EP0936205B1 - Non-detonatable pyrotechnic materials for microsystems - Google Patents

Non-detonatable pyrotechnic materials for microsystems Download PDF

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Publication number
EP0936205B1
EP0936205B1 EP99400281A EP99400281A EP0936205B1 EP 0936205 B1 EP0936205 B1 EP 0936205B1 EP 99400281 A EP99400281 A EP 99400281A EP 99400281 A EP99400281 A EP 99400281A EP 0936205 B1 EP0936205 B1 EP 0936205B1
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EP
European Patent Office
Prior art keywords
weight
substance according
energetic
ammonium perchlorate
nitramine
Prior art date
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Expired - Lifetime
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EP99400281A
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German (de)
French (fr)
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EP0936205A1 (en
Inventor
Bernard Finck
Alain Lefumeux
Bernard Mahe
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Safran Ceramics SA
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Societe Nationale des Poudres et Explosifs
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Classifications

    • 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)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
    • 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
    • C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/11—Particle size of a component
    • Y10S149/113—Inorganic oxygen-halogen salt

Definitions

  • the invention relates to pyrotechnic materials non-detonable of very thin thickness or low mass and whose combustion is self-sustaining after initiation punctual by low energy as well as their uses. It also concerns the compositions energy to obtain these materials.
  • the invention relates to non-detonable pyrotechnic materials, thick less than 500 ⁇ m or mass less than 15 mg, and able to burn after specific initiation by a electrical power between 150 mW and 800 mW, for a short time.
  • These new materials can be integrated into microsystems and are useful due to gases and / or the heat they give off as actuators, by example by inflating membranes, triggering microvalves, by transferring orders in circuits pyrotechnic transmission logics, causing the fusion in micro fuses of electrical transmission, causing a micropropulsion or initiating the ignition of other materials.
  • the initiation power they receive in these microsystems is very small and applied for a short time.
  • the energetic compositions must allow to obtain materials of very fine thickness, such as for example in the form of sheets, films, ribbons or layers or very low mass, for example in the form of pearls and the constitution of the materials obtained must be homogeneous.
  • They can be in any form but this form must have according to one of the achievements, thickness less than 500 ⁇ m, preferably less than or equal to 300 ⁇ m. They can for example be in the form of films, sheets, ribbons or layers. The thickness of these films, sheets, ribbons, or layers is generally equal to or greater than 50 ⁇ m, preferably equal to or greater than 100 ⁇ m.
  • this form has a mass generally less than 15 mg, preferably less than or equal to 3 mg.
  • Materials can be for example in the form of pearls. Generally, the mass of these materials is 0.1 mg or more, preferably 0.2 mg or more.
  • the compounds that form the binders contained in the materials of the present invention are the compounds known usually used in the field pyrotechnic. They are in the trade or they are prepared according to known methods.
  • binder in addition to the main components previously mentioned which form the binder, we also include in it, the usual additives such as in particular polymerization catalysts and crosslinkers.
  • additives such as in particular polymerization catalysts and crosslinkers.
  • the materials comprise from 30% to 80%, preferably from 40% to 60%, in weight of the energy binder based on PAG or BAMO and from 20% to 70%, preferably from 40% to 60% by weight of ammonium perchlorate.
  • the preferred binder is based of glycidyl polyazide.
  • polyesters and polyethers we may mention the polyadipates of alkylene glycol or of polyalkylene glycol and polyalkylene glycols.
  • energetic plasticizers we may include nitroglycerin (Ngl), trinitrate butanetriol (BTTN), trimethylolethane trinitrate (TMETN) and triethylene glycol dinitrate (TRENO). Of preferably we use a mixture of several plasticizers.
  • Binders based on polyesters or polyethers and at least one energy plasticizer represent preferably from 35% to 50% by weight of the compositions.
  • a polyester-based binder that works well includes a diethylene glycol polyadipate crosslinked by a polyisocyanate such as tri (isocyanato-6-hexyl) bi-uret (BTHI).
  • BTHI tri (isocyanato-6-hexyl) bi-uret
  • the energy plasticizer is preferably a mixture of TMETN and BTTN.
  • the amount of ammonium perchlorate is in these materials preferably from 20% to 32% by weight.
  • the nitramine (s) preferably represent 20% to 35% by weight of these materials.
  • the size of the dispersed perchlorate grains in the binders according to the invention is important so to obtain the pyrotechnic materials which have the desired properties.
  • This dimension is preferably chosen in the range from 1 to 10 ⁇ m.
  • the power P of the point initiation that the materials can receive is very low. She is such that 150 mW ⁇ P ⁇ 800 mW. Preferably P is ⁇ to 300 mW. It must be applied for a time t, such than 20 ms ⁇ t ⁇ 600 ms, preferably t ⁇ 125 ms. This condition does not mean that every power P can be applied for any time including t in this range to initiate the material but that there exists at least one time t included in this fork allowing its initiation.
  • point initiation means an initiation carried out on a very small surface of the material, of the order of 0.2 mm 2 , for example on an area of 0.1 mm x 2 mm.
  • the power needed to activate the material can be provided by various known means such as by example by a mini electrical resistance or by a laser beam.
  • the main gases that are formed are hydrogen, nitrogen, water vapor, gas carbon dioxide and / or carbon monoxide.
  • Another object of the present invention relates to the compositions for obtaining the materials such as described previously. They include binders energy, ammonium perchlorate and possibly the nitramine (s) and the quantities of these components as mentioned previously.
  • the different components are mixed according to known techniques, generally by kneading.
  • the materials can be obtained from these compositions using different known techniques, for example by placing the compositions between two plates or in a mold and hardening them under the effect of heat or by evaporating the solvent, or by cutting in a hardened block of more dimensions important, obtained beforehand, or using the deposition technique by screen printing followed by curing.
  • Another object of the present invention relates to several uses of new materials fireworks.
  • microsystems are suitable to be part of microsystems as microgenerators of gases, micropropellers or microgenerators heat. In particular, they are useful for realize micropump or microvalve systems. Such microsystems are found in particular in devices for administering drugs by route Transdermal. They are also useful for transferring orders in logical transmission circuits pyrotechnic, to form microfuse elements electrical transmission circuit, to serve ignition initiators or to form the charge propellant of micropropellants used for example for modify the positioning or trajectory of satellites.
  • a composition was prepared with the following compounds: % in weight PAG-diol of molecular weight 2000, 57 BTHI 9.5 Triacetin (plasticizer) 3.5 NH 4 ClO 4 (grain size 1 ⁇ m) 30
  • the compounds were mixed in a mixer horizontal at 50 ° C for 3 hours.
  • a composition was prepared with the following compounds: % in weight PAG-diol of molecular weight 2000, 40.76 BTHI 6.74 Triacetin (plasticizer) 2.5 Tin dibutyl dilaurate (catalyst) 50 ppm NH 4 ClO 4 (grain size 3 ⁇ m) 50
  • the compounds were mixed in a mixer horizontal at 50 ° C for 3 hours.
  • the amount of heat produced by combustion is 3654 kJ / g.
  • the gases released are mainly of hydrogen, nitrogen and carbon monoxide.
  • a composition was prepared with the following compounds: % in weight Diethylene glycol polyadipate 8.33 with a molecular mass of 3800 Bridging agent 0.25 Nitro methyl aniline (NMA) 0.05 Dinitro phenyl amine (2-NDPA) 0.78 TMETN 19,15 BTTN 4.78 BTHI 1.66 NH 4 ClO 4 32 HMX 33
  • the compounds were mixed in a mixer horizontal at 50 ° C for 3 hours.
  • the theoretical gas yield of the material is 0.6 l / g.
  • the main gases released are carbon, carbon dioxide, hydrogen, nitrogen and water vapor.

