeners, combustion retarders, flame inhibitors.
  • the combustion retarders are in particular chosen from diatoms and carbon graphite.
  • An example of a preferred flame inhibitor is sodium hydrogencarbonate.
  • the preferred additives are flame retardants and flame inhibitors.
  • the present invention also relates to a pyrotechnic device comprising a container in which is housed the payload of pyrotechnic composition according to the invention.
  • the pyrotechnic composition according to the invention is shaped by compression.
  • the container is typically a smoke pot or a grenade capable of being launched by a launcher or manually.
  • the present invention also relates to a method of masking a target comprising the production of a smoke screen preventing the transmission of infrared radiation between the target and the threat using a pyrotechnic composition, preferably smoke, comprising a polyaromatic or substituted polyheteroaromatic compound with 1 to 3 bromine atoms as fuel, in which the pyrotechnic composition is a composition according to the invention.
  • a pyrotechnic composition preferably smoke, comprising a polyaromatic or substituted polyheteroaromatic compound with 1 to 3 bromine atoms as fuel, in which the pyrotechnic composition is a composition according to the invention.
  • the enthalpy of formation of 1,4-dibromonaphthalene was defined as being equal to 27.6 kCal / mol using Hyperchem software and data from the literature.
  • thermodynamic calculation was carried out in the absence of oxygen from the air, under 2 atmospheres of pressure and at a temperature of 2000K.
  • the mass fractions of the species emitted resulting from this calculation mainly show a toxic species which is HBr. Its mass fraction is given by the Coppelia calculation as being equal to 0.3436.
  • the maximum concentration near the source of the smoke i.e. the burning smoke pot of HBr can be estimated at 300 ppm. This concentration decreases rapidly by dilution as soon as one moves away from this source.
  • compositions tested contain 1,4-dibromonaphthalene as fuel. It is this fuel which, associated with the oxidizing reducing couple, makes it possible to ensure the broadband masking performance.
  • the binder used is a fluoropolymer of Viton® type. This binder also serves as an oxidant in the composition.
  • the reducer used is magnesium. 1,4-dibromonaphthalene is present in the composition in an amount of approximately 70%, the Viton® binder represents 11% by weight of the composition, the reducing agent constitutes 19% of the mixture.
  • the binder used is an epoxy resin associated with its hardener.
  • the oxidant used in the composition is a fluoropolymer of the polytetrafluoroethylene type.
  • the reducing agent used is magnesium.
  • a combustion retarder is also used in the composition, it is graphite carbon. 1,4-Dibromonaphthalene is present in this composition at 68%, the binder at 3%, the reducing agent at 17%, the oxidant at 10% and the combustion retarder represents 2% in mass of the composition.
  • compositions tested are compressed in the form of cylindrical smoke pots.
  • the mass of composition contained in each jar is approximately 400g.
  • test means make it possible to move the smoke cloud at a controlled speed so as to cause it to pass in a controlled and reproducible manner in front of the measuring means described below.
  • the smoke curtain moves and passes in front of the measuring means, thus making it possible to measure the infrared performance of the smoke under controlled and reproducible conditions.
  • compositions 1 and 2 in the 3-5 ⁇ m and 8-12 ⁇ m spectral windows are shown in the figures 1 to 4 .
  • composition 1 the combustion of said composition offers a camouflage coefficient in the spectral window 8 to 12 ⁇ m and 3-5 ⁇ m greater than 50%, for at least 20 seconds.
  • composition 1 offers a camouflage coefficient greater than 70% for 15 seconds in the 3-5 ⁇ m spectral band and greater than 60% for 15 seconds in the 8-12 ⁇ m spectral window.
  • Composition 2 provides a camouflage coefficient greater than 70% for 30 seconds in the 3-5 ⁇ m spectral band and greater than 60% for 20 seconds in the 8-12 ⁇ m spectral window.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Organic Chemistry (AREA)
  • Botany (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Claims (9)

