EP1087919B1 - Gas-generating solid pyrotechnic loads based on compositions containing water - Google Patents

Gas-generating solid pyrotechnic loads based on compositions containing water Download PDF

Info

Publication number
EP1087919B1
EP1087919B1 EP99920902A EP99920902A EP1087919B1 EP 1087919 B1 EP1087919 B1 EP 1087919B1 EP 99920902 A EP99920902 A EP 99920902A EP 99920902 A EP99920902 A EP 99920902A EP 1087919 B1 EP1087919 B1 EP 1087919B1
Authority
EP
European Patent Office
Prior art keywords
composition according
composition
binder
water
nitrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99920902A
Other languages
German (de)
French (fr)
Other versions
EP1087919A1 (en
Inventor
Christian Perut
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Societe Nationale des Poudres et Explosifs
Original Assignee
Societe Nationale des Poudres et Explosifs
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Societe Nationale des Poudres et Explosifs filed Critical Societe Nationale des Poudres et Explosifs
Publication of EP1087919A1 publication Critical patent/EP1087919A1/en
Application granted granted Critical
Publication of EP1087919B1 publication Critical patent/EP1087919B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • 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

Definitions

  • the present invention relates to the field of pyrotechnic compositions generating cold gases, non-toxic and free of solid residues. More precisely the invention relates to the field of solid composite pyrotechnic compositions at amorphous structure comprising one or more oxidants and an organic binder in the gel state.
  • the essays according to the invention are well suited to constitute loads intended to inflate cushions protection or to ensure the functioning of a pyrotechnic fire extinguisher.
  • cold, non-toxic, residue-free gases solid.
  • the term "cold" gases means gases which are products at a temperature below about 1800 ° C.
  • liquid propellants consisting of aqueous solutions of compounds such as hydroxylammonium nitrate, triethanolammonium nitrate, aminotetrazole nitrate, nitrate aminotriazole, urea nitrate, biuret nitrate, etc.
  • liquid propellants are for example described in US Patents 5,060,973 and US 5,684,269.
  • these liquid propellants require suitable gas generators, the structure of which is complex and which are of a high cost price.
  • compositions constituted by a binder such as polyvinyl alcohol and by solid eutectics to based on ammonium nitrate and guanidine nitrates or aminoguanidine in the presence of nitrate or potassium perchlorate.
  • binder such as polyvinyl alcohol
  • solid eutectics to based on ammonium nitrate and guanidine nitrates or aminoguanidine in the presence of nitrate or potassium perchlorate.
  • the object of the present invention is precisely to meet this need.
  • Polyvinyl alcohol is the preferred binder because it improves the chemical stability of the compositions according to the invention.
  • the solid compositions according to the invention thus present an amorphous structure in which the binder is in the form of a solid impregnated gel by the aqueous hydroxylammonium phase.
  • the binder is in the form of a solid impregnated gel by the aqueous hydroxylammonium phase.
  • the water content by weight of the compositions according to the invention will be between 5 and 20%.
  • the invention thus makes it possible to have compositions which contain water contents much higher than the contents in humidity of previously known compositions.
  • the weight of the nitrate of hydroxylammonium represents at least 50% of the total weight of the composition, the content of the latter in hydroxylammonium nitrate preferably being between 60% and 70%.
  • One of the advantages of the present invention resides in the fact that at the indicated contents the mixtures water / hydroxylammonium nitrate remain liquid from the as long as the temperature does not drop below zero degrees Celsius.
  • the compositions according to the invention also contain secondary oxidants which are advantageously chosen in the group consisting of ammonium nitrate, hexogen (RDX) and octogen (HMX). These oxidants allow to increase the number of gaseous molecules produced by the combustion of a given volume of composition without the temperature of combustion gas does not increase too much thanks to the water contained in the composition.
  • secondary oxidants which are advantageously chosen in the group consisting of ammonium nitrate, hexogen (RDX) and octogen (HMX).
  • compositions when the compositions are intended to constitute loads pyrotechnics for gas generators in front inflate protective cushions for occupants of a motor vehicle, avoid the use of nitrate ammonium or in any case limit the content by weight of the ammonium nitrate composition to a few percent.
  • compositions will most often contain stabilizing additives who will be chosen from bipyridine, ammonium hydrogen phosphate and ammonium acetate.
  • the weight content of these stabilizers in the composition will be close to 2%.
  • Bipyridine and ammonium hydrogen phosphate are stabilizers preferred.
  • compositions will contain thickening additives which will be chosen from the group consisting of water-soluble isocyanates, melamine-formaldehyde resins and borax which is a sodium tetraborate of formula: Na 2 B 4 O 7 , 10H 2 O.
  • the kneading and extrusion apparatus is a twin-screw extruder.
  • the binder with gelling effect is polyvinyl alcohol and the twin-screw extruder is heated to a temperature between 50 ° C. and 60 ° C., the temperature inside the oven being close to 80 ° C.
  • all the constituents other than the binder and which are soluble in water will be mixed with the liquid phase containing the water and the hydroxylammonium nitrate before introduction of the latter into the twin-screw extruder.
  • the pyrotechnic charges thus obtained can in particular be used either in pyrotechnic extinguishers to constitute the source of engine gas in these fire extinguishers, either in pyrotechnic gas generators intended to inflate protective cushions for vehicle occupants automobile.
  • the installation shown in FIG. 1 basically comprises a twin-screw extruder 1 extended by an extrusion head 2, a conveyor belt 3 passing inside an oven 4 and a cutting system 5.
  • the first device consists of a pipe 6 connected via a tap 7 to a tank 8 provided with an agitator 9.
  • a second device feed consisting of a hopper 10 and a belt carrier 11.
  • the tank 8 contains a liquid mixture A consisting with water, hydroxylammonium nitrate and, if applicable constituents other than the binder and soluble in water such as ammonium nitrate.
  • the reactive constituents with respect to water are not incorporated into this aqueous liquid phase.
  • the conveyor belt 11 feeds the hopper 10 with a mixture of granules B comprising granules of binder and, if necessary, granules of additives not soluble in water and in particular oxidizing granules not soluble in water such as hexogen or octogen.
  • Extruder 1 is temperature controlled to have an internal temperature between 50 ° C and 60 ° C when the binder is polyvinyl alcohol.
  • the liquid phase A and the granules B are mixed in the extruder 1 to form, by gelation of the binder, a composite paste with an amorphous structure which is extruded through the extrusion head 2 in the form of a profiled rod 12.
  • This rod may be a simple cylindrical strand, possibly provided with internal channels, to give, after cutting, loose grains or be a rod of larger dimensions, with, if necessary, a worked external profile, to give after cutting. solid or annular blocks.
  • This rod 12 is led through the conveyor belt 3 through a heated oven to cause hardening of the gelled binder.
  • the binder is polyvinyl alcohol
  • the temperature of the oven will be close to 80 ° C. and the residence time of the rod in the oven will be a few minutes.
  • Example 1 Example 2 water 8 15% polyvinyl alcohol 20% 15% hydroxylammonium nitrate 68.5% 66.5% ammonium nitrate 3.5% 3.5%