Description

L'invention concerne des matériaux pyrotechniques non détonables d'épaisseur très mince ou de masse faible et dont la combustion s'auto-entretient après initiation ponctuelle par une faible énergie ainsi que leurs utilisations. Elle concerne également les compositions énergétiques pour obtenir ces matériaux.The invention relates to pyrotechnic materials non-detonable of very thin thickness or low mass and whose combustion is self-sustaining after initiation punctual by low energy as well as their uses. It also concerns the compositions energy to obtain these materials.

Plus particulièrement, l'invention concerne des matériaux pyrotechniques non détonables, d'épaisseur inférieure à 500 µm ou de masse inférieure à 15 mg, et capables de brûler après initiation ponctuelle par une puissance électrique comprise entre 150 mW et 800 mW, pendant un temps bref.More particularly, the invention relates to non-detonable pyrotechnic materials, thick less than 500 µm or mass less than 15 mg, and able to burn after specific initiation by a electrical power between 150 mW and 800 mW, for a short time.

Ces nouveaux matériaux sont intégrables dans des microsystèmes et sont utiles en raison des gaz et/ou de la chaleur qu'ils dégagent comme actionneurs, par exemple en gonflant des membranes, en déclenchant des microvannes, en transférant des ordres dans des circuits logiques de transmission pyrotechnique, en provoquant la fusion dans des microfusibles de circuits de transmission électrique, en provoquant une micropropulsion ou en initiant l'allumage d'autres matériaux.These new materials can be integrated into microsystems and are useful due to gases and / or the heat they give off as actuators, by example by inflating membranes, triggering microvalves, by transferring orders in circuits pyrotechnic transmission logics, causing the fusion in micro fuses of electrical transmission, causing a micropropulsion or initiating the ignition of other materials.

