EP2707345B1 - Pyrotechnic gas generator compounds - Google Patents

Pyrotechnic gas generator compounds Download PDF

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Publication number
EP2707345B1
EP2707345B1 EP12725124.7A EP12725124A EP2707345B1 EP 2707345 B1 EP2707345 B1 EP 2707345B1 EP 12725124 A EP12725124 A EP 12725124A EP 2707345 B1 EP2707345 B1 EP 2707345B1
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Prior art keywords
compound
combustion
titanate
composition
pyrotechnic
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EP12725124.7A
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German (de)
French (fr)
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EP2707345A2 (en
Inventor
Frédéric MARLIN
Stéphane BESOMBES
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ArianeGroup SAS
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ArianeGroup SAS
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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)
    • C06D3/00—Generation of smoke or mist (chemical part)
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • C06B33/12—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being two or more oxygen-yielding compounds
    • C06B33/14—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being two or more oxygen-yielding compounds at least one being an inorganic nitrogen-oxygen salt
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • 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
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • 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
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • the present invention relates to pyrotechnic compounds (or pyrotechnic objects) which generate gas simultaneously having a moderate combustion temperature (less than 2200 K) and a high combustion speed (equal to or greater than 20 mm / s at 20 MPa) and generating combustion residues in agglomerated form, thus easily filterable residues.
  • Said gas-generating pyrotechnic compounds are particularly suitable for use in systems for protecting the occupants of motor vehicles, more especially for inflating front shock absorbing cushions (called “airbags”) (see below).
  • Front airbags differ from side airbags essentially in the time required for deployment and installation of the airbag. Typically, this time is higher for a front airbag (of the order of 40-50 ms, against 10-20 ms for a side airbag).
  • pyrotechnic composition for obtaining gas-generating pyrotechnic compounds particularly suitable for use in systems for protecting the occupants of motor vehicles, have already been proposed to date.
  • the pyrotechnic compounds which seem to offer the best compromise, in terms of combustion temperature, gas yield, toxicity of combustion gases and pyrotechnic safety of implementation, contain, in their composition, as main ingredients of guanidine nitrate (NG) as a reducing filler and basic copper nitrate (BCN) as an oxidizing filler.
  • NG guanidine nitrate
  • BCN basic copper nitrate
  • the use of the NG / BCN couple makes it possible to obtain a low combustion temperature, typically of the order of 1800 K.
  • the patent US 5,608,183 describes compounds of this type obtained by a wet manufacturing process. These compounds, however, remain difficult to ignite and intrinsically exhibit a combustion rate at best equal to 20 mm / s at 20 MPa.
  • additives based on a transition metal oxide, playing the role of ballistic catalyst.
  • Such additives are well known to those skilled in the art, in that they are traditionally used in the field of propellants (as a ballistic catalyst) to increase the combustion speed, both at low, medium and high. pressure.
  • a ballistic catalyst is thus described, consisting of an oxide chosen from Al 2 O 3 , TiO 2 , ZnO, MgO and ZrO 2 , at a mass rate of 0.5% up to 5% .
  • metal oxides and hydroxides playing the role of ballistic catalyst (qualified as combustion adjustment agent) are also mentioned, such as Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Fe 3 O 4 , CuO, Cu 2 O, CoO, V 2 O 5 , WO 3 , ZnO, NiO, Cu (OH) 2 . They can be incorporated up to 10% by mass.
  • the pyrotechnic compounds formulated from basic copper nitrate (BCN) have the major drawback of generating, during combustion, a high rate of solid residues which are difficult to filter.
  • This low filterability results from the fact that the copper residues, in liquid form at the combustion temperature in the gas generator, inherently have poor agglomeration and can easily be entrained with the flow of combustion gases to solidify at the outlet of said generator. .
  • the resulting hot solid particles are then liable to damage the wall of the airbag. Due to the high level of BCN in the pyrotechnic compounds described above, it is therefore necessary to equip the gas generator with a substantial filter system in order to guarantee satisfactory capture of the copper particles, to the detriment of the sizing. , the weight and therefore the cost of the gas generator.
  • patent US 6,143,102 and patent applications EP 1 342 705 and EP 1,568,673 also describe the use of an agglomerating agent, such as SiO 2 , Si 3 N 4 , SiC or clay, in addition to a ballistic catalyst additive, at a mass rate which may also range from 0.5% to 5% or even 10%.
  • an agglomerating agent such as SiO 2 , Si 3 N 4 , SiC or clay
  • the first additive playing the role of ballistic catalyst
  • the second additive ensuring the agglomeration of copper residues
  • the first additive can represent up to 10%, or even 15%, by mass of the composition of the compound, which contributes to a detrimental decrease in the gas yield value of said composition.
  • Patent applications EP 0 949 225 and EP 1 006 096 thus describe compositions which contain, as main ingredients, a reducing charge consisting of or containing a guanidine derivative and an oxidizing charge containing BCN and a metal oxide, associated with a chlorate, perchlorate and / or nitrate.
  • the metal oxide introduced at a high mass rate (20 to 70%, or even 80%, by mass of the total mass of oxidizing charge), acts as an oxidizing charge in its own right. It helps to regulate the overall oxygen balance of the composition.
  • Said metal oxide generally consists of CuO but other oxides such as Cr 2 O 3 and MnO 2 are mentioned.
  • compositions of pyrotechnic gas-generating compounds incorporating, as main ingredients, NG and BCN and containing two types of additives: a combustion catalyst (consisting of a metal oxide) and an agglomerating agent (such as SiO 2 , nitride or silicon carbide). It also describes compositions containing NG and BCN as well as a high level of metal oxide, as a substitution oxidizing charge (partial, or even total) for said BCN.
  • compositions which can incorporate a strontium derivative such as SrO, SrCO 3 , Sr (OH) 2 or SrTiO 3 , are described in the patent application. JP 2009 137 821 .
  • These compositions contain a reducing agent, an oxidizing agent, a binder, a phosphorus-containing agent for reducing the combustion temperature and a strontium derivative whose role is to limit the production of phosphorus oxide during combustion.
  • Additives of the type of those mentioned above can also be present in these compositions.
  • These compositions are not of the type of those of the invention.
  • the teaching of this document in no way suggests the bi-function of SrTiO 3 within the compositions of the compounds of the invention (see below).
  • NG guanidine nitrate
  • BCN basic copper nitrate
  • the inventors wished to propose improved pyrotechnic compounds (improved pyrotechnic objects), particularly suitable for use in front airbags. More precisely, the inventors wished to propose pyrotechnic compounds in the composition of which the presence of a single (type of) bi-functional additive (at a low rate, ie with a limited impact on the gas yield) makes it possible to jointly satisfy the technical problem of the agglomeration of combustion residues and that of obtaining a high combustion speed (in this case at least as high as that of the compounds of the prior art described in the patent US 6,143,102 ).
  • the solid pyrotechnic gas-generating compounds (objects) of the invention are of the conventional NG / BCN-based type and their composition typically contains at least one inorganic titanate the melting point of which is greater than 2100 K. Said at less one inorganic titanate acts as an agglomeration agent for solid combustion residues and as a ballistic catalyst.
  • Said at least one titanate is a refractory compound, the melting point of which (greater than 2100 K) is significantly higher than the combustion temperatures of the NG / BCN bases in which it is present. Thus, it retains its physical state as a pulverulent solid (it obviously occurs in this form) at the combustion temperature, a characteristic necessary to obtain an effect of agglomeration of the liquid copper residues.
  • said at least one titanate is a refractory compound, the melting point of which is significantly higher than the combustion temperatures of the NG / BCN bases in which it is present, it is specified what follows.
  • the combustion temperature of any NG / BCN base is in fact always less than 1950 K.
  • an NG (53.7% by mass) / BCN base (46.3 % by mass) exhibiting an oxygen balance value of -3.3%, has a combustion temperature of 1940 K at 20 MPa and 1941 K at 50 MPa.
  • the maximum combustion temperature of an NG / BCN base is obtained for a ratio of 53.5% by mass of NG and 46.5% by mass of BCN, exhibiting an oxygen balance value of -3.2% , its value is 1942 K at 20 MPa, 1943 K at 50 MPa. This further confirms the fact that the combustion temperature is only likely to vary by a few degrees Kelvin with the operating pressure of the gas generator, and always remains below 1950 K, whatever the operating pressure of the gas generator. gas. Thus the required value, greater than 2100 K, for the melting point of said at least one titanate (original bi-functional additive of the compositions of the compounds of the invention) is always significantly higher (by at least 150 K) than the maximum combustion value of an NG / BCN base.
  • the at least one inorganic titanate, the melting point of which is greater than 2100 K, present in the composition of the compounds of the invention, is advantageously chosen from metal titanates, alkaline earth titanates and their mixtures. It very advantageously consists of a metal titanate or an alkaline earth titanate.
  • the composition of the compounds of the invention contains strontium titanate (SrTiO 3 ) and / or calcium titanate (CaTiO 3 ) and / or aluminum titanate (Al 2 TiO 5 ).
  • the at least one bifunctional additive of the invention is between 1 and 5% (limits included) by mass, advantageously between 2 and 4% by mass (limits included), within the composition (by weight) of the compounds of the invention.
  • composition of the compounds of the invention is generally free of binder (preferred variant). Indeed, the rheo-plastic behavior of guanidine nitrate a priori makes the presence of any binder superfluous, in particular for obtaining, by dry process, formed pyrotechnic objects, granules, pellets and compressed monolith blocks. (see below). However, the presence of such a binder cannot be completely excluded.
  • the compounds of the invention incorporating a binder can in particular exist in the form of monolithic blocks obtained by extrusion, optionally in the wet process.
  • the ingredients of the three types above can quite represent 100% by mass of the total mass of the compounds of the invention.
  • the possible presence of at least one other additive, chosen, for example, from processing aids (calcium stearate, graphite, silica in particular), is expressly provided for, at a rate of less than 0.5% by mass.
  • Such at least one other additive does not consist of a binder.
  • the ingredients of the three types above (guanidine nitrate, basic copper nitrate, bi-functional additive (s)) therefore generally represent more than 99.5% by mass of the composition of the pyrotechnic compound which is free from binder.
  • strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ), and aluminum titanate (Al 2 TiO 5 ) therefore have a refractory character (their temperature melting temperature is, respectively, 2353 K, 2248 K and 2133 K, ie significantly higher than the combustion temperature of the NG / BCN base, which is always lower than 1950 K (see above)).
  • these additives retain their physical state as a pulverulent solid (they obviously occur in this form) at the combustion temperature of the composition, a characteristic necessary to obtain an agglomeration effect of the liquid copper residues.
  • said at least one bifunctional additive is in a fine pulverulent form (of micrometric dimension, advantageously of nanometric dimension): with a median diameter of less than 5 ⁇ m, advantageously of less than 1 ⁇ m. It advantageously has a specific surface area greater than 1 m 2 / g (advantageously greater than 5 m 2 / g or more).
  • Guanidine nitrate is preferred as a reducing agent, among others for reasons of pyrotechnic safety and for its rheoplastic behavior, suitable for the implementation of the compacting and pelletizing phases of a dry process (see below ), ensuring good densification of the starting powder pyrotechnic composition while limiting the compressive force to be applied.
  • the manufacture of compounds of the invention by a dry process can comprise up to four main steps (see below), which have in particular been described in the patent application. WO 2006/134311 .
  • the at least one additive (bifunctional, chosen from inorganic titanates whose melting point is greater than 2100 K) is advantageously involved with the other constituent ingredients, NG + BCN mainly, or even exclusively (at the start of the manufacturing process) or is added, more downstream, in the manufacturing process of the compounds of the invention.
  • the pyrotechnic compounds of the invention can also be obtained by a wet process.
  • said method comprises the extrusion of a paste containing the constituents of the compound.
  • said method includes a step of dissolving all or some main constituents in aqueous solution comprising a solubilization of at least one of the main constituents (reducing agent) and then obtaining a powder by spray drying, the addition to the powder obtained of the constituent (s) which have not been added in solution, then shaping the powder in the form of objects by the usual dry process.
  • the preferential process for obtaining the pyrotechnic compounds of the invention includes a dry compacting stage of a mixture of powdered constituent ingredients of said compounds (except, optionally, said at least one additive which can be added later). Dry compaction is generally carried out, in a manner known per se , in a roller compactor, at a compaction pressure of between 10 8 and 6.10 8 Pa. It can be carried out according to different variants (with a characteristic step "simple" compaction followed by at least one complementary step or with a characteristic compacting step coupled with a shaping step).
  • the pyrotechnic compounds of the invention can also be obtained in the dry process by simple pelletizing of the powder obtained by mixing their constituents.
  • the constituent ingredients of the compounds of the invention advantageously have a fine particle size, less than or equal to 20 ⁇ m.
  • Said particle size (value of the median diameter) is generally between 1 and 20 ⁇ m.
  • the compounds described in the present invention express their full potential if they are obtained by a dry process from powders having a median diameter of between 5 to 15 ⁇ m for guanidine nitrate, between 2 to 7 ⁇ m for nitrate. basic copper and between 0.5 to 5 ⁇ m for the at least one bi-functional additive.
  • the present invention relates to a pulverulent composition (mixture of powders), precursor of a compound of the invention, the composition of which therefore corresponds to that of a compound of the invention (see above).
  • the present invention relates to gas generators containing a pyrotechnic solid charge which generates gas; said charge containing at least one pyrotechnic compound of the invention.
  • Said generators, loaded in particular with pellets of the invention, are perfectly suitable for airbags, in particular front airbags (see above).
  • Table 1 shows three examples (Ex.1, Ex.2 and Ex.3) of the composition of compounds of the present invention, as well as the performances of said compounds compared to those of a compound of the art previous (Ref. 1) according to US 6,143,102 (said compounds of the invention and of the prior art were produced by a dry process).
  • the compounds were evaluated by means of thermodynamic calculations or from physical measurements carried out on granules or pellets made from the compositions via the process of mixing powders - compacting - granulation - and optionally dry pelletizing.
  • the reference compound 1 (Ref. 1) of the prior art contains guanidine nitrate, basic copper nitrate as well as an aluminum oxide (Al 2 O 3 ) as a ballistic catalyst and silica ( SiO 2 ) as an agglomerating additive (“slaggant” additive).
  • the compounds of Examples 1 to 3 contain in their composition, in addition to the two components guanidine nitrate and basic copper nitrate of reference 1, a single bifunctional additive as described in the present invention.
  • the levels of the constituents were adjusted in order to keep an oxygen balance value close to -3.3%, so as to be able to directly compare the performance of these compounds.
  • Examples 1 and 2 of Table 1 show that the addition, at a moderate rate (mass content of 4%), of an additive, strontium titanate (SrTiO 3 ) or calcium titanate (CaTiO 3 ), in a composition of the type of that of reference compound 1, leads to the production of agglomerated combustion residues (in the form of a skeleton of the pyrotechnic block) and, to a combustion rate value over the pressure range 10 MPa - 20 MPa greater than a pressure exponent value lower than an inflation surface flow rate higher than those of the reference compound 1 of the prior art.
  • a moderate rate mass content of 4%
  • an additive strontium titanate
  • CaTiO 3 calcium titanate
  • Example 3 of Table 1 show that the addition, at a reduced rate (mass content of 2.7%) of calcium titanate (CaTiO 3 ) compared to Example 2 (mass content of 4% ), improves the performances (increase of the combustion speed value over the range 10-20 MPa, of the gas yield value and ultimately of the inflation surface flow value) compared to those of the compound according to the example 2, while making it possible to maintain a quality of agglomeration of combustion residues satisfying the functional need.
  • Table 1 ⁇ /u> Examples Ref. 1 Ex. 1 Ex. 2 Ex.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Description