  1. Pyrotechnische Zusammensetzung, vorzugsweise rauchentwickelnd, bestehend aus mindestens einem Reduktionsmittel, einem Bindemittel und mindestens einer polyaromatischen oder polyheteroaromatischen Verbindung, substituiert mit ein bis drei Bromatomen als Brennstoff, und gegebenenfalls einem Oxidationsmittel, in folgenden Anteilen:
    - 5 bis 25 Gew.-% Reduktionsmittel,
    - 2 bis 25 Gew.-% eines Bindemittels, eventuell gemischt mit einem Weichmacher, und
    - 50 bis 90 Gew.-% eines Brennstoffs, der mindestens eine polyaromatische oder polyheteroaromatische Verbindung enthält, substituiert mit ein bis drei Bromatomen,
    - optional 5 bis 15 Gew.-% Oxidationsmittel und
    - optional 2 bis 10 Gew.-% Zusatzstoffe bezogen auf das Gesamtgewicht der Zusammensetzung, wobei die Zusammensetzung keine chlorierte organische Verbindung enthält.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass die polyaromatische oder polyheteroaromatische Verbindung mit zwei Bromatomen substituiert wird.
  3. Zusammensetzung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die polyaromatische oder polyheteroaromatische Verbindung ein Dibromnaphthalin oder ein Dibromchinolin ist.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Reduktionsmittel ausgewählt wird aus Magnesium, Aluminium, Zirkonium, Titan, Silizium und Bor oder deren Mischungen, z. B. in Form von Metallpulver, wobei das Reduktionsmittel vorzugsweise im Wesentlichen aus Magnesiumpulver oder einer Mischung aus Zirkonium und Magnesium besteht.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Oxidationsmittel ausgewählt wird aus Kaliumchlorat, Ammoniumchlorat, Kaliumperchlorat, Ammoniumperchlorat, Kaliumnitrat oder Ammoniumnitrat, Fluorelastomeren oder deren Mischungen.
  6. Zusammensetzung nach Anspruch 5, dadurch gekennzeichnet, dass das Bindemittel ausgewählt wird aus Phenolpolymeren, Epoxidharzen und Polybutadien.
  7. Zusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Bindemittel auch als Oxidationsmittel dient, und vorzugsweise ausgewählt wird aus Fluorelastomeren, vorzugsweise Polytetrafluorethylen, Poly(Kohlenstoffmonofluorid) oder einem Copolymer aus Vinylidenfluorid, Hexafluorpropylen, Perfluormethylvinylether und/oder Tetrafluorethylen oder deren Mischungen.
  8. Pyrotechnische Vorrichtung umfassend einen Behälter, typischerweise einen Nebeltopf oder eine Granate, der bzw. die von einer Abschussvorrichtung oder von Hand geworfen werden kann, in dem bzw. der die Nutzlast der pyrotechnischen Zusammensetzung nach einem der Ansprüche 1 bis 7 untergebracht ist.
  9. Verfahren zum Verbergen eines Ziels, umfassend das Erzeugen einer Nebelwand, die die Übertragung von Infrarotstrahlung zwischen dem Ziel und der Bedrohung verhindert, mithilfe einer pyrotechnischen, vorzugsweise rauchentwickelnden, Zusammensetzung, die eine polyaromatische oder polyheteroaromatische Verbindung, substituiert mit ein bis drei Bromatomen als Brennstoff, enthält, wobei die pyrotechnische Zusammensetzung nach einem der Ansprüche 1 bis 7 definiert ist.
EP15707643.1A 2014-03-03 2015-03-03 Pyrotechnische rauchzusammensetzungen mit geringer toxizität zur breitbandigen verdeckung Active EP3114099B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1451689A FR3018073B1 (fr) 2014-03-03 2014-03-03 Compositions pyrotechniques fumigenes de masquage large bande de faible toxicite
PCT/EP2015/054432 WO2015132266A1 (fr) 2014-03-03 2015-03-03 Compositions pyrotechniques fumigenes de masquage large bande de faible toxicite

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EP3114099A1 EP3114099A1 (de) 2017-01-11
EP3114099B1 true EP3114099B1 (de) 2021-05-26

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EP (1) EP3114099B1 (de)
KR (1) KR102325489B1 (de)
ES (1) ES2883403T3 (de)
FR (1) FR3018073B1 (de)
WO (1) WO2015132266A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1025879B1 (fr) * 2018-01-08 2019-08-06 Mecar Sa Utilisation d'un sel halogéné de tetraphenyl phosphonium comme agent fumigène et composition pyrotechnique fumigène incorporant un tel matériau
KR102481792B1 (ko) * 2021-07-14 2022-12-27 엘아이지넥스원 주식회사 수중 설치 구조물 은폐장치 및 그 제어방법

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
US4096005A (en) * 1977-06-13 1978-06-20 Nuclei Engineering, Inc. Pyrotechnic cloud seeding composition
DE2819850C2 (de) * 1978-05-05 1980-03-20 Buck Chemisch-Technische Werke Gmbh & Co, 8230 Bad Reichenhall Pyrotechnischer Nebelsatz
FR2560186B1 (fr) * 1982-07-27 1987-06-05 France Etat Armement Composition pyrotechnique generatrice de fumee opaque au rayonnement infrarouge et munition fumigene obtenue
DE4030430C1 (de) * 1990-09-26 1993-12-02 Buck Chem Tech Werke IR-undurchlässigen Nebel erzeugende Zusammensetzung
DE102006030679A1 (de) 2006-07-04 2008-01-10 Diehl Bgt Defence Gmbh & Co. Kg Pyrotechnischer Satz

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KR102325489B1 (ko) 2021-11-11
EP3114099A1 (de) 2017-01-11
WO2015132266A1 (fr) 2015-09-11
ES2883403T3 (es) 2021-12-07
KR20170007244A (ko) 2017-01-18
FR3018073A1 (fr) 2015-09-04
FR3018073B1 (fr) 2016-04-01

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