L'utilisation de matériaux pyrotechniques d'épaisseur inférieure à 500 µm ou de masse inférieure à 15 mg dans des microsystèmes fonctionnant à la pression atmosphérique, se heurte à plusieurs difficultés.The use of pyrotechnic materials less than 500 µm thick or less than 15 mg in pressure-operated microsystems atmospheric, faces several difficulties.

D'une part la puissance d'initiation qu'ils reçoivent dans ces microsystèmes est très faible et appliquée pendant un temps court.On the one hand, the initiation power they receive in these microsystems is very small and applied for a short time.

D'autre part, une partie de l'énergie qui se forme au fur et à mesure de la combustion du matériau ne reste pas au sein de celui-ci en raison de sa faible épaisseur ou de sa faible masse, mais se dissipe dans le milieu ambiant. La combustion ne peut donc pas s'auto-entretenir. Le matériau pyrotechnique ne brûle pas complètement et le volume de gaz ou la chaleur souhaités ne peuvent pas être obtenus.On the other hand, part of the energy that forms as the material burns, nothing remains not within it due to its thinness or its low mass, but dissipates in the middle ambient. Combustion cannot therefore be self-sustaining. Pyrotechnic material does not burn completely and the desired volume of gas or heat cannot be obtained.

Lorsque les matériaux pyrotechniques sont utilisés dans des microsystèmes destinés au domaine médical, les résidus de la combustion doivent être inexistants ou en quantité la plus faible possible, et ne pas être nocifs. De même, les gaz qui se dégagent doivent eux aussi être compatibles avec cette application.When pyrotechnic materials are used in microsystems intended for the medical field, the combustion residues must be non-existent or as small as possible, and not be harmful. Likewise, the gases released must also be compatible with this application.

Les compositions énergétiques doivent permettre d'obtenir des matériaux d'épaisseur très fine, tels que par exemple sous la forme de feuilles, films, rubans ou couches ou de masse très faible, par exemple sous forme de perles et la constitution des matériaux obtenus doit être homogène.The energetic compositions must allow to obtain materials of very fine thickness, such as for example in the form of sheets, films, ribbons or layers or very low mass, for example in the form of pearls and the constitution of the materials obtained must be homogeneous.

Il était donc important de trouver de nouveaux matériaux pyrotechniques ne présentant pas les désavantages précités et qui répondent aux exigences requises pour leur utilisation dans des microsystèmes fonctionnant à la pression atmosphérique ou à une pression voisine de celle-ci, et les nouvelles compositions pour les obtenir.It was therefore important to find new pyrotechnic materials not having the disadvantages mentioned above and which meet the requirements required for their use in microsystems operating at atmospheric pressure or at a pressure close to it, and the news compositions to obtain them.

Un objet de la présente invention concerne donc les matériaux pyrotechniques non détonables, auto-combustibles à la pression atmosphérique ou à une pression voisine de celle-ci, comprenant un liant énergétique et du perchlorate d'ammonium, caractérisés en ce qu'ils ont une épaisseur inférieure à 500 µm ou une masse inférieure à 15 mg, qu'ils sont auto-combustibles après initiation ponctuelle par une puissance électrique P, telle que 150 mW ≤ P ≤ 800 mW, pendant un temps t, tel que 20 ms ≤ t ≤ 600 ms, et qu'ils comprennent :

  • de 25% à 80% en poids d'un liant énergétique à base de polyazoture de glycidyle (PAG), ou de poly-3,3-bis(azidométhyl)oxétane (BAMO), ou de polyester et d'au moins un plastifiant énergétique, ou de polyéther et d'au moins un plastifiant énergétique,
  • de 10% à 70% en poids de perchlorate d'ammonium dont la dimension des grains est comprise entre 0,5 et 30 µm, et
  • de 0% à 45% en poids d'au moins une nitramine.
An object of the present invention therefore relates to non-detonable pyrotechnic materials which are self-combustible at atmospheric pressure or at a pressure close to it, comprising an energy binder and ammonium perchlorate, characterized in that they have a thickness less than 500 µm or a mass less than 15 mg, they are self-combustible after specific initiation by an electrical power P, such as 150 mW ≤ P ≤ 800 mW, for a time t, such as 20 ms ≤ t ≤ 600 ms, and that they include:
  • from 25% to 80% by weight of an energy binder based on poly (glycidyl azide), or poly-3,3-bis (azidomethyl) oxetane (BAMO), or polyester and at least one plasticizer energy, or polyether and at least one energy plasticizer,
  • from 10% to 70% by weight of ammonium perchlorate whose grain size is between 0.5 and 30 μm, and
  • from 0% to 45% by weight of at least one nitramine.

Ces matériaux en raison de leur faible épaisseur ou de leur faible masse, de leur faculté d'être initiés par une très faible puissance et de s'auto-consummer en dégageant très rapidement une grande quantité de gaz et de chaleur, sont très utiles pour agir dans des microsystèmes fonctionnant à la pression atmosphérique ou à une pression voisine de celle-ci.These materials due to their thinness or their low mass, their ability to be initiated by a very low power and to consume itself in rapidly releasing a large amount of gas and are very useful for acting in microsystems operating at atmospheric pressure or at a pressure close to it.