La présente invention a pour objet des composés pyrotechniques (ou objets pyrotechniques) générateurs de gaz présentant simultanément une température de combustion modérée (inférieure à 2200 K) et une vitesse de combustion élevée (égale ou supérieure à 20 mm/s à 20 MPa) et générant des résidus de combustion sous forme agglomérée, résidus ainsi aisément filtrables.The present invention relates to pyrotechnic compounds (or pyrotechnic objects) which generate gas simultaneously having a moderate combustion temperature (less than 2200 K) and a high combustion speed (equal to or greater than 20 mm / s at 20 MPa) and generating combustion residues in agglomerated form, thus easily filterable residues.

Lesdits composés pyrotechniques générateurs de gaz conviennent particulièrement pour une utilisation dans des systèmes de protection d'occupants de véhicules automobiles, plus spécialement pour le gonflage des coussins amortissants (dits "airbags") frontaux (voir ci-dessous).Said gas-generating pyrotechnic compounds are particularly suitable for use in systems for protecting the occupants of motor vehicles, more especially for inflating front shock absorbing cushions (called "airbags") (see below).

Le domaine technique relatif à la protection des occupants de véhicules automobiles a connu un essor très important durant les vingt dernières années. Les véhicules de dernière génération intègrent dorénavant au sein de l'habitacle plusieurs systèmes de sécurité de type coussin gonflable amortissant (dit "airbag") dont le fonctionnement est assuré par les gaz de combustion de composés pyrotechniques. Parmi les systèmes de type coussin amortissant, on distingue les airbags frontaux (conducteur ou passager) et les airbags latéraux (rideau, protection thorax).The technical field relating to the protection of occupants of motor vehicles has experienced a very significant development during the last twenty years. The latest generation vehicles now integrate several safety systems of the shock-absorbing airbag type (called “airbag”) within the passenger compartment, the operation of which is ensured by the combustion gases of pyrotechnic compounds. Among the damping cushion-type systems, a distinction is made between front airbags (driver or passenger) and side airbags (curtain, thorax protection).

Les airbags frontaux se différencient des airbags latéraux essentiellement par le temps requis pour le déploiement et la mise en place du coussin gonflable. Typiquement, ce temps est plus élevé pour un airbag frontal (de l'ordre de 40-50 ms, contre 10-20 ms pour un airbag latéral).Front airbags differ from side airbags essentially in the time required for deployment and installation of the airbag. Typically, this time is higher for a front airbag (of the order of 40-50 ms, against 10-20 ms for a side airbag).