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Business, Economics & Management (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Emergency Management (AREA)
  • Inorganic Chemistry (AREA)
  • Air Bags (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatment Of Sludge (AREA)
  • Glanulating (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

The invention concerns the field of gas-generating solid pyrotechnic compositions consisting of a binding agent with gelling effect, such as polyvinyl alcohol, impregnated with a water and hydroxylammonium nitrate solution in the presence, optionally, of oxidants such as ammonium nitrate or nitramines, stabilising and thickening agents. The invention also concerns the continuous manufacture of pyrotechnic loads (13) by forming said compositions in an extruder (1). The resulting loads are useful in pyrotechnic extinguishers and in gas generators designed for safety in motor vehicles.

Description

La présente invention se rapporte au domaine des compositions pyrotechniques génératrices de gaz froids, non toxiques et exempts de résidus solides. Plus précisément l'invention concerne le domaine des compositions pyrotechniques composites solides à structure amorphe comprenant un ou plusieurs oxydants et un liant organique à l'état de gel. Les compositions selon l'invention conviennent bien pour constituer des chargements destinés à gonfler des coussins de protection ou à assurer le fonctionnement d'un extincteur pyrotechnique.The present invention relates to the field of pyrotechnic compositions generating cold gases, non-toxic and free of solid residues. More precisely the invention relates to the field of solid composite pyrotechnic compositions at amorphous structure comprising one or more oxidants and an organic binder in the gel state. The essays according to the invention are well suited to constitute loads intended to inflate cushions protection or to ensure the functioning of a pyrotechnic fire extinguisher.

Pour de nombreuses applications comme la sécurité automobile ou la lutte contre les incendies sont recherchées des compositions pyrotechniques génératrices de gaz froids, non toxiques et exempts de résidus solides. On entend par gaz "froids" des gaz qui sont produits à une température inférieure à environ 1800°C.For many applications such as security automobile or fire fighting are sought after pyrotechnic compositions cold, non-toxic, residue-free gases solid. The term "cold" gases means gases which are products at a temperature below about 1800 ° C.