Ils peuvent se présenter sous une forme quelconque mais cette forme doit avoir selon une des réalisations, une épaisseur inférieure à 500 µm, de préférence inférieure ou égale à 300 µm. Ils peuvent par exemple être sous forme de films, de feuilles, de rubans ou de couches. L'épaisseur de ces films, feuilles, rubans, ou couches est généralement égale ou supérieure à 50 µm, de préférence égale ou supérieure à 100 µm.They can be in any form but this form must have according to one of the achievements, thickness less than 500 µm, preferably less than or equal to 300 µm. They can for example be in the form of films, sheets, ribbons or layers. The thickness of these films, sheets, ribbons, or layers is generally equal to or greater than 50 µm, preferably equal to or greater than 100 µm.

Selon une autre réalisation, cette forme a une masse généralement inférieure à 15 mg, de préférence inférieure ou égale à 3 mg. Les matériaux peuvent être par exemple sous forme de perles. Généralement, la masse de ces matériaux est égale ou supérieure à 0,1 mg, de préférence égale ou supérieure à 0,2 mg.According to another embodiment, this form has a mass generally less than 15 mg, preferably less than or equal to 3 mg. Materials can be for example in the form of pearls. Generally, the mass of these materials is 0.1 mg or more, preferably 0.2 mg or more.

Les composés qui forment les liants contenus dans les matériaux de la présente invention sont les composés connus habituellement utilisés dans le domaine pyrotechnique. Ils se trouvent dans le commerce ou ils se préparent selon des procédés connus. The compounds that form the binders contained in the materials of the present invention are the compounds known usually used in the field pyrotechnic. They are in the trade or they are prepared according to known methods.

En plus des composants principaux précédemment mentionnés qui forment le liant, on inclut également dans celui-ci, les additifs habituels tels que notamment les catalyseurs de polymérisation et les réticulants.In addition to the main components previously mentioned which form the binder, we also include in it, the usual additives such as in particular polymerization catalysts and crosslinkers.

Selon une variante de l'invention, les matériaux comprennent de 30% à 80%, de préférence de 40% à 60%, en poids du liant énergétique à base de PAG ou de BAMO et de 20% à 70%, de préférence de 40% à 60% en poids de perchlorate d'ammonium.According to a variant of the invention, the materials comprise from 30% to 80%, preferably from 40% to 60%, in weight of the energy binder based on PAG or BAMO and from 20% to 70%, preferably from 40% to 60% by weight of ammonium perchlorate.

Le liant préféré, selon cette variante, est à base de polyazoture de glycidyle.The preferred binder, according to this variant, is based of glycidyl polyazide.

Selon une autre variante de l'invention les matériaux comprennent :

  • de 25% à 70% en poids du liant énergétique à base de polyester ou de polyéther et d'au moins un plastifiant énergétique
  • de 10% à 35% en poids de perchlorate d'ammonium, et
  • de 0% à 45% en poids d'au moins une nitramine.
According to another variant of the invention, the materials include:
  • from 25% to 70% by weight of the energy binder based on polyester or polyether and at least one energy plasticizer
  • from 10% to 35% by weight of ammonium perchlorate, and
  • from 0% to 45% by weight of at least one nitramine.

Comme exemples de polyesters et de polyéthers, on peut citer les polyadipates d'alkylèneglycol ou de polyalkylèneglycol et les polyalkylèneglycols.As examples of polyesters and polyethers, we may mention the polyadipates of alkylene glycol or of polyalkylene glycol and polyalkylene glycols.

Comme exemples de plastifiants énergétiques, on peut citer la nitroglycérine (Ngl), le trinitrate de butanetriol (BTTN), le trinitrate de triméthyloléthane (TMETN) et le dinitrate de triéthylèneglycol (TRENO). De préférence on utilise un mélange de plusieurs plastifiants.As examples of energetic plasticizers, we may include nitroglycerin (Ngl), trinitrate butanetriol (BTTN), trimethylolethane trinitrate (TMETN) and triethylene glycol dinitrate (TRENO). Of preferably we use a mixture of several plasticizers.

Les liants à base de polyesters ou polyéthers et d'au moins un plastifiant énergétique représentent de préférence de 35% à 50% en poids des compositions.Binders based on polyesters or polyethers and at least one energy plasticizer represent preferably from 35% to 50% by weight of the compositions.

Un liant à base de polyester qui convient bien comprend un polyadipate de diéthylèneglycol réticulé par un polyisocyanate tel que le tri(isocyanato-6-hexyl)bi-uret (BTHI).A polyester-based binder that works well includes a diethylene glycol polyadipate crosslinked by a polyisocyanate such as tri (isocyanato-6-hexyl) bi-uret (BTHI).