Les systèmes airbags frontaux font pour l'essentiel appel à des générateurs de gaz dits entièrement pyrotechniques, incluant au moins un chargement pyrotechnique constitué d'au moins un composé (objet) pyrotechnique. Ce type de conception impose en retour que le composé pyrotechnique, puisse satisfaire conjointement aux exigences suivantes :

  1. 1) tout d'abord, le rendement gazeux d'un tel composé pyrotechnique (c'est-à-dire la quantité de gaz généré par la combustion), exprimé en mole/g, doit être élevé afin de conduire à un fort pouvoir de gonflage ;
  2. 2) un tel composé pyrotechnique doit présenter une valeur de débit surfacique de gonflage (lequel débit est estimé par le produit ρ x n x Tc x Vc, où ρ est la masse volumique du composé pyrotechnique (exprimée en g/cm3), n est le rendement molaire gazeux de la combustion (exprimé en mole/g), Tc est la température de combustion (exprimée en Kelvin) et Vc est la vitesse de combustion (exprimée en mm/s)) permettant le gonflage du sac sur la durée requise. Ainsi, pour un airbag frontal, le besoin fonctionnel de gonflage du sac sur un temps de l'ordre de 40-50 ms impose de recourir à un composé pyrotechnique présentant une vitesse de combustion suffisamment élevée. Une vitesse de combustion d'environ 15 mm/s à 20 MPa, plus avantageusement égale ou supérieure à 20 mm/s à 20 MPa, est suffisante pour concevoir et fabriquer un chargement adapté ;
  3. 3) afin d'assurer une mise en régime satisfaisante du système, le composé pyrotechnique doit également présenter de bonnes caractéristiques d'allumabilité. La difficulté d'allumage se trouve exacerbée du fait de la forte surface initiale du chargement induite par sa géométrie de type à plusieurs pastilles ; on trouve ainsi avantage à ce que le chargement puisse se présenter sous la forme de pastilles de dimension suffisamment élevée (idéalement des pastilles de diamètre supérieur ou égal à 5 mm) ;
  4. 4) compte tenu du profil de surface généralement dégressif des chargements employés (de type à plusieurs pastilles), le composé pyrotechnique doit présenter une vitesse de combustion stable et suffisamment élevée à basse pression, idéalement non nulle à la pression atmosphérique, ceci de manière à éviter les risques d'extinction en fin de fonctionnement, conduisant à des combustions incomplètes du chargement des pastilles. Le composé doit en outre présenter un faible exposant de pression à moyenne et haute pression (typiquement inférieur ou égal à 0,5), mais aussi à basse pression. Un faible exposant de pression permet en effet de réduire de manière très significative la variabilité du fonctionnement du composé dans le domaine d'utilisation du générateur de gaz. La reproductibilité du fonctionnement est de ce fait améliorée et la dimension de la structure métallique du générateur peut être avantageusement réduite ;
  5. 5) les gaz générés par la combustion du composé pyrotechnique doivent être non toxiques, c'est-à-dire présenter une teneur faible en monoxyde de carbone (CO), en ammoniac (NH3) et en oxydes d'azote (NOx). Cette contrainte est tout particulièrement importante pour un générateur frontal conducteur ou passager pouvant contenir entre 40 g et 80 g de composé pyrotechnique. Par ailleurs, la forte dégressivité de la surface en combustion, dans le contexte d'un chargement à géométrie de type à plusieurs pastilles, induit une longue queue de combustion à basse pression. Cette longue queue de combustion à basse pression est la source de l'émission de la majorité des espèces toxiques présentes dans les gaz servant à gonfler le coussin. Pour s'affranchir de ce problème, il est donc avantageux de disposer d'un composé pyrotechnique présentant une vitesse de combustion non nulle à pression atmosphérique ;
  6. 6) la température de combustion dudit composé pyrotechnique ne doit pas être trop élevée afin que la température des gaz dans le coussin amortissant demeure suffisamment basse pour ne pas porter atteinte à l'intégrité physique de l'occupant. Préférentiellement, une valeur de température de combustion inférieure à 2200 K, idéalement inférieure à 2000 K, est requise. Par ailleurs, une température de combustion basse permet, d'une part, de limiter l'épaisseur du sac, d'autre part, de simplifier la conception du générateur de gaz en permettant de diminuer la présence de chicanes et de filtres au sein de celui-ci. Au final, le générateur de gaz présente un poids et un volume réduit, et ce, à un coût moindre ;
  7. 7) enfin, il existe de surcroît des contraintes liées à la quantité de particules solides générées par la combustion du composé, laquelle doit demeurer faible. Lesdites particules solides sont susceptibles d'être expulsées hors du générateur de gaz lors du fonctionnement et de constituer des points chauds pouvant endommager la paroi interne du coussin gonflable.
The front airbag systems mainly use so-called fully pyrotechnic gas generators, including at least one pyrotechnic charge consisting of at least one compound (object) pyrotechnic. This type of design requires in return that the pyrotechnic compound can jointly meet the following requirements:
  1. 1) first of all, the gas yield of such a pyrotechnic compound (that is to say the quantity of gas generated by combustion), expressed in mole / g, must be high in order to lead to a high power inflation;
  2. 2) such a pyrotechnic compound must have an inflation surface flow value (which flow rate is estimated by the product ρ xnx Tc x Vc, where ρ is the density of the pyrotechnic compound (expressed in g / cm 3 ), n is the gaseous molar efficiency of combustion (expressed in mole / g), Tc is the combustion temperature (expressed in Kelvin) and Vc is the combustion rate (expressed in mm / s)) allowing inflation of the bag over the required time. Thus, for a front airbag, the functional need for inflation of the bag over a time of the order of 40-50 ms requires the use of a pyrotechnic compound having a sufficiently high combustion rate. A burning rate of about 15 mm / s at 20 MPa, more preferably equal to or greater than 20 mm / s at 20 MPa, is sufficient to design and manufacture a suitable charge;
  3. 3) in order to ensure satisfactory start-up of the system, the pyrotechnic compound must also exhibit good ignitability characteristics. The difficulty of ignition is exacerbated because of the high initial surface area of the loading induced by its geometry of the type with several pellets; it is thus advantageous that the charge can be in the form of pellets of sufficiently large size (ideally pellets with a diameter greater than or equal to 5 mm);
  4. 4) taking into account the generally decreasing surface profile of the loads employed (of the type with several pellets), the compound pyrotechnics must have a stable and sufficiently high combustion rate at low pressure, ideally non-zero at atmospheric pressure, so as to avoid the risk of extinction at the end of operation, leading to incomplete combustion of the loading of the pellets. The compound must also exhibit a low pressure exponent at medium and high pressure (typically less than or equal to 0.5), but also at low pressure. A low pressure exponent in fact makes it possible to very significantly reduce the variability of the operation of the compound in the field of use of the gas generator. The reproducibility of the operation is thereby improved and the size of the metal structure of the generator can be advantageously reduced;
  5. 5) the gases generated by the combustion of the pyrotechnic compound must be non-toxic, i.e. have a low content of carbon monoxide (CO), ammonia (NH 3 ) and nitrogen oxides (NOx) . This constraint is very particularly important for a driver's or passenger's frontal generator which can contain between 40 g and 80 g of pyrotechnic compound. Furthermore, the strong degressivity of the combustion surface, in the context of a loading with a geometry of the type with several pellets, induces a long combustion tail at low pressure. This long tail of combustion at low pressure is the source of the emission of the majority of the toxic species present in the gases used to inflate the cushion. To overcome this problem, it is therefore advantageous to have a pyrotechnic compound having a non-zero combustion rate at atmospheric pressure;
  6. 6) the combustion temperature of said pyrotechnic compound must not be too high so that the temperature of the gases in the damping cushion remains sufficiently low so as not to harm the physical integrity of the occupant. Preferably, a value of Combustion temperature below 2200 K, ideally below 2000 K, is required. Furthermore, a low combustion temperature makes it possible, on the one hand, to limit the thickness of the bag, on the other hand, to simplify the design of the gas generator by making it possible to reduce the presence of baffles and filters within this one. In the end, the gas generator has a reduced weight and volume, and this at a lower cost;
  7. 7) finally, there are in addition constraints linked to the quantity of solid particles generated by the combustion of the compound, which must remain low. Said solid particles are liable to be expelled out of the gas generator during operation and to constitute hot spots which may damage the internal wall of the airbag.

Ainsi, l'homme du métier est à la recherche de composés pyrotechniques présentant simultanément :

  • une température de combustion modérée (inférieure à 2200 K) ;
  • une vitesse de combustion suffisamment élevée (idéalement supérieure ou égale à 20 mm/s à 20 MPa) avec un faible exposant de pression à moyenne et haute pression (inférieur à 0,5) ;
  • une pression limite de fonctionnement inférieure ou égale à la pression atmosphérique ou, plus avantageusement, une vitesse de combustion non nulle à pression atmosphérique (idéalement supérieure ou égale à 1 mm/s) ;
  • un taux de particules solides générées par la combustion suffisamment faible ;
afin que lesdits composés conviennent pour une utilisation dans des générateurs de gaz entièrement pyrotechniques destinés à des airbags frontaux.Thus, those skilled in the art are looking for pyrotechnic compounds simultaneously exhibiting:
  • a moderate combustion temperature (less than 2200 K);
  • a sufficiently high combustion rate (ideally greater than or equal to 20 mm / s at 20 MPa) with a low pressure exponent at medium and high pressure (less than 0.5);
  • a limit operating pressure less than or equal to atmospheric pressure or, more advantageously, a non-zero combustion rate at atmospheric pressure (ideally greater than or equal to 1 mm / s);
  • a sufficiently low rate of solid particles generated by combustion;
so that said compounds are suitable for use in fully pyrotechnic gas generators for front airbags.