Par ailleurs l'homme de métier souhaite, dans ces domaines d'applications, pouvoir disposer de compositions pouvant être fabriquées et mises en forme par des procédés continus.
   Pour obtenir des gaz froids et exempts de résidus solides, l'homme de métier a recherché à développer des propergols liquides constitués par des solutions aqueuses de composés comme le nitrate d'hydroxylammonium, le nitrate de triéthanolammonium, le nitrate d'aminotétrazole, le nitrate d'aminotriazole, le nitrate d'urée, le nitrate de biuret, etc... Furthermore, those skilled in the art wish, in these fields of application, to be able to have available compositions which can be manufactured and shaped by continuous processes.
To obtain cold gases and free of solid residues, the skilled person sought to develop liquid propellants consisting of aqueous solutions of compounds such as hydroxylammonium nitrate, triethanolammonium nitrate, aminotetrazole nitrate, nitrate aminotriazole, urea nitrate, biuret nitrate, etc.

De tels propergols liquides sont par exemple décrits dans les brevets US 5,060,973 et US 5,684,269. Néanmoins ces propergols liquides nécessitent des générateurs de gaz adaptés, dont la structure est complexe et qui sont d'un prix de revient élevé.Such liquid propellants are for example described in US Patents 5,060,973 and US 5,684,269. However, these liquid propellants require suitable gas generators, the structure of which is complex and which are of a high cost price.

Dans le domaine des chargements solides l'homme de métier a cherché à développer dans ce but des compositions composites constituées par un liant comme l'alcool polyvinylique et par des eutectiques solides à base de nitrate d'ammonium et de nitrates de guanidine ou d'aminoguanidine en présence de nitrate ou de perchlorate de potassium. Ces compositions qui sont par exemples décrites dans la demande PCT WO 97/46502 présentent cependant le double inconvénient de ne pas se prêter à une mise en oeuvre en continu puisqu'elles sont mises en forme par compression et, par ailleurs, de fournir des gaz encore relativement chauds.In the field of solid loads the man of profession sought to develop for this purpose composite compositions constituted by a binder such as polyvinyl alcohol and by solid eutectics to based on ammonium nitrate and guanidine nitrates or aminoguanidine in the presence of nitrate or potassium perchlorate. These compositions which are by examples described in PCT application WO 97/46502 have the double disadvantage of not being lend to continuous implementation since they are shaped by compression and, moreover, provide still relatively hot gases.

Enfin dans le domaine de la propulsion solide il a été proposé, par exemple par le brevet US 5,386,777, des chargements solides constitués par un enroulement de feuilles d'alcool polyvinylique imprégnées par un eutectique liquide à base des nitrates précédemment cités, les dits chargements contenant en plus de l'aluminium comme réducteur. Comme la technique précédemment mentionnée, cette solution fournit des gaz trop chauds et ne se prête pas à une mise en oeuvre en continu.Finally in the field of solid propulsion it has been proposed, for example by patent US 5,386,777, solid loads constituted by a winding of polyvinyl alcohol sheets impregnated with a liquid eutectic based on nitrates previously mentioned, the said loads containing in more aluminum as a reducing agent. Like technique previously mentioned, this solution provides gases too hot and not suitable for use in continued.

Il existe donc un besoin non satisfait de compositions pyrotechniques solides qui fournissent par combustion des gaz "froids", non toxiques et exempts de résidus solides et qui puissent être fabriquées et mises en forme en continu. There is therefore an unmet need for solid pyrotechnic compositions which provide by combustion of "cold" gases, non-toxic and free of solid residue that can be manufactured and disposed of continuously shaped.

L'objet de la présente invention est précisément de répondre à ce besoin.The object of the present invention is precisely to meet this need.

L'invention concerne donc des compositions pyrotechniques solides produisant par combustion des gaz exempts de résidus solides et constituées par au moins un liant organique à effet gélifiant et par au moins un système oxydant principal en phase liquide absorbée par le dit liant, les dites compositions étant caractérisées en ce que :

  • i) le dit liant organique à effet gélifiant est choisi dans le groupe constitué par l'alcool polyvinylique, l'hydroxyéthylcellulose, et la gomme xanthame.
  • ii) le dit système oxydant principal en phase liquide est constitué par un mélange d'eau et de nitrate d'hydroxylammonium (HAN), la teneur pondérale en eau de ladite composition étant comprise entre 5 et 20 %.
    • The invention therefore relates to solid pyrotechnic compositions producing by combustion gases free of solid residues and constituted by at least one organic binder with gelling effect and by at least one main oxidizing system in liquid phase absorbed by said binder, said compositions being characterized in that:
  • i) the said organic binder with gelling effect is chosen from the group consisting of polyvinyl alcohol, hydroxyethylcellulose, and xantham gum.
  • ii) said main oxidizing system in the liquid phase consists of a mixture of water and hydroxylammonium nitrate (HAN), the water content by weight of said composition being between 5 and 20%.