Le plastifiant énergétique est de préférence un mélange de TMETN et de BTTN.The energy plasticizer is preferably a mixture of TMETN and BTTN.

La quantité de perchlorate d'ammonium est dans ces matériaux de préférence de 20% à 32% en poids.The amount of ammonium perchlorate is in these materials preferably from 20% to 32% by weight.

On peut également ajouter dans ces matériaux une autre charge énergétique qui est choisie parmi les composés appartenant à la classe des nitramines tel que par exemple l'octogène ou l'hexogène. Un mélange de plusieurs nitramines peut être utilisé.One can also add in these materials a other energy charge which is chosen from among compounds belonging to the class of nitramines such as for example octogen or hexogen. A mix of more nitramines can be used.

La ou les nitramines représentent de préférence de 20% à 35% en poids de ces matériaux.The nitramine (s) preferably represent 20% to 35% by weight of these materials.

La dimension des grains de perchlorate dispersée dans les liants selon l'invention est importante afin d'obtenir les matériaux pyrotechniques qui possèdent les propriétés souhaitées. Cette dimension est de préférence choisie dans la gamme de 1 à 10 µm.The size of the dispersed perchlorate grains in the binders according to the invention is important so to obtain the pyrotechnic materials which have the desired properties. This dimension is preferably chosen in the range from 1 to 10 µm.

La puissance P de l'initiation ponctuelle que les matériaux peuvent recevoir est très faible. Elle est telle que 150 mW ≤ P ≤ 800 mW. De préférence P est ≥ à 300 mW. Elle doit être appliquée pendant un temps t, tel que 20 ms ≤ t ≤ 600 ms, de préférence t ≤ 125 ms. Cette condition ne signifie pas que chaque puissance P peut être appliquée pendant n'importe quel temps t compris dans cette fourchette pour initier le matériau, mais qu'il existe au moins un temps t compris dans cette fourchette permettant son initiation.The power P of the point initiation that the materials can receive is very low. She is such that 150 mW ≤ P ≤ 800 mW. Preferably P is ≥ to 300 mW. It must be applied for a time t, such than 20 ms ≤ t ≤ 600 ms, preferably t ≤ 125 ms. This condition does not mean that every power P can be applied for any time including t in this range to initiate the material but that there exists at least one time t included in this fork allowing its initiation.

Par initiation ponctuelle, on entend une initiation réalisée sur une très faible surface du matériau, de l'ordre de 0,2 mm2, par exemple sur une surface de 0,1 mm x 2 mm.By point initiation means an initiation carried out on a very small surface of the material, of the order of 0.2 mm 2 , for example on an area of 0.1 mm x 2 mm.

La puissance nécessaire pour activer le matériau peut être apportée par divers moyens connus tels que par exemple par une minirésistance électrique ou par un faisceau laser. The power needed to activate the material can be provided by various known means such as by example by a mini electrical resistance or by a laser beam.

L'inflammation ponctuelle du matériau pyrotechnique étant réalisée, la combustion se propage au travers du matériau très rapidement sans qu'aucun autre apport d'énergie soit nécessaire. Il se produit alors un grand dégagement de gaz et de chaleur.Point ignition of pyrotechnic material being carried out, the combustion propagates to the through material very quickly without any other energy supply is required. Then there is a great release of gas and heat.

Les principaux gaz qui se forment sont de l'hydrogène, de l'azote, de la vapeur d'eau, du gaz carbonique et/ou de l'oxyde de carbone.The main gases that are formed are hydrogen, nitrogen, water vapor, gas carbon dioxide and / or carbon monoxide.

Un autre objet de la présente invention concerne les compositions pour obtenir les matériaux tels que décrits précédemment. Elles comprennent les liants énergétiques, le perchlorate d'ammonium et éventuellement la ou les nitramines et les quantités de ces composants tels que mentionnés précédemment.Another object of the present invention relates to the compositions for obtaining the materials such as described previously. They include binders energy, ammonium perchlorate and possibly the nitramine (s) and the quantities of these components as mentioned previously.

On peut également ajouter dans ces compositions les additifs habituels tels que plastifiants, stabilisants, pigments, solvants ou charges qui améliorent leurs mises en oeuvre ou les propriétés des matériaux.We can also add in these compositions the usual additives such as plasticizers, stabilizers, pigments, solvents or fillers which improve their implementation or the properties of materials.

Les différents composants sont mélangés selon des techniques connues, généralement par malaxage.The different components are mixed according to known techniques, generally by kneading.