Divers types de composition pyrotechnique, pour l'obtention de composés pyrotechniques générateurs de gaz convenant particulièrement pour une utilisation dans des systèmes de protection d'occupants de véhicules automobiles, ont déjà été proposés à ce jour. Actuellement, pour les airbags frontaux, les composés pyrotechniques qui semblent offrir le meilleur compromis, en termes de température de combustion, de rendement gazeux, de toxicité des gaz de combustion et de sécurité pyrotechnique de mise en œuvre, contiennent, dans leur composition, comme ingrédients principaux du nitrate de guanidine (NG) en tant que charge réductrice et du nitrate basique de cuivre (BCN) en tant que charge oxydante. L'emploi du couple NG/BCN permet l'obtention d'une température de combustion faible, typiquement de l'ordre de 1800 K. Le brevet US 5 608 183 décrit des composés de ce type, obtenus par un procédé de fabrication en voie humide. Ces composés demeurent cependant difficiles à allumer et présentent intrinsèquement une vitesse de combustion au mieux égale à 20 mm/s à 20 MPa.Various types of pyrotechnic composition, for obtaining gas-generating pyrotechnic compounds particularly suitable for use in systems for protecting the occupants of motor vehicles, have already been proposed to date. Currently, for front airbags, the pyrotechnic compounds which seem to offer the best compromise, in terms of combustion temperature, gas yield, toxicity of combustion gases and pyrotechnic safety of implementation, contain, in their composition, as main ingredients of guanidine nitrate (NG) as a reducing filler and basic copper nitrate (BCN) as an oxidizing filler. The use of the NG / BCN couple makes it possible to obtain a low combustion temperature, typically of the order of 1800 K. The patent US 5,608,183 describes compounds of this type obtained by a wet manufacturing process. These compounds, however, remain difficult to ignite and intrinsically exhibit a combustion rate at best equal to 20 mm / s at 20 MPa.

Dans l'optique d'améliorer la vitesse de combustion, on a proposé, selon l'art antérieur, d'incorporer des additifs, à base d'un oxyde de métal de transition, jouant le rôle de catalyseur balistique. De tels additifs sont bien connus de l'homme du métier, en cela qu'ils sont traditionnellement utilisés dans le domaine des propergols (en tant que catalyseur balistique) pour augmenter la vitesse de combustion, aussi bien à basse, moyenne qu'à haute pression. Dans le brevet US 6 143 102 , il est ainsi décrit l'incorporation d'un catalyseur balistique, constitué d'un oxyde choisi parmi Al2O3, TiO2, ZnO, MgO et ZrO2, à un taux massique de 0,5 % jusqu'à 5 %. Dans les demandes de brevet EP 1 342 705 et EP 1 568 673 , des oxydes et hydroxydes métalliques, jouant le rôle de catalyseur balistique (qualifiés d'agent d'ajustement de la combustion) sont aussi cités, tels Cr2O3, MnO2, Fe2O3, Fe3O4, CuO, Cu2O, CoO, V2O5, WO3, ZnO, NiO, Cu(OH)2. Ils peuvent être incorporés jusqu'à 10 % en masse.With a view to improving the combustion rate, it has been proposed, according to the prior art, to incorporate additives, based on a transition metal oxide, playing the role of ballistic catalyst. Such additives are well known to those skilled in the art, in that they are traditionally used in the field of propellants (as a ballistic catalyst) to increase the combustion speed, both at low, medium and high. pressure. In the patent US 6,143,102 , the incorporation of a ballistic catalyst is thus described, consisting of an oxide chosen from Al 2 O 3 , TiO 2 , ZnO, MgO and ZrO 2 , at a mass rate of 0.5% up to 5% . In patent applications EP 1 342 705 and EP 1,568,673 , metal oxides and hydroxides, playing the role of ballistic catalyst (qualified as combustion adjustment agent) are also mentioned, such as Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Fe 3 O 4 , CuO, Cu 2 O, CoO, V 2 O 5 , WO 3 , ZnO, NiO, Cu (OH) 2 . They can be incorporated up to 10% by mass.

Par ailleurs, l'homme du métier sait que les composés pyrotechniques formulés à partir de nitrate basique de cuivre (BCN) présentent comme inconvénient majeur de générer, lors de la combustion, un taux élevé de résidus solides difficilement filtrables. Cette faible filtrabilité provient du fait que les résidus de cuivre, sous forme liquide à la température de combustion dans le générateur de gaz, présentent intrinsèquement une médiocre agglomération et peuvent être aisément entraînés avec le flux des gaz de combustion pour se solidifier en sortie dudit générateur. Les particules solides chaudes résultantes sont alors susceptibles d'endommager la paroi du coussin gonflable. Du fait du taux élevé de BCN dans les composés pyrotechniques décrits précédemment, il est de ce fait nécessaire d'équiper le générateur de gaz d'un système de filtre conséquent afin de garantir un captage satisfaisant des particules de cuivre, ceci au détriment du dimensionnement, du poids et donc du coût du générateur de gaz.Moreover, those skilled in the art know that the pyrotechnic compounds formulated from basic copper nitrate (BCN) have the major drawback of generating, during combustion, a high rate of solid residues which are difficult to filter. This low filterability results from the fact that the copper residues, in liquid form at the combustion temperature in the gas generator, inherently have poor agglomeration and can easily be entrained with the flow of combustion gases to solidify at the outlet of said generator. . The resulting hot solid particles are then liable to damage the wall of the airbag. Due to the high level of BCN in the pyrotechnic compounds described above, it is therefore necessary to equip the gas generator with a substantial filter system in order to guarantee satisfactory capture of the copper particles, to the detriment of the sizing. , the weight and therefore the cost of the gas generator.

En réponse à ce problème technique de captage des particules solides de cuivre, il a été proposé, selon l'art antérieur, d'incorporer, dans la composition des composés pyrotechniques, un additif (agent « slaggant » ou « agent agglomérant ») qui a pour fonction d'agglomérer les résidus de cuivre générés par la combustion. Il en résulte, en fin de combustion, un agglomérat se présentant sous la forme d'un squelette du bloc pyrotechnique initial, lequel peut alors être plus facilement capté par le système de filtration du générateur de gaz. Ainsi, le brevet US 6 143 102 et les demandes de brevet EP 1 342 705 et EP 1 568 673 décrivent aussi l'emploi d'un agent agglomérant, tels SiO2, Si3N4, SiC ou l'argile, en sus d'un additif catalyseur balistique, à un taux massique pouvant également aller de 0,5 % à 5 %, voire 10 %.In response to this technical problem of capturing solid copper particles, it has been proposed, according to the prior art, to incorporate, in the composition of pyrotechnic compounds, an additive (“slaggant” or “agglomerating agent”) which has the function of agglomerating the copper residues generated by combustion. This results, at the end of the combustion, in an agglomerate in the form of a skeleton of the initial pyrotechnic block, which can then be more easily captured by the filtration system of the gas generator. Thus, the patent US 6,143,102 and patent applications EP 1 342 705 and EP 1,568,673 also describe the use of an agglomerating agent, such as SiO 2 , Si 3 N 4 , SiC or clay, in addition to a ballistic catalyst additive, at a mass rate which may also range from 0.5% to 5% or even 10%.

Au final, selon l'enseignement dudit brevet US 6 143 102 et desdites demandes de brevet EP 1 342 705 et EP 1 568 673 , le premier additif (jouant le rôle de catalyseur balistique) et le second additif (assurant l'agglomération des résidus de cuivre) peuvent représenter jusqu'à 10 %, voire 15 %, en masse de la composition du composé, ce qui contribue à une diminution préjudiciable de la valeur de rendement gazeux de ladite composition.In the end, according to the teaching of the said patent US 6,143,102 and said patent applications EP 1 342 705 and EP 1,568,673 , the first additive (playing the role of ballistic catalyst) and the second additive (ensuring the agglomeration of copper residues) can represent up to 10%, or even 15%, by mass of the composition of the compound, which contributes to a detrimental decrease in the gas yield value of said composition.

Selon une autre approche, dans le but notamment d'améliorer la rétention des résidus solides, on a proposé, selon l'art antérieur, de diminuer la température de combustion et/ou le taux de BCN au profit d'une autre charge oxydante. Les demandes de brevet EP 0 949 225 et EP 1 006 096 décrivent ainsi des compositions qui renferment, comme ingrédients principaux, une charge réductrice consistant en ou contenant un dérivé de la guanidine et une charge oxydante contenant du BCN et un oxyde métallique, associés à un chlorate, perchlorate et/ou nitrate. L'oxyde métallique, introduit à un taux massique élevé (20 à 70 %, voire 80 %, en masse de la masse totale de charge oxydante), joue le rôle de charge oxydante à part entière. Il contribue à régler globalement la balance en oxygène de la composition. Ledit oxyde métallique consiste généralement en CuO mais d'autres oxydes tels Cr2O3 et MnO2 sont cités.According to another approach, with the aim in particular of improving the retention of solid residues, it has been proposed, according to the prior art, to reduce the combustion temperature and / or the level of BCN in favor of another oxidizing charge. Patent applications EP 0 949 225 and EP 1 006 096 thus describe compositions which contain, as main ingredients, a reducing charge consisting of or containing a guanidine derivative and an oxidizing charge containing BCN and a metal oxide, associated with a chlorate, perchlorate and / or nitrate. The metal oxide, introduced at a high mass rate (20 to 70%, or even 80%, by mass of the total mass of oxidizing charge), acts as an oxidizing charge in its own right. It helps to regulate the overall oxygen balance of the composition. Said metal oxide generally consists of CuO but other oxides such as Cr 2 O 3 and MnO 2 are mentioned.

L'art antérieur décrit donc des compositions de composés pyrotechniques générateurs de gaz incorporant, comme ingrédients principaux, NG et BCN et renfermant deux types d'additifs : un catalyseur de combustion (constitué d'un oxyde métallique) et un agent agglomérant (comme le SiO2, le nitrure ou carbure de silicium). Il décrit aussi des compositions renfermant NG et BCN ainsi qu'un taux élevé d'oxyde métallique, à titre de charge oxydante de substitution (partielle, voire totale) audit BCN.The prior art therefore describes compositions of pyrotechnic gas-generating compounds incorporating, as main ingredients, NG and BCN and containing two types of additives: a combustion catalyst (consisting of a metal oxide) and an agglomerating agent (such as SiO 2 , nitride or silicon carbide). It also describes compositions containing NG and BCN as well as a high level of metal oxide, as a substitution oxidizing charge (partial, or even total) for said BCN.