    • L'alcool polyvinylique est le liant préféré car il améliore la stabilité chimique des compositions selon l'invention.Polyvinyl alcohol is the preferred binder because it improves the chemical stability of the compositions according to the invention.

    Les compositions solides selon l'invention présentent ainsi une structure amorphe dans laquelle le liant se présente sous forme d'un gel solide imprégné par la phase aqueuse d'hydroxylammonium. Par combustion ces compositions libèrent l'eau incluse dans le gel sous forme de vapeur d'eau qui contribue à abaisser très sensiblement la température des gaz de combustion. The solid compositions according to the invention thus present an amorphous structure in which the binder is in the form of a solid impregnated gel by the aqueous hydroxylammonium phase. By combustion these compositions release the water included in the gel under form of water vapor which helps to lower very appreciably the temperature of the combustion gases.

    La teneur pondérale en eau des compositions selon l'invention sera comprise entre 5 et 20%. L'invention permet ainsi de disposer de compositions qui contiennent des teneurs en eau très supérieures aux teneurs en humidité des compositions antérieurement connues.The water content by weight of the compositions according to the invention will be between 5 and 20%. The invention thus makes it possible to have compositions which contain water contents much higher than the contents in humidity of previously known compositions.

    Avantageusement le poids du nitrate d'hyroxylammonium représente au moins 50% du poids total de la composition, la teneur de cette dernière en nitrate d'hydroxylammonium étant préférentiellement comprise entre 60% et 70%.Advantageously the weight of the nitrate of hydroxylammonium represents at least 50% of the total weight of the composition, the content of the latter in hydroxylammonium nitrate preferably being between 60% and 70%.

    Un des avantages de la présente invention réside dans le fait qu'aux teneurs indiquées les mélanges eau/nitrate d'hydroxylammonium demeurent liquides du moment que la température de ces derniers ne descend pas en dessous de zéro degrés Celsius.One of the advantages of the present invention resides in the fact that at the indicated contents the mixtures water / hydroxylammonium nitrate remain liquid from the as long as the temperature does not drop below zero degrees Celsius.

    Selon une première variante préférée, les compositions selon l'invention contiennent également des oxydants secondaires qui sont avantageusement choisis dans le groupe constitué par le nitrate d'ammonium, l'hexogène (RDX) et l'octogène (HMX). Ces oxydants secondaires permettent d'augmenter le nombre de molécules gazeuses produites par la combustion d'un volume donné de composition sans que la température des gaz de combustion n'augmente trop grâce à l'eau contenue dans la composition.According to a first preferred variant, the compositions according to the invention also contain secondary oxidants which are advantageously chosen in the group consisting of ammonium nitrate, hexogen (RDX) and octogen (HMX). These oxidants allow to increase the number of gaseous molecules produced by the combustion of a given volume of composition without the temperature of combustion gas does not increase too much thanks to the water contained in the composition.

    Selon une seconde variante préférée, lorsque les compositions sont destinées à constituer des chargements pyrotechniques pour des générateurs de gaz devant gonfler des coussins de protection pour les occupants d'un véhicule automobile, on évitera l'emploi du nitrate d'ammonium ou en tout cas on limitera la teneur pondérale de la composition en nitrate d'ammonium à quelques pourcents. According to a second preferred variant, when the compositions are intended to constitute loads pyrotechnics for gas generators in front inflate protective cushions for occupants of a motor vehicle, avoid the use of nitrate ammonium or in any case limit the content by weight of the ammonium nitrate composition to a few percent.

    Pour cette application les compositions contiendront le plus souvent des additifs stabilisants qui seront choisis parmi la bipyridine, l'hydrogénophosphate d'ammonium et l'acétate d'ammonium. La teneur pondérale de ces stabilisants dans la composition sera voisine de 2%. La bipyridine et l'hydrogénophosphate d'ammonium sont des stabilisants préférés.For this application the compositions will most often contain stabilizing additives who will be chosen from bipyridine, ammonium hydrogen phosphate and ammonium acetate. The weight content of these stabilizers in the composition will be close to 2%. Bipyridine and ammonium hydrogen phosphate are stabilizers preferred.

    Avantageusement encore, pour les applications destinées à la sécurité automobile, les compositions contiendront des additifs épaississants qui seront choisis dans le groupe constitué par les isocyanates hydrodiluables, les résines mélamine-formol et le borax qui est un tétraborate de sodium de formule : Na2B4O7,10H2O.Advantageously also, for applications intended for automotive safety, the compositions will contain thickening additives which will be chosen from the group consisting of water-soluble isocyanates, melamine-formaldehyde resins and borax which is a sodium tetraborate of formula: Na 2 B 4 O 7 , 10H 2 O.