On peut obtenir les matériaux à partir de ces compositions au moyen de différentes techniques connues, par exemple en plaçant les compositions entre deux plaques ou dans un moule et en les faisant durcir sous l'effet de la chaleur ou en évaporant le solvant, ou par découpage dans un bloc durci de dimensions plus importantes, obtenu préalablement, ou bien en utilisant la technique de dépôt par sérigraphie suivi du durcissement.The materials can be obtained from these compositions using different known techniques, for example by placing the compositions between two plates or in a mold and hardening them under the effect of heat or by evaporating the solvent, or by cutting in a hardened block of more dimensions important, obtained beforehand, or using the deposition technique by screen printing followed by curing.

Un autre objet de la présente invention concerne plusieurs utilisations des nouveaux matériaux pyrotechniques.Another object of the present invention relates to several uses of new materials fireworks.

Ces utilisations sont très variées. Compte tenu des caractéristiques de ces matériaux, ils conviennent pour faire partie de microsystèmes comme microgénérateurs de gaz, micropropulseurs ou microgénérateurs de chaleur. En particulier, ils sont utiles pour réaliser des systèmes de micropompes ou de microvannes. De tels microsystèmes se trouvent notamment dans des dispositifs pour administrer des médicaments par voie transdermique. Ils sont également utiles pour transférer des ordres dans des circuits logiques de transmission pyrotechnique, pour former des éléments de microfusibles de circuit de transmission électrique, pour servir d'initiateurs d'allumage ou pour former le chargement propulsif de micropropulseurs employés par exemple pour modifier le positionnement ou la trajectoire de satellites.These uses are very varied. Considering characteristics of these materials, they are suitable to be part of microsystems as microgenerators of gases, micropropellers or microgenerators heat. In particular, they are useful for realize micropump or microvalve systems. Such microsystems are found in particular in devices for administering drugs by route Transdermal. They are also useful for transferring orders in logical transmission circuits pyrotechnic, to form microfuse elements electrical transmission circuit, to serve ignition initiators or to form the charge propellant of micropropellants used for example for modify the positioning or trajectory of satellites.

Les exemples qui suivent illustrent l'invention sans toutefois la limiter :The following examples illustrate the invention without however limiting it:

Exemple 1Example 1

On a préparé une composition avec les composés suivants : % en poids PAG-diol de masse moléculaire 2000, 57 BTHI 9,5 Triacétine (plastifiant) 3,5 NH4ClO4 (dimension des grains 1 µm) 30 A composition was prepared with the following compounds: % in weight PAG-diol of molecular weight 2000, 57 BTHI 9.5 Triacetin (plasticizer) 3.5 NH 4 ClO 4 (grain size 1 µm) 30

Les composés ont été mélangés dans un malaxeur horizontal à 50°C pendant 3 heures.The compounds were mixed in a mixer horizontal at 50 ° C for 3 hours.

Avec cette composition, on a formé un film de dimensions 2 mm x 2 mm et d'épaisseur 0,1 mm par polymérisation entre deux plaques métalliques.With this composition, we formed a film of dimensions 2 mm x 2 mm and thickness 0.1 mm by polymerization between two metal plates.

On a ensuite initié le film avec une puissance de 400 mW appliquée sur une surface rectangulaire de 0,1 mm x 2 mm pendant 600 ms au moyen d'une minirésistance électrique. Il brûle alors très rapidement avec une flamme régulière.We then started the film with power 400 mW applied on a rectangular surface of 0.1 mm x 2 mm for 600 ms by means of a mini-resistance electric. It then burns very quickly with a regular flame.

Exemple 2Example 2

On a préparé une composition avec les composés suivants : % en poids PAG-diol de masse moléculaire 2000, 40,76 BTHI 6,74 Triacétine (plastifiant) 2,5 Dibutyl-dilaurate d'étain (catalyseur) 50 ppm NH4ClO4 (dimension des grains 3 µm) 50 A composition was prepared with the following compounds: % in weight PAG-diol of molecular weight 2000, 40.76 BTHI 6.74 Triacetin (plasticizer) 2.5 Tin dibutyl dilaurate (catalyst) 50 ppm NH 4 ClO 4 (grain size 3 µm) 50

Les composés ont été mélangés dans un malaxeur horizontal à 50°C pendant 3 heures.The compounds were mixed in a mixer horizontal at 50 ° C for 3 hours.

Avec cette composition, on a formé par polymérisation entre deux plaques métalliques un film de dimensions 2 mm x 2 mm et d'épaisseur 0,2 mm. On a initié le film avec une puissance de 800 mW appliquée sur une surface rectangulaire de 0,1 mm x 2 mm pendant un temps de 20 ms au moyen d'une minirésistance électrique. La température d'initiation est alors de 300°C. Le film brûle très rapidement à une vitesse de 2,3 mm/s.With this composition, we formed by polymerization between two metal plates a film of dimensions 2 mm x 2 mm and thickness 0.2 mm. We have initiated the film with a power of 800 mW applied on a rectangular surface of 0.1 mm x 2 mm for a time of 20 ms by means of a mini-resistance electric. The initiation temperature is then 300 ° C. The film burns very quickly at a speed of 2.3 mm / s.