Par ailleurs, des compositions pouvant incorporer un dérivé du strontium, tel SrO, SrCO3, Sr(OH)2 ou SrTiO3, sont décrites dans la demande de brevet JP 2009 137 821 . Ces compositions contiennent un réducteur, un oxydant, un liant, un agent phosphoré de réduction de la température de combustion et un dérivé du strontium dont le rôle est de limiter la production d'oxyde de phosphore lors de la combustion. Des additifs du type de ceux précédemment cités peuvent aussi être présents dans ces compositions. Ces compositions ne sont pas du type de celles de l'invention. L'enseignement de ce document ne suggère en rien la bi-fonction du SrTiO3 au sein des compositions des composés de l'invention (voir ci-après).Furthermore, compositions which can incorporate a strontium derivative, such as SrO, SrCO 3 , Sr (OH) 2 or SrTiO 3 , are described in the patent application. JP 2009 137 821 . These compositions contain a reducing agent, an oxidizing agent, a binder, a phosphorus-containing agent for reducing the combustion temperature and a strontium derivative whose role is to limit the production of phosphorus oxide during combustion. Additives of the type of those mentioned above can also be present in these compositions. These compositions are not of the type of those of the invention. The teaching of this document in no way suggests the bi-function of SrTiO 3 within the compositions of the compounds of the invention (see below).

En partant des performances connues des mélanges nitrate de guanidine (NG) / nitrate basique de cuivre (BCN), les inventeurs ont souhaité proposer des composés pyrotechniques améliorés (des objets pyrotechniques améliorés), convenant tout particulièrement pour une utilisation dans les airbags frontaux. Plus précisément, les inventeurs ont souhaité proposer des composés pyrotechniques dans la composition desquels la présence d'un unique (type d') additif bi-fonctionnel (à un faible taux, i.e. avec une incidence limitée sur le rendement gazeux) permet de satisfaire conjointement au problème technique de l'agglomération des résidus de combustion et à celui de l'obtention d'une vitesse de combustion élevée (en l'occurrence au moins aussi élevée que celle des composés de l'art antérieur décrits dans le brevet US 6 143 102 ).On the basis of the known performances of guanidine nitrate (NG) / basic copper nitrate (BCN) mixtures, the inventors wished to propose improved pyrotechnic compounds (improved pyrotechnic objects), particularly suitable for use in front airbags. More precisely, the inventors wished to propose pyrotechnic compounds in the composition of which the presence of a single (type of) bi-functional additive (at a low rate, ie with a limited impact on the gas yield) makes it possible to jointly satisfy the technical problem of the agglomeration of combustion residues and that of obtaining a high combustion speed (in this case at least as high as that of the compounds of the prior art described in the patent US 6,143,102 ).

Il a été constaté que la présence, au sein de la composition des composés de l'invention, d'un faible taux (faible pourcentage massique) d'un seul type d'additif (avantageusement d'un unique additif de ce type), à caractère réfractaire, a permis de répondre au souci d'amélioration recherché par les inventeurs à savoir l'obtention conjointe d'un effet d'agglomération des résidus de combustion du BCN et d'une vitesse de combustion élevée (aussi élevée que celle des composés de l'art antérieur), tout en conservant une température de combustion modérée.It has been observed that the presence, within the composition of the compounds of the invention, of a low rate (low percentage by mass) of a single type of additive (advantageously of a single additive of this type), refractory, made it possible to respond to the concern for improvement sought by the inventors, namely to obtain jointly an agglomeration effect of the combustion residues of the BCN and a speed of high combustion (as high as that of the compounds of the prior art), while maintaining a moderate combustion temperature.

Ainsi, la composition (précisée ci-après) des composés (objets) pyrotechniques générateurs de gaz de la présente invention (convenant tout particulièrement pour des applications airbag frontaux) renferment :

  • du nitrate de guanidine (en tant que charge réductrice),
  • du nitrate basique de cuivre (en tant que charge oxydante), et
  • au moins (un additif bi-fonctionnel consistant en) un titanate inorganique dont la température de fusion est supérieure à 2100 K.
Thus, the composition (specified below) of the pyrotechnic gas-generating compounds (objects) of the present invention (particularly suitable for front airbag applications) contain:
  • guanidine nitrate (as reducing filler),
  • basic copper nitrate (as an oxidizing charge), and
  • at least (a bi-functional additive consisting of) an inorganic titanate with a melting point above 2100 K.

Les composés (objets) solides pyrotechniques générateurs de gaz de l'invention sont du type à base conventionnelle NG/BCN et leur composition renferme, de façon caractéristique, au moins un titanate inorganique dont la température de fusion est supérieure à 2100 K. Ledit au moins un titanate inorganique joue le rôle d'agent d'agglomération des résidus solides de combustion et de catalyseur balistique.The solid pyrotechnic gas-generating compounds (objects) of the invention are of the conventional NG / BCN-based type and their composition typically contains at least one inorganic titanate the melting point of which is greater than 2100 K. Said at less one inorganic titanate acts as an agglomeration agent for solid combustion residues and as a ballistic catalyst.

Ledit au moins un titanate est un composé réfractaire, dont la température de fusion (supérieure à 2100 K) est significativement supérieure aux températures de combustion des bases NG/BCN dans lesquelles il est présent. Ainsi, il conserve son état physique de solide pulvérulent (il intervient évidemment sous cette forme) à la température de combustion, caractéristique nécessaire à l'obtention d'un effet d'agglomération des résidus liquide de cuivre.Said at least one titanate is a refractory compound, the melting point of which (greater than 2100 K) is significantly higher than the combustion temperatures of the NG / BCN bases in which it is present. Thus, it retains its physical state as a pulverulent solid (it obviously occurs in this form) at the combustion temperature, a characteristic necessary to obtain an effect of agglomeration of the liquid copper residues.

A l'appui de l'affirmation ci-dessus selon laquelle ledit au moins un titanate est un composé réfractaire, dont la température de fusion est significativement supérieure aux températures de combustion des bases NG/BCN dans lesquelles il est présent, on précise ce qui suit. La température de combustion d'une quelconque base NG/BCN est en effet toujours inférieure à 1950 K. A titre d'illustration, on peut indiquer ici qu'une base NG (53,7 % en masse)/BCN (46,3 % en masse), présentant une valeur de balance en oxygène de -3,3 %, a une température de combustion de 1940 K à 20 MPa et de 1941 K à 50 MPa. La température maximale de combustion d'une base NG/BCN est obtenue pour un ratio de 53,5 % en masse de NG et de 46,5 % en masse de BCN, présentant une valeur de balance en oxygène de -3,2 %, elle a pour valeur 1942 K à 20 MPa, 1943 K à 50 MPa. Ceci confirmant par ailleurs le fait que la température de combustion n'est susceptible de varier que de quelques degrés Kelvin avec la pression de fonctionnement du générateur de gaz, et reste toujours inférieure à 1950 K, quelle que soit la pression de fonctionnement du générateur de gaz. Ainsi la valeur exigée, supérieure à 2100 K, pour la température de fusion dudit au moins un titanate (additif bi-fonctionnel original des compositions des composés de l'invention) est-elle toujours significativement supérieure (d'au moins 150 K) à la valeur maximale de combustion d'une base NG/BCN.In support of the above assertion that said at least one titanate is a refractory compound, the melting point of which is significantly higher than the combustion temperatures of the NG / BCN bases in which it is present, it is specified what follows. The combustion temperature of any NG / BCN base is in fact always less than 1950 K. By way of illustration, we can indicate here that an NG (53.7% by mass) / BCN base (46.3 % by mass), exhibiting an oxygen balance value of -3.3%, has a combustion temperature of 1940 K at 20 MPa and 1941 K at 50 MPa. The maximum combustion temperature of an NG / BCN base is obtained for a ratio of 53.5% by mass of NG and 46.5% by mass of BCN, exhibiting an oxygen balance value of -3.2% , its value is 1942 K at 20 MPa, 1943 K at 50 MPa. This further confirms the fact that the combustion temperature is only likely to vary by a few degrees Kelvin with the operating pressure of the gas generator, and always remains below 1950 K, whatever the operating pressure of the gas generator. gas. Thus the required value, greater than 2100 K, for the melting point of said at least one titanate (original bi-functional additive of the compositions of the compounds of the invention) is always significantly higher (by at least 150 K) than the maximum combustion value of an NG / BCN base.

Le au moins un titanate inorganique, dont la température de fusion est supérieure à 2100 K, présent dans la composition des composés de l'invention, est avantageusement choisi parmi les titanates métalliques, les titanates d'alcalino-terreux et leurs mélanges. Il consiste très avantageusement en un titanate métallique ou un titanate d'alcalino-terreux.The at least one inorganic titanate, the melting point of which is greater than 2100 K, present in the composition of the compounds of the invention, is advantageously chosen from metal titanates, alkaline earth titanates and their mixtures. It very advantageously consists of a metal titanate or an alkaline earth titanate.

De façon préférée, la composition des composés de l'invention renferme du titanate de strontium (SrTiO3) et/ou du titanate de calcium (CaTiO3) et/ou du titanate d'aluminium (Al2TiO5). De façon particulièrement préférée, elle renferme du titanate de strontium (SrTiO3), du titanate de calcium (CaTiO3) ou du titanate d'aluminium (Al2TiO5).Preferably, the composition of the compounds of the invention contains strontium titanate (SrTiO 3 ) and / or calcium titanate (CaTiO 3 ) and / or aluminum titanate (Al 2 TiO 5 ). Particularly preferably, it contains strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ) or aluminum titanate (Al 2 TiO 5 ).