    L'invention concerne également un procédé de fabrication en continu de chargements pyrotechniques solides à structure amorphe dont la composition correspond aux compositions décrites ci-dessus et qui est caractérisé en ce que :

  • i) on alimente en continu un appareil de malaxage et d'extrusion d'une part avec une phase liquide contenant au moins de l'eau et du nitrate d'hydroxylammonium et d'autre part avec des granulés solides comprenant au moins un liant à effet gélifiant,
  • ii) après malaxage on extrude un jonc profilé qui est durci en étuve et découpé à la longueur voulue, par exemple sous forme de tubes ou de couronnes.
    • The invention also relates to a process for the continuous production of solid pyrotechnic charges with an amorphous structure, the composition of which corresponds to the compositions described above and which is characterized in that:
  • i) a kneading and extrusion apparatus is fed continuously on the one hand with a liquid phase containing at least water and hydroxylammonium nitrate and on the other hand with solid granules comprising at least one binder gelling effect,
  • ii) after mixing, a profiled rod is extruded which is hardened in an oven and cut to the desired length, for example in the form of tubes or crowns.

    • Avantageusement l'appareil de malaxage et d'extrusion est une extrudeuse bi-vis.
       Selon une réalisation préférée du procédé selon l'invention le liant à effet gélifiant est de l'alcool polyvinylique et l'extrudeuse bi-vis est chauffée à une température comprise entre 50°C et 60°C, la température à l'intérieur de l'étuve étant voisine de 80°C. De manière particulièrement préférée tous les consitutants autres que le liant et qui sont solubles dans l'eau seront mélangés à la phase liquide contenant l'eau et le nitrate d'hydroxylammonium avant introduction de cette dernière dans l'extrudeuse bi-vis.    Advantageously, the kneading and extrusion apparatus is a twin-screw extruder.
    According to a preferred embodiment of the process according to the invention, the binder with gelling effect is polyvinyl alcohol and the twin-screw extruder is heated to a temperature between 50 ° C. and 60 ° C., the temperature inside the oven being close to 80 ° C. In a particularly preferred manner all the constituents other than the binder and which are soluble in water will be mixed with the liquid phase containing the water and the hydroxylammonium nitrate before introduction of the latter into the twin-screw extruder.

    Les chargements pyrotechniques ainsi obtenus peuvent notamment être utilisés soit dans les extincteurs pyrotechniques pour constituer la source de gaz moteur dans ces extincteurs, soit dans les générateurs pyrotechniques de gaz destinés à gonfler des coussins de protection pour les occupants d'un véhicule automobile.The pyrotechnic charges thus obtained can in particular be used either in pyrotechnic extinguishers to constitute the source of engine gas in these fire extinguishers, either in pyrotechnic gas generators intended to inflate protective cushions for vehicle occupants automobile.

    on donne ci-après une description détaillée d'une réalisation préférée de l'invention en se référant à la figure 1 qui représente le schéma d'une installation de fabrication en continu de chargements selon l'invention.a detailed description is given below preferred embodiment of the invention with reference to the Figure 1 which represents the diagram of an installation of continuous manufacturing of loads according to the invention.

    L'installation représentée à la figure 1 comprend fondamentalement une boudineuse bi-vis 1 prolongée par une tête d'extrusion 2, une bande transporteuse 3 passant à l'intérieur d'une étuve 4 et un système de découpe 5. Au début de l'extrudeuse sont prévus deux dispositifs d'alimentation.
       Le premier dispositif consiste en un tuyau 6 relié par l'intermédiaire d'un robinet 7 à un bac 8 muni d'un agitateur 9.     The installation shown in FIG. 1 basically comprises a twin-screw extruder 1 extended by an extrusion head 2, a conveyor belt 3 passing inside an oven 4 and a cutting system 5. At the start of the 'extruder are provided two feed devices.
    The first device consists of a pipe 6 connected via a tap 7 to a tank 8 provided with an agitator 9.

    En aval dans le sens de fonctionnement de la boudineuse 1 se trouve un second dispositif d'alimentation constitué par une trémie 10 et un tapis transporteur 11.Downstream in the operating direction of the extruder 1 is a second device feed consisting of a hopper 10 and a belt carrier 11.

    Le bac 8 contient un mélange liquide A constitué par de l'eau, du nitrate d'hydroxylammonium et, le cas échéant, les constituants autres que le liant et solubles dans l'eau comme le nitrate d'ammonium. Les constituants réactifs vis-à-vis de l'eau ne sont pas incorporés à cette phase liquide aqueuse.The tank 8 contains a liquid mixture A consisting with water, hydroxylammonium nitrate and, if applicable constituents other than the binder and soluble in water such as ammonium nitrate. The reactive constituents with respect to water are not incorporated into this aqueous liquid phase.