La quantité de chaleur produite par la combustion est de 3654 kJ/g.The amount of heat produced by combustion is 3654 kJ / g.

Les gaz qui se dégagent sont principalement de l'hydrogène, de l'azote et de l'oxyde de carbone.The gases released are mainly of hydrogen, nitrogen and carbon monoxide.

Exemple 3Example 3

On a préparé une composition avec les composés suivants : % en poids Polyadipate de diéthylène glycol 8,33 de masse moléculaire 3800 Agent pontant 0,25 Nitro méthyl aniline (NMA) 0,05 Dinitro phényl amine (2-NDPA) 0,78 TMETN 19,15 BTTN 4,78 BTHI 1,66 NH4ClO4 32 Octogène 33 A composition was prepared with the following compounds: % in weight Diethylene glycol polyadipate 8.33 with a molecular mass of 3800 Bridging agent 0.25 Nitro methyl aniline (NMA) 0.05 Dinitro phenyl amine (2-NDPA) 0.78 TMETN 19,15 BTTN 4.78 BTHI 1.66 NH 4 ClO 4 32 HMX 33

Les composés ont été mélangés dans un malaxeur horizontal à 50°C pendant 3 heures.The compounds were mixed in a mixer horizontal at 50 ° C for 3 hours.

Le rendement gazeux théorique du matériau est de 0,6 l/g.The theoretical gas yield of the material is 0.6 l / g.

Les principaux gaz dégagés sont de l'oxyde de carbone, du gaz carbonique, de l'hydrogène, de l'azote et de la vapeur d'eau.The main gases released are carbon, carbon dioxide, hydrogen, nitrogen and water vapor.

Claims (12)

  1. Non-detonatable pyrotechnic substance, that is auto-combustible at atmospheric pressure or at a pressure close thereto, comprising an energetic binder and ammonium perchlorate, characterized in that it has a thickness less than 500 µm or a mass less than 15 mg, that it is auto-combustible after localised initiation by electric power P, such that 150 mW ≤ P ≤ 800 mW, for a time t, such that 20 ms ≤ t s 600 ms, and that it comprises:
    from 25% to 80% by weight of an energetic binder based on glycidyl polyazide (GPA) or poly-3,3-bis(azidomethyl)oxetane (BAMO), or polyester and at least one energetic plasticizer, or polyether and at least one energetic plasticizer,
    from 10% to 70% by weight of ammonium perchlorate of which the particle size lies between 0.5 and 30 µm, and
    from 0% to 45% by weight of at least one nitramine.
  2. Substance according to claim 1, characterized in that it has a thickness less than or equal to 300 µm or a mass less than or equal to 3 mg.
  3. Substance according to claim 1 or 2, characterized in that it comprises:
    from 30% to 80% by weight of the energetic binder based on GPA or BAMO, and
    from 20% to 70% by weight of ammonium perchlorate.
  4. Substance according to claim 1 or 2, characterized in that it comprises:
    from 25% to 70% by weight of the energetic binder based on polyester or polyether and at least one energetic plasticizer,
    from 10% to 35% by weight of ammonium perchlorate, and
    from 0% to 45% by weight of at least one nitramine.
  5. Substance according to claim 1, 2 or 3, characterized in that it comprises:
    from 40% to 60% by weight of the energetic binder based on GPA or BAMO, and
    from 40% to 60% by weight of ammonium perchlorate.
  6. Substance according to any one of claims 1 to 3 and 5, characterized in that the energetic binder is based on GPA.
  7. Substance according to claim 4, characterized in that it comprises:
    from 35% to 50% by weight of binder based on polyester or polyether and at least one energetic plasticizer,
    from 20% to 32% by weight of ammonium perchlorate, and
    from 20% to 35% by weight of at least one nitramine.
  8. Substance according to claim 1, 2, 4 or 7 characterized in that the polyester is chosen from the polyadipates of alkyleneglycol or polyalkyleneglycol, the polyether is chosen from polyalkyleneglycols, the energetic plasticizer is chosen from the group consisting of nitroglycerine, butanetriol trinitrate, trimethylolethane trinitrate, triethyleneglycol trinitrate and mixtures of these compounds, the nitramine is octogen or hexogen or a mixture of these compounds.
  9. Substance according to any one of the preceding claims, characterized in that the particle size of the ammonium perchlorate is chosen from the range 1 to 10 µm.
  10. Substance according to any one of the preceding claims, characterized in that it is in the form of beads.
  11. Non-hardened energetic composition for producing a substance according to one of claims 1 to 10, characterized in that it comprises the compounds and proportions thereof as stated in claim 5 or 7.
  12. Use of the substance according to any one of claims 1 to 10 as a gas micro-generator, micropropellant or heat microgenerator.
EP99400281A 1998-02-10 1999-02-08 Non-detonatable pyrotechnic materials for microsystems Expired - Lifetime EP0936205B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR9801538 1998-02-10
FR9801538A FR2774684B1 (en) 1998-02-10 1998-02-10 NEW NON-DETONATED PYROTECHNIC MATERIALS FOR MICROSYSTEMS
NO19991464A NO311210B1 (en) 1998-02-10 1999-03-25 Non-detonable pyrotechnic material, use of the material, and mixture for the preparation of the material
CA002267512A CA2267512C (en) 1998-02-10 1999-03-26 New non-detonatable pyrotechnical materials for microsystems