Le au moins un additif bi-fonctionnel de l'invention (titanate inorganique) présent l'est entre 1 et 5 % (bornes comprises) en masse, avantageusement entre 2 à 4 % en masse (bornes comprises), au sein de la composition (massique) des composés de l'invention.The at least one bifunctional additive of the invention (inorganic titanate) present is between 1 and 5% (limits included) by mass, advantageously between 2 and 4% by mass (limits included), within the composition (by weight) of the compounds of the invention.

La composition des composés de l'invention est généralement exempte de liant (variante préférée). En effet, le comportement rhéo-plastique du nitrate de guanidine rend a priori la présence d'un quelconque liant superflu, notamment pour l'obtention, par voie sèche, d'objets pyrotechniques formés, de granulés, de pastilles et de blocs monolithes comprimés (voir ci-après). On ne saurait toutefois absolument exclure la présence d'un tel liant. Les composés de l'invention incorporant un liant peuvent notamment exister sous la forme de blocs monolithes obtenus par extrusion, éventuellement en voie humide.The composition of the compounds of the invention is generally free of binder (preferred variant). Indeed, the rheo-plastic behavior of guanidine nitrate a priori makes the presence of any binder superfluous, in particular for obtaining, by dry process, formed pyrotechnic objects, granules, pellets and compressed monolith blocks. (see below). However, the presence of such a binder cannot be completely excluded. The compounds of the invention incorporating a binder can in particular exist in the form of monolithic blocks obtained by extrusion, optionally in the wet process.

Les ingrédients des trois types ci-dessus (nitrate de guanidine, nitrate basique de cuivre, additif(s) bi-fonctionnel(s) = titanate(s) inorganique(s)) représentent généralement plus de 99,5 % en masse de la composition du composé pyrotechnique. Les ingrédients des trois types ci-dessus peuvent tout à fait représenter 100 % en masse de la masse totale des composés de l'invention. L'éventuelle présence d'au moins un autre additif, choisi, par exemple parmi les auxiliaires de fabrication (stéarate de calcium, graphite, silice notamment), est expressément prévue, à un taux inférieur à 0,5 % en masse. Un tel au moins un autre additif ne consiste pas en un liant. Les ingrédients des trois types ci-dessus (nitrate de guanidine, nitrate basique de cuivre, additif(s) bi-fonctionnel(s)) représentent donc généralement plus de 99,5 % en masse de la composition du composé pyrotechnique qui est exempte de liant.The ingredients of the three types above (guanidine nitrate, basic copper nitrate, bi-functional additive (s) = inorganic titanate (s)) generally represent more than 99.5% by mass of the composition of the pyrotechnic compound. The ingredients of the three types above can quite represent 100% by mass of the total mass of the compounds of the invention. The possible presence of at least one other additive, chosen, for example, from processing aids (calcium stearate, graphite, silica in particular), is expressly provided for, at a rate of less than 0.5% by mass. Such at least one other additive does not consist of a binder. The ingredients of the three types above (guanidine nitrate, basic copper nitrate, bi-functional additive (s)) therefore generally represent more than 99.5% by mass of the composition of the pyrotechnic compound which is free from binder.

La composition des composés de l'invention renferme, exprimée en pourcentages massiques :

  • de 45 à 60 % de nitrate de guanidine,
  • de 37 à 52 % de nitrate basique de cuivre, et
  • de 1 à 5 %, avantageusement 2 à 4 %, d'au moins un titanate inorganique dont la température de fusion est supérieure à 2100 K (additif bi-fonctionnel).
Une telle composition est, comme indiqué ci-dessus, généralement exempte de liant (variante préférée).The composition of the compounds of the invention contains, expressed in percentages by mass:
  • from 45 to 60% of guanidine nitrate,
  • from 37 to 52% basic copper nitrate, and
  • from 1 to 5%, advantageously 2 to 4%, of at least one inorganic titanate whose melting point is greater than 2100 K (bifunctional additive).
Such a composition is, as indicated above, generally free of binder (preferred variant).

Les additifs bi-fonctionnels préférés selon l'invention, le titanate de strontium (SrTiO3), le titanate de calcium (CaTiO3), et le titanate d'aluminium (Al2TiO5), ont donc un caractère réfractaire (leur température de fusion est, respectivement, de 2353 K, 2248 K et 2133 K, i.e. significativement supérieure à la température de combustion de la base NG/BCN, qui est toujours elle inférieure à 1950 K (voir ci-dessus)). Ainsi, ces additifs conservent leur état physique de solide pulvérulent (ils interviennent évidemment sous cette forme) à la température de combustion de la composition, caractéristique nécessaire à l'obtention d'un effet d'agglomération des résidus liquide de cuivre.The preferred bi-functional additives according to the invention, strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ), and aluminum titanate (Al 2 TiO 5 ), therefore have a refractory character (their temperature melting temperature is, respectively, 2353 K, 2248 K and 2133 K, ie significantly higher than the combustion temperature of the NG / BCN base, which is always lower than 1950 K (see above)). Thus, these additives retain their physical state as a pulverulent solid (they obviously occur in this form) at the combustion temperature of the composition, a characteristic necessary to obtain an agglomeration effect of the liquid copper residues.

On comprend donc que, dans le cadre de la présente invention, la double fonction de l'additif est d'une part, d'agglomérer de façon suffisante les résidus de combustion (ceci en augmentant la viscosité de la phase condensée constituée de cuivre liquide) afin de faciliter leur filtrabilité (en vue de pouvoir réduire les systèmes de filtration du générateur de gaz), et d'autre part, de conférer au composé pyrotechnique les propriétés balistiques nécessaires au besoin fonctionnel, à savoir :

  • une vitesse de combustion égale, voire supérieure, à celle des composés de l'art antérieur ;
  • un exposant de pression faible ;
  • une combustion non nulle et auto-entretenue à pression atmosphérique.
It is therefore understood that, in the context of the present invention, the dual function of the additive is, on the one hand, to sufficiently agglomerate the combustion residues (this by increasing the viscosity of the condensed phase consisting of liquid copper ) in order to facilitate their filterability (in order to be able to reduce the filtration systems of the gas generator), and on the other hand, to give the pyrotechnic compound the ballistic properties necessary for the functional need, namely:
  • a combustion rate equal or even greater than that of the compounds of the prior art;
  • a low pressure exponent;
  • non-zero and self-sustaining combustion at atmospheric pressure.

De façon préférée, ledit au moins un additif bi-fonctionnel se présente sous une forme pulvérulente fine (de dimension micrométrique, avantageusement de dimension nanométrique) : avec un diamètre médian inférieur à 5 µm, avantageusement inférieur à 1 µm. Il présente avantageusement une surface spécifique supérieure à 1 m2/g (avantageusement supérieure à 5 m2/g ou plus).Preferably, said at least one bifunctional additive is in a fine pulverulent form (of micrometric dimension, advantageously of nanometric dimension): with a median diameter of less than 5 μm, advantageously of less than 1 μm. It advantageously has a specific surface area greater than 1 m 2 / g (advantageously greater than 5 m 2 / g or more).

Le nitrate de guanidine est préféré comme réducteur, entre-autres pour des raisons de sécurité pyrotechnique et pour son comportement rhéo-plastique, adapté à la mise en oeuvre des phases de compactage et de pastillage d'un procédé voie sèche (voir ci-après), assurant une bonne densification de la composition pyrotechnique pulvérulente de départ tout en limitant l'effort de compression à appliquer. La fabrication de composés de l'invention par un procédé voie sèche peut comprendre jusqu'à quatre étapes principales (voir ci-après), qui ont notamment été décrites dans la demande brevet WO 2006/134311 .Guanidine nitrate is preferred as a reducing agent, among others for reasons of pyrotechnic safety and for its rheoplastic behavior, suitable for the implementation of the compacting and pelletizing phases of a dry process (see below ), ensuring good densification of the starting powder pyrotechnic composition while limiting the compressive force to be applied. The manufacture of compounds of the invention by a dry process can comprise up to four main steps (see below), which have in particular been described in the patent application. WO 2006/134311 .

Le au moins un additif (bi-fonctionnel, choisi parmi les titanates inorganiques dont la température de fusion est supérieure à 2100 K) intervient avantageusement avec les autres ingrédients constitutifs, NG + BCN principalement, voire exclusivement (au début du procédé de fabrication) ou est ajouté, plus en aval, dans le procédé de fabrication des composés de l'invention.The at least one additive (bifunctional, chosen from inorganic titanates whose melting point is greater than 2100 K) is advantageously involved with the other constituent ingredients, NG + BCN mainly, or even exclusively (at the start of the manufacturing process) or is added, more downstream, in the manufacturing process of the compounds of the invention.

Les composés pyrotechniques de l'invention peuvent également être obtenus suivant un procédé voie humide. Selon une variante, ledit procédé comprend l'extrusion d'une pâte contenant les constituants du composé. Selon une autre variante, ledit procédé inclut une étape de mise en solution aqueuse de tous ou certains constituants principaux comprenant une solubilisation d'au moins l'un des constituants principaux (réducteur) puis l'obtention d'une poudre par séchage par atomisation, l'ajout à la poudre obtenue du ou des constituants qui n'ont pas été mis en solution, puis la mise en forme de la poudre sous la forme d'objets par les procédés usuels en voie sèche.The pyrotechnic compounds of the invention can also be obtained by a wet process. According to one variant, said method comprises the extrusion of a paste containing the constituents of the compound. According to another variant, said method includes a step of dissolving all or some main constituents in aqueous solution comprising a solubilization of at least one of the main constituents (reducing agent) and then obtaining a powder by spray drying, the addition to the powder obtained of the constituent (s) which have not been added in solution, then shaping the powder in the form of objects by the usual dry process.