    Le tapis transporteur 11 alimente la trémie 10 avec un mélange de granulés B comprenant des granulés de liant et, le cas échéant, des granulés d'additifs non solubles dans l'eau et notamment des granulés d'oxydants non solubles dans l'eau comme l'hexogène ou l'octogène.The conveyor belt 11 feeds the hopper 10 with a mixture of granules B comprising granules of binder and, if necessary, granules of additives not soluble in water and in particular oxidizing granules not soluble in water such as hexogen or octogen.

    L'extrudeuse 1 est régulée en température pour présenter une température interne comprise entre 50°C et 60°C lorsque le liant est de l'alcool polyvinylique.Extruder 1 is temperature controlled to have an internal temperature between 50 ° C and 60 ° C when the binder is polyvinyl alcohol.

    La phase liquide A et les granulés B sont mélangés dans l'extrudeuse 1 pour former, par gélification du liant, une pâte composite à structure amorphe qui est extrudée au travers de la tête d'extrusion 2 sous forme d'un jonc profilé 12. Ce jonc peut-être un simple brin cylindrique, éventuellement pourvu de canaux internes, pour donner, après découpage, des grains en vrac ou être un jonc de dimensions plus importantes, avec, le cas échéant, un profil extérieur travaillé, pour donner après découpage des blocs pleins ou annulaires.
       Ce jonc 12 est conduit par l'intermédiaire de la bande transporteuse 3 au travers d'une étuve chauffée pour provoquer le durcissement du liant gélifié. Lorsque le liant est l'alcool polyvinylique la température de l'étuve sera voisine de 80°C et le temps de séjour du jonc dans l'étuve sera de quelques minutes.    The liquid phase A and the granules B are mixed in the extruder 1 to form, by gelation of the binder, a composite paste with an amorphous structure which is extruded through the extrusion head 2 in the form of a profiled rod 12. This rod may be a simple cylindrical strand, possibly provided with internal channels, to give, after cutting, loose grains or be a rod of larger dimensions, with, if necessary, a worked external profile, to give after cutting. solid or annular blocks.
    This rod 12 is led through the conveyor belt 3 through a heated oven to cause hardening of the gelled binder. When the binder is polyvinyl alcohol, the temperature of the oven will be close to 80 ° C. and the residence time of the rod in the oven will be a few minutes.

    En sortie d'étuve le jonc 12 est découpé grâce au système de découpe 5 en chargements élémentaires 13 qui sont stockés dans un container 14.On leaving the oven the rod 12 is cut thanks to the cutting system 5 in elementary loads 13 which are stored in a container 14.

    Exemples 1 et 2Examples 1 and 2

    On a ainsi fabriqué des chargements en forme de couronnes cylindriques. Ces chargements avaient les compositions suivantes : Exemple 1 Exemple 2 eau 8 15% alcool polyvinylique 20% 15% nitrate d'hydroxylammonium 68,5% 66,5% nitrate d'ammonium 3,5% 3,5% We thus produced loads in the form of cylindrical crowns. These loads had the following compositions: Example 1 Example 2 water 8 15% polyvinyl alcohol 20% 15% hydroxylammonium nitrate 68.5% 66.5% ammonium nitrate 3.5% 3.5%

    Claims (14)