Publications (2)

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EP0936205A1 EP0936205A1 (en) 1999-08-18
EP0936205B1 true EP0936205B1 (en) 2002-10-02

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EP99400281A Expired - Lifetime EP0936205B1 (en) 1998-02-10 1999-02-08 Non-detonatable pyrotechnic materials for microsystems

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US (1) US6080248A (en)
EP (1) EP0936205B1 (en)
CA (1) CA2267512C (en)
DE (1) DE69903205T2 (en)
FR (1) FR2774684B1 (en)
NO (1) NO311210B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7923662B2 (en) 2004-05-20 2011-04-12 Alexza Pharmaceuticals, Inc. Stable initiator compositions and igniters
US8387612B2 (en) 2003-05-21 2013-03-05 Alexza Pharmaceuticals, Inc. Self-contained heating unit and drug-supply unit employing same

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Publication number Priority date Publication date Assignee Title
DE19616627A1 (en) * 1996-04-26 1997-11-06 Dynamit Nobel Ag Kindling mixtures
FR2807946B1 (en) * 2000-04-19 2002-06-07 Poudres & Explosifs Ste Nale NEEDLELESS SYRINGE OPERATING WITH A TWO-COMPOSITION PYROTECHNIC LOAD
DE10118005B4 (en) * 2001-04-10 2005-11-10 Schwesinger, Norbert, Prof.Dr.-Ing. Micro engine
FR2827377B1 (en) 2001-07-13 2003-12-05 Poudres & Explosifs Ste Nale IGNITION DEVICE FOR PYROTECHNIC MICROCHARGES
FR2836907B1 (en) * 2002-03-11 2005-03-18 Commissariat Energie Atomique MICROVANNE WITH PYROTECHNIC ACTUATION

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GB1283691A (en) * 1961-09-11 1972-08-02 Thiokol Chemical Corp Solid propellant and method of making the same
US3791892A (en) * 1966-01-24 1974-02-12 Us Navy Castable polyurethane composite propellants
US3745076A (en) * 1966-02-02 1973-07-10 Us Navy Propellant composition with a nitro containing cross-linked binder
DE3523953A1 (en) * 1985-07-04 1987-01-15 Fraunhofer Ges Forschung METHOD AND DEVICE FOR PRODUCING SOLID FUELS
US5059175A (en) * 1990-10-09 1991-10-22 University Of Utah Research Foundation Implantable drug delivery system with piston actuation
US5616884A (en) * 1991-04-02 1997-04-01 Thiokol Corporation Propellant gas-generation system for canister ejection
AU7952994A (en) * 1993-10-06 1995-05-01 Thiokol Corporation Bamo/ammo propellant formulations
GB2296248A (en) * 1994-12-22 1996-06-26 Secr Defence Inert and energetic prepolymers co-cured with isocyanate
CZ294564B6 (en) * 1996-11-21 2005-02-16 Laboratoires D'hygiene Et De Dietetique Miniature valve, accessories for filling a feed tank provided with such a valve, apparatus provided with the accessories and intended for transdermal application of a medicament and method of making such a miniature valve

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8387612B2 (en) 2003-05-21 2013-03-05 Alexza Pharmaceuticals, Inc. Self-contained heating unit and drug-supply unit employing same
US8991387B2 (en) 2003-05-21 2015-03-31 Alexza Pharmaceuticals, Inc. Self-contained heating unit and drug-supply unit employing same
US9370629B2 (en) 2003-05-21 2016-06-21 Alexza Pharmaceuticals, Inc. Self-contained heating unit and drug-supply unit employing same
US7923662B2 (en) 2004-05-20 2011-04-12 Alexza Pharmaceuticals, Inc. Stable initiator compositions and igniters

Also Published As

Publication number Publication date
FR2774684B1 (en) 2000-03-03
EP0936205A1 (en) 1999-08-18
FR2774684A1 (en) 1999-08-13
DE69903205D1 (en) 2002-11-07
NO311210B1 (en) 2001-10-29
NO991464D0 (en) 1999-03-25
DE69903205T2 (en) 2003-06-26
CA2267512A1 (en) 2000-09-26
US6080248A (en) 2000-06-27
NO991464L (en) 2000-09-26
CA2267512C (en) 2009-06-16

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