Le procédé d'obtention préférentiel des composés pyrotechniques de l'invention (procédé par voie sèche) inclut une étape de compactage à sec d'un mélange des ingrédients constitutifs en poudre desdits composés (excepté, éventuellement, ledit au moins un additif qui peut être ajouté plus tard). Le compactage à sec est généralement mis en œuvre, de façon connue per se, dans un compacteur à cylindres, à une pression de compactage comprise entre 108 et 6.108 Pa. Il peut être mis en œuvre selon différentes variantes (avec une étape caractéristique de compactage "simple" suivie d'au moins une étape complémentaire ou avec une étape caractéristique de compactage couplée à une étape de mise en forme).The preferential process for obtaining the pyrotechnic compounds of the invention (dry process) includes a dry compacting stage of a mixture of powdered constituent ingredients of said compounds (except, optionally, said at least one additive which can be added later). Dry compaction is generally carried out, in a manner known per se , in a roller compactor, at a compaction pressure of between 10 8 and 6.10 8 Pa. It can be carried out according to different variants (with a characteristic step "simple" compaction followed by at least one complementary step or with a characteristic compacting step coupled with a shaping step).

Ainsi, les composés pyrotechniques (objets pyrotechniques) de l'invention sont susceptibles d'exister sous différentes formes (notamment au fil du procédé de fabrication conduisant aux composés finaux):

  • à l'issue d'un compactage à sec couplé à une mise en forme (par utilisation d'au moins un cylindre de compactage, dont la surface externe présente des alvéoles), on obtient des plaques avec motifs en relief que l'on peut casser pour l'obtention directe d'objets pyrotechniques formés ;
  • à l'issue d'un compactage à sec (compactage "simple") suivi d'une granulation, on obtient des granulés ;
  • à l'issue d'un compactage à sec (compactage "simple") suivi d'une granulation puis d'un pastillage (compression à sec), on obtient des pastilles ou des blocs monolithiques comprimés ;
  • à l'issue d'un compactage à sec (compactage "simple") suivi d'une granulation puis du mélange des granulés obtenus avec un liant extrudable et de l'extrusion dudit liant chargé en lesdits granulés, on obtient des blocs monolithiques extrudés (chargés avec lesdits granulés).
On comprend que cette variante de procédé n'est pas préférée dans la mesure où elle fait intervenir un liant.Thus, the pyrotechnic compounds (pyrotechnic objects) of the invention are likely to exist in different forms (in particular during the manufacturing process leading to the final compounds):
  • at the end of a dry compaction coupled with a shaping (by using at least one compacting cylinder, the outer surface of which has cells), plates are obtained with patterns in relief that can be breaking for direct obtaining of formed pyrotechnic objects;
  • after dry compaction (“simple” compaction) followed by granulation, granules are obtained;
  • after dry compaction ("simple" compaction) followed by granulation and then pelletizing (dry compression), compressed monolithic pellets or blocks are obtained;
  • at the end of dry compaction ("simple" compaction) followed by granulation and then mixing the granules obtained with an extrudable binder and the extrusion of said binder loaded with said granules, extruded monolithic blocks are obtained ( loaded with said granules).
It will be understood that this variant of the process is not preferred insofar as it involves a binder.

Les composés pyrotechniques de l'invention sont donc notamment susceptibles d'exister sous la forme d'objets de type:

  • granulés ;
  • pastilles ;
  • blocs monolithes (comprimés ou extrudés, avantageusement comprimés.).
The pyrotechnic compounds of the invention are therefore particularly likely to exist in the form of objects of the type:
  • granules;
  • lozenges ;
  • monolithic blocks (compressed or extruded, advantageously compressed.).

Les composés pyrotechniques de l'invention peuvent aussi être obtenus en voie sèche par simple pastillage de la poudre obtenue par mélange de leurs constituants.The pyrotechnic compounds of the invention can also be obtained in the dry process by simple pelletizing of the powder obtained by mixing their constituents.

De façon nullement limitative, on peut indiquer ici :

  • que les granulés de l'invention présentent généralement une granulométrie (un diamètre médian) comprise entre 200 et 1000 µm (ainsi qu'une masse volumique apparente comprise entre 0,8 et 1,2 g/cm3) ;
  • que les pastilles de l'invention présentent généralement une épaisseur comprise entre 1 et 6 mm.
In no way limiting, we can indicate here:
  • that the granules of the invention generally have a particle size (a median diameter) of between 200 and 1000 μm (as well as an apparent density of between 0.8 and 1.2 g / cm 3 );
  • that the pellets of the invention generally have a thickness of between 1 and 6 mm.

Lorsque les composés de l'invention sont obtenus par un procédé en voie sèche, les ingrédients constitutifs des composés de l'invention présentent avantageusement une granulométrie fine, inférieure ou égale à 20 µm. Ladite granulométrie (valeur du diamètre médian) est généralement comprise entre 1 et 20 µm. Les composés décrits dans la présente invention expriment tout leur potentiel s'ils sont obtenus par un procédé en voie sèche à partir de poudres présentant un diamètre médian compris entre 5 à 15 µm pour le nitrate de guanidine, entre 2 à 7 µm pour le nitrate basique de cuivre et entre 0,5 à 5 µm pour le au moins un additif bi-fonctionnel.When the compounds of the invention are obtained by a dry process, the constituent ingredients of the compounds of the invention advantageously have a fine particle size, less than or equal to 20 μm. Said particle size (value of the median diameter) is generally between 1 and 20 μm. The compounds described in the present invention express their full potential if they are obtained by a dry process from powders having a median diameter of between 5 to 15 μm for guanidine nitrate, between 2 to 7 μm for nitrate. basic copper and between 0.5 to 5 µm for the at least one bi-functional additive.

Selon un autre de ses objets, la présente invention concerne une composition pulvérulente (mélange de poudres), précurseur d'un composé de l'invention, dont la composition correspond donc à celle d'un composé de l'invention (voir ci-dessus).According to another of its objects, the present invention relates to a pulverulent composition (mixture of powders), precursor of a compound of the invention, the composition of which therefore corresponds to that of a compound of the invention (see above).

Selon un autre de ses objets, la présente invention concerne les générateurs de gaz renfermant un chargement solide pyrotechnique générateur de gaz ; ledit chargement contenant au moins un composé pyrotechnique de l'invention. Lesdits générateurs, chargés notamment en pastilles de l'invention, conviennent parfaitement pour les airbags, notamment frontaux (voir ci-dessus).According to another of its objects, the present invention relates to gas generators containing a pyrotechnic solid charge which generates gas; said charge containing at least one pyrotechnic compound of the invention. Said generators, loaded in particular with pellets of the invention, are perfectly suitable for airbags, in particular front airbags (see above).

On se propose maintenant d'illustrer, de façon nullement limitative, l'invention.It is now proposed to illustrate, in no way limiting, the invention.

A. Le tableau 1 ci-après présente trois exemples (Ex.1, Ex.2 et Ex.3) de composition de composés de la présente invention, ainsi que les performances desdits composés comparées à celles d'un composé de l'art antérieur (Réf.1) selon US 6 143 102 (lesdits composés de l'invention et de l'art antérieur ont été fabriqués via un procédé voie sèche). A. Table 1 below shows three examples (Ex.1, Ex.2 and Ex.3) of the composition of compounds of the present invention, as well as the performances of said compounds compared to those of a compound of the art previous (Ref. 1) according to US 6,143,102 (said compounds of the invention and of the prior art were produced by a dry process).

Les composés ont été évalués au moyen de calculs thermodynamiques ou à partir de mesures physiques menées sur des granulés ou pastilles fabriqués à partir des compositions via le procédé de mélange de poudres - compactage - granulation - et éventuellement pastillage en voie sèche.The compounds were evaluated by means of thermodynamic calculations or from physical measurements carried out on granules or pellets made from the compositions via the process of mixing powders - compacting - granulation - and optionally dry pelletizing.

Le composé de référence 1 (Réf.1) de l'art antérieur renferme du nitrate de guanidine, du nitrate basique de cuivre ainsi qu'un oxyde d'aluminium (Al2O3) en tant que catalyseur balistique et de la silice (SiO2) en tant qu'additif agglomérant (additif « slaggant »).The reference compound 1 (Ref. 1) of the prior art contains guanidine nitrate, basic copper nitrate as well as an aluminum oxide (Al 2 O 3 ) as a ballistic catalyst and silica ( SiO 2 ) as an agglomerating additive (“slaggant” additive).

Les composés des exemples 1 à 3 renferment dans leur composition, en plus des deux constituants nitrate de guanidine et nitrate basique de cuivre de la référence 1, un unique additif bi-fonctionnel tel que décrit dans la présente invention.The compounds of Examples 1 to 3 contain in their composition, in addition to the two components guanidine nitrate and basic copper nitrate of reference 1, a single bifunctional additive as described in the present invention.

Les taux des constituants ont été ajustés afin de conserver une valeur de balance en oxygène proche de -3,3%, de manière à pouvoir directement comparer les performances de ces composés.The levels of the constituents were adjusted in order to keep an oxygen balance value close to -3.3%, so as to be able to directly compare the performance of these compounds.