    1. Solid pyrotechnic composition producing by combustion gases free from solid residues and consisting of at least one organic binder having a gelling effect and by at least one main oxidizing system in the liquid phase absorbed by the said binder, characterized in that :
      i) the said organic binder having a gelling effect is chosen from the group consisting of polyvinyl alcohol, hydroxyethyl cellulose and xanthan gum,
      ii) the said main oxidizing system in the liquid phase consists of a mixture of water and hydroxylammonium nitrate, the water content by weight in the said composition being between 5 and 20 %.
    2. Composition according to claim 1, characterized in that the weight of the said hydroxylammonium nitrate represents at least 50 % of the total weight of the composition.
    3. Composition according to claim 2, characterized in that the content by weight of hydroxylammonium nitrate in the said composition is between 60 % and 70 %.
    4. Composition according to claim 1, characterized in that it contains secondary oxidants.
    5. Composition according to claim 4, characterized in that the said secondary oxidants are chosen from the group consisting of ammonium nitrate, hexogen and octogen.
    6. Composition according to claim 1, characterized in that it contains stabilizing additives.
    7. Composition according to claim 6, characterized in that the said stabilizing additives are chosen from the group consisting of bipyridine, ammonium hydrogenophosphate and ammonium acetate.
    8. Composition according to claim 7, characterized in that the stabilizing additive is chosen from the group consisting of bipyridine and ammonium hydrogenophosphate.
    9. Composition according to claim 1, characterized in that it contains thickening additives.
    10. Composition according to claim 9, characterized in that the said thickening additives are chosen from the group consisting of isocyanates, melamine-formaldehyde resins and borax.
    11. Method for manufacturing solid pyrotechnic charges with an amorphous structure of which the composition corresponds to any one of claims 1 to 10, characterized in that :
      i) a blending and extruding apparatus (1) is fed continuously on the one hand with a liquid phase (A) containing at least water and hydroxylammonium nitrate and on the other hand with solid granules (B) containing at least one binder having a gelling effect,
      ii) after blending, a profiled bead (12) is extruded which is hardened in an oven (4) and cut to the desired length.
    12. Method according to claim 11, characterized in that the blending and extruding apparatus is a twin-screw extruder.
    13. Method according to claim 12, characterized in that the binder having a gelling effect is polyvinyl alcohol and in that the twin-screw extruder is heated to a temperature of between 50°C and 60°C, the temperature inside the oven being close to 80°C.
    14. Method according to claim 13, characterized in that all the constituents other than the binder and those soluble in water are mixed with the liquid phase containing water and hydroxylammonium nitrate before the latter is introduced into the twin-screw extruder.
    EP99920902A 1998-06-05 1999-05-21 Gas-generating solid pyrotechnic loads based on compositions containing water Expired - Lifetime EP1087919B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    FR9807090A FR2779426B1 (en) 1998-06-05 1998-06-05 SOLID PYROTECHNICAL CHARGES GAS GENERATORS BASED ON COMPOSITIONS CONTAINING WATER
    FR9807090 1998-06-05
    PCT/FR1999/001206 WO1999064375A1 (en) 1998-06-05 1999-05-21 Gas-generating solid pyrotechnic loads based on compositions containing water

    Publications (2)

    Publication Number Publication Date
    EP1087919A1 EP1087919A1 (en) 2001-04-04
    EP1087919B1 true EP1087919B1 (en) 2002-12-04

    Family

    ID=9527056

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP99920902A Expired - Lifetime EP1087919B1 (en) 1998-06-05 1999-05-21 Gas-generating solid pyrotechnic loads based on compositions containing water

    Country Status (6)

    Country Link
    EP (1) EP1087919B1 (en)
    JP (1) JP2002517376A (en)
    AT (1) ATE228984T1 (en)
    DE (1) DE69904326T2 (en)
    FR (1) FR2779426B1 (en)
    WO (1) WO1999064375A1 (en)

    Families Citing this family (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CN100357235C (en) * 2006-04-14 2007-12-26 安徽盾安化工集团有限公司 TNT-free powdered modified ammonium nitrate-fuel oil explosive and preparation process thereof
    CN100357234C (en) * 2006-04-14 2007-12-26 安徽盾安化工集团有限公司 Powdered ammonium nitrate-fuel oil explosive and production process thereof
    JP5110256B2 (en) * 2006-12-12 2012-12-26 独立行政法人 宇宙航空研究開発機構 Gas generant composition
    JP2009190911A (en) * 2008-02-13 2009-08-27 Daicel Chem Ind Ltd Gas generator composition
    DE102012104087A1 (en) * 2012-05-09 2013-11-14 Bayern-Chemie Gesellschaft Für Flugchemische Antriebe Mbh Gas generator fuel

    Family Cites Families (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    ZA835342B (en) * 1982-08-02 1985-01-30 Jet Research Center A stable single phase liquid explosive
    GB2293820B (en) * 1988-12-20 1996-07-03 Aerojet General Co Liquid oxidizer compositions and their use in energetic formulations
    US5060973A (en) * 1990-07-23 1991-10-29 General Electric Company Liquid propellant inflator for vehicle occupant restraint apparatus
    US5386777A (en) * 1992-02-10 1995-02-07 Aero-Jet General Corporation Rocket motor construction from porous binder core
    US5684269A (en) * 1996-03-15 1997-11-04 Morton International, Inc. Hydroxylammonium nitrate/water/self-deflagrating fuels as gas generating pyrotechnics for use in automotive passive restraint systems
    US5703323A (en) * 1996-09-17 1997-12-30 Olin Corporation Pyridine and pyridone stabilizers for hydroxylammonium nitrate and hydroxylamine-containing compositions

    Also Published As

    Publication number Publication date
    DE69904326T2 (en) 2003-08-28
    FR2779426B1 (en) 2000-07-13
    FR2779426A1 (en) 1999-12-10
    WO1999064375A1 (en) 1999-12-16
    ATE228984T1 (en) 2002-12-15
    JP2002517376A (en) 2002-06-18
    DE69904326D1 (en) 2003-01-16
    EP1087919A1 (en) 2001-04-04

    Similar Documents

    Publication Publication Date Title
    EP1037864B1 (en) Pyrotechnic mixtures generating non-toxic gases based on ammonium perchlorate
    EP1934158A2 (en) Rapid gas generating pyrotechnical composition and method for obtaining same
    US6682616B1 (en) Gas generating composition for use in a pretensioner
    EP0950647B1 (en) Gas generating composition for air bag
    FR2703990A1 (en) A gas generator composition comprising a deoxidized agent and an oxidizing agent.
    US20070039671A1 (en) Flash-ignitable energetic material
    JP4575395B2 (en) Especially combustible gas generating compositions and ignition products for automobile safety devices
    FR2964656A1 (en) PYROTECHNIC COMPOUNDS GENERATORS OF GAS
    EP0576326B1 (en) Pyrotechnic composition, which generates a hot non-toxic gas and use thereof in a protection system for motor vehicle occupants
    FR2818636A1 (en) HYDROCARBON-BINDING GAS-GENERATING PYROTECHNIC COMPOSITIONS AND CONTINUOUS MANUFACTURING METHOD
    CA2784311A1 (en) Malleable solid explosive and method for obtaining it
    EP1087919B1 (en) Gas-generating solid pyrotechnic loads based on compositions containing water
    JPH06219882A (en) Gas generating substance for air bag
    FR2876372A1 (en) GENERATING COMPOSITION OF GAS.
    FR2926545A1 (en) NITROGEN GENERATING COMPOSITION COMPRISING AZODICARBONAMIDE AND PROCESS FOR GENERATING NITROGEN GAS BY DECOMPOSITION OF SAID COMPOSITION
    WO2008001005A2 (en) Pyrotechnic compositions initiable by heat, and their use
    EP1496036A2 (en) Pyrotechnic gas generating composition for car safety systems having a combustion temperature below 2200 degree K
    JP5044219B2 (en) Thermal pre-ignition agent
    EP0930284B1 (en) Ablative solid material for hybrid gas generator
    FR2870845A1 (en) Composition, useful e.g. for production of gas, comprises a fuel and an oxidizing agent, where the fuel comprises a product (glycine or its derivatives)

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 20010105

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    17Q First examination report despatched

    Effective date: 20010417

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20021204

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

    Effective date: 20021204

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20021204

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20021204

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20021204

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20021204

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20021204

    REF Corresponds to:

    Ref document number: 228984

    Country of ref document: AT

    Date of ref document: 20021215

    Kind code of ref document: T

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: FRENCH

    REF Corresponds to:

    Ref document number: 69904326

    Country of ref document: DE

    Date of ref document: 20030116

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20030304

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20030305

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20030315

    REG Reference to a national code

    Ref country code: SE

    Ref legal event code: TRGR

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030521

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20030521

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030531

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030531

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030531

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030531

    GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

    Effective date: 20021204

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    Ref document number: 1087919E

    Country of ref document: IE

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20030905

    BERE Be: lapsed

    Owner name: *SNPE

    Effective date: 20030531

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: TP

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: CD

    Owner name: HERAKLES, FR

    Effective date: 20130213

    Ref country code: FR

    Ref legal event code: CA

    Effective date: 20130213

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R082

    Ref document number: 69904326

    Country of ref document: DE

    Representative=s name: CBDL PATENTANWAELTE, DE

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R082

    Ref document number: 69904326

    Country of ref document: DE

    Representative=s name: CBDL PATENTANWAELTE, DE

    Effective date: 20130528

    Ref country code: DE

    Ref legal event code: R082

    Ref document number: 69904326

    Country of ref document: DE

    Representative=s name: CBDL PATENTANWAELTE, DE

    Effective date: 20130513

    Ref country code: DE

    Ref legal event code: R081

    Ref document number: 69904326

    Country of ref document: DE

    Owner name: HERAKLES, FR

    Free format text: FORMER OWNER: SME, PARIS, FR

    Effective date: 20130528

    Ref country code: DE

    Ref legal event code: R081

    Ref document number: 69904326

    Country of ref document: DE

    Owner name: HERAKLES, FR

    Free format text: FORMER OWNER: SNPE MATERIAUX ENERGETIQUES, PARIS, FR

    Effective date: 20130513

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: SE

    Payment date: 20130517

    Year of fee payment: 15

    Ref country code: DE

    Payment date: 20130513

    Year of fee payment: 15

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20130607

    Year of fee payment: 15

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 69904326

    Country of ref document: DE

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20140522

    REG Reference to a national code

    Ref country code: SE

    Ref legal event code: EUG

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 69904326

    Country of ref document: DE

    Effective date: 20141202

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20150130

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20141202

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20140602