Les résultats des exemples 1 et 2 du tableau 1 montrent que l'ajout, à un taux modéré (teneur massique de 4%), d'un additif, titanate de strontium (SrTiO3) ou titanate de calcium (CaTiO3), dans une composition du type de celle du composé de référence 1, conduit à l'obtention de résidus de combustion agglomérés (sous la forme d'un squelette du bloc pyrotechnique) et, à une valeur de vitesse de combustion sur la plage de pression 10 MPa - 20 MPa supérieure à, une valeur d'exposant de pression plus faible que, une valeur de débit surfacique de gonflage plus élevée que, celles du composé de référence 1 de l'art antérieur.The results of Examples 1 and 2 of Table 1 show that the addition, at a moderate rate (mass content of 4%), of an additive, strontium titanate (SrTiO 3 ) or calcium titanate (CaTiO 3 ), in a composition of the type of that of reference compound 1, leads to the production of agglomerated combustion residues (in the form of a skeleton of the pyrotechnic block) and, to a combustion rate value over the pressure range 10 MPa - 20 MPa greater than a pressure exponent value lower than an inflation surface flow rate higher than those of the reference compound 1 of the prior art.

Les résultats de l'exemple 3 du tableau 1 montrent que l'ajout, à un taux abaissé (teneur massique de 2,7%) de titanate de calcium (CaTiO3) par rapport à l'exemple 2 (teneur massique de 4%), améliore les performances (accroissement de la valeur de vitesse de combustion sur la plage 10-20 MPa, de la valeur de rendement gazeux et au final de la valeur de débit surfacique de gonflage) par rapport à celles du composé selon l'exemple 2, tout en permettant de conserver une qualité d'agglomération des résidus de combustion répondant de manière satisfaisante au besoin fonctionnel. Tableau 1 Exemples Réf. 1 Ex. 1 Ex. 2 Ex. 3 Ingrédients Nitrate de Guanidine (NG) % 52,3 52 52 52,7 Nitrate Basique de Cuivre (BCN) % 44,5 44 44 44,6 Alumine (Al2O3) % 2,7 - - - Silice (SiO2) % 0,5 - - - Titanate de strontium (SrTiO3) 4 - - Titanate de calcium (CaTiO3) % - - 4 2.7 Caractéristiques Balance en oxygène % -3,3 -3,3 -3,3 -3,3 Température de combustion à 20 MPa K 1897 1889 1892 1905 Densité g/cm3 1,99 2,01 2,00 1,98 Rendement qazeux à 1bar - 1000 K mole/kg 29,4 29,2 29.2 29.6 Taux de résidus à 1bar - 1000 K % 26,7 27,3 27,3 26,3 Vitesse de combustion à 10 MPa 16,3 16,5 16,6 17,0 Vitesse de combustion à 20 MPa mm/s 21,3 22,7 21,8 22,5 Exposant de pression (plage 7 à 35 MPa) 0,37 0,28 0,23 0,20 Vitesse de combustion à pression atmosphérique (1) mm/s 1,2 1,1 1,0 1,0 Débit surfacique de gonflage (ρ x n x Tc x Vc) à 20 MPa mole.K/cm2.s 236 252 241 251 Aspect aggloméré des résidus de combustion sous la forme d'un squelette du bloc pyrotechnique (2) oui oui oui oui (1) valeur mesurée sur granulés en enceinte manométrique (en paille strand burner)
(2) après tirs en enceinte manométrique 40 cm3 ; composé pyrotechnique sous forme initiale de pastilles de diamètre 6,35 mm et d'épaisseur 2,1 mm. The results of Example 3 of Table 1 show that the addition, at a reduced rate (mass content of 2.7%) of calcium titanate (CaTiO 3 ) compared to Example 2 (mass content of 4% ), improves the performances (increase of the combustion speed value over the range 10-20 MPa, of the gas yield value and ultimately of the inflation surface flow value) compared to those of the compound according to the example 2, while making it possible to maintain a quality of agglomeration of combustion residues satisfying the functional need. <u> Table 1 </u> Examples Ref. 1 Ex. 1 Ex. 2 Ex. 3 Ingredients Guanidine nitrate (NG) % 52.3 52 52 52.7 Basic Copper Nitrate (BCN) % 44.5 44 44 44.6 Alumina (Al 2 O 3 ) % 2.7 - - - Silica (SiO 2 ) % 0.5 - - - Strontium titanate (SrTiO 3 ) 4 - - Calcium titanate (CaTiO 3 ) % - - 4 2.7 Characteristics Oxygen balance % -3.3 -3.3 -3.3 -3.3 Combustion temperature at 20 MPa K 1897 1889 1892 1905 Density g / cm 3 1.99 2.01 2.00 1.98 Gas yield at 1bar - 1000 K mole / kg 29.4 29.2 29.2 29.6 Residue rate at 1bar - 1000 K % 26.7 27.3 27.3 26.3 Burning rate at 10 MPa 16.3 16.5 16.6 17.0 Burn rate at 20 MPa mm / s 21.3 22.7 21.8 22.5 Pressure exponent (range 7 to 35 MPa) 0.37 0.28 0.23 0.20 Burning rate at atmospheric pressure (1) mm / s 1.2 1.1 1.0 1.0 Surface inflation rate (ρ xnx T c x V c ) at 20 MPa mole.K / cm 2 .s 236 252 241 251 Agglomerated appearance of combustion residues in the form of a skeleton of the pyrotechnic block (2) Yes Yes Yes Yes (1) value measured on granules in a manometric chamber (in strand burner straw)
(2) after firing in a 40 cm 3 manometric chamber; pyrotechnic compound in the initial form of pellets with a diameter of 6.35 mm and a thickness of 2.1 mm.

B. Le tableau 2 ci-après démontre que l'apport bénéfique observé avec le titanate de strontium ou le titanate de calcium est bien le résultat d'une sélection et ne peut être obtenu de façon systématique par l'emploi d'un quelconque constituant réfractaire (également autre que les constituants décrits dans l'art antérieur), tel que l'oxyde de lanthane La2O3 (température de fusion de 2590 K), ou par l'emploi d'un autre constituant de type titanate tel que le titanate de baryum BaTiO3 (température de fusion de 1895 K). Il n'est pas observé avec ces deux additifs d'effet cumulé d'agglomération des résidus de combustion et d'obtention d'une valeur de vitesse de combustion suffisant pour présenter un intérêt. Tableau 2 Exemples CEx.1 CEx.2 Ingrédients Nitrate de Guanidine (NG) % 51,5 52 Nitrate Basique de Cuivre (BCN) % 43,5 44 Oxyde de lanthane (La2O3) % 5 - Titanate de baryum (BaTiO3 % - 4 Caractéristiques Vitesse de combustion à 10 MPa mm/s 14,2 16,5 Vitesse de combustion à 20 MPa mm/s 18,0 21,9 Aspect aggloméré des résidus de combustion sous la forme d'un squelette du bloc pyrotechnique (1) non non (1) après tirs en enceinte manométrique 40 cm3 ; composé pyrotechnique sous forme initiale de pastilles de diamètre 6,35 mm et d'épaisseur 2,1 mm. B. Table 2 below demonstrates that the beneficial contribution observed with strontium titanate or calcium titanate is indeed the result of selection and cannot be systematically obtained by the use of any constituent refractory (also other than the constituents described in the prior art), such as lanthanum oxide La 2 O 3 (melting point of 2590 K), or by the use of another constituent of titanate type such as barium titanate BaTiO 3 (melting point of 1895 K). With these two additives, a cumulative effect of agglomeration of combustion residues and of obtaining a combustion rate value sufficient to be of interest is not observed. Table 2 Examples CEx.1 CEx.2 Ingredients Guanidine nitrate (NG) % 51.5 52 Basic Copper Nitrate (BCN) % 43.5 44 Lanthanum oxide (La 2 O 3 ) % 5 - Barium titanate (BaTiO 3 % - 4 Characteristics Burning rate at 10 MPa mm / s 14.2 16.5 Burn rate at 20 MPa mm / s 18.0 21.9 Agglomerated appearance of combustion residues in the form of a skeleton of the pyrotechnic block (1) no no (1) after firing in a 40 cm 3 manometric chamber; pyrotechnic compound in the initial form of pellets with a diameter of 6.35 mm and a thickness of 2.1 mm.

Claims (13)

  1. A gas-generating pyrotechnic solid compound, the composition of which, expressed as weight percentages, contains:
    - 45% to 60% of guanidine nitrate,
    - 37% to 52% of basic copper nitrate,
    - 1% to 5% of at least one inorganic titanate whose melting point is greater than 2100 K.
  2. The compound as claimed in claim 1, characterized in that its composition contains at least one inorganic titanate chosen from metal titanates, alkaline-earth metal titanates, and mixtures thereof.
  3. The compound as claimed in claim 1 or 2, characterized in that its composition contains strontium titanate (SrTiO3).
  4. The compound as claimed in any one of claims 1 to 3, characterized in that its composition contains calcium titanate (CaTiO3).
  5. The compound as claimed in any one of claims 1 to 4, characterized in that its composition contains aluminum titanate (Al2TiO5).
  6. The compound as claimed in any one of claims 1 to 5, characterized in that its composition, expressed as weight percentages, contains between 2% and 4 % of said at least one inorganic titanate.
  7. The compound as claimed in any one of claims 1 to 6, characterized in that its composition consists, for at least 99.5% by weight, or even 100% by weight, of said guanidine nitrate, basic copper nitrate and inorganic titanate(s).
  8. The compound as claimed in any one of claims 1 to 7, characterized in that said at least one inorganic titanate has a median diameter of less than 5 µm.
  9. The compound as claimed in any one of claims 1 to 8, characterized in that said at least one inorganic titanate has a median diameter of less than 1 µm.
  10. The compound as claimed in any one of claims 1 to 9, characterized in that it is obtained via a dry-route process, which comprises a step of compacting of a pulverulent mixture containing its constituent ingredients in powder form, optionally followed by a granulation step, which is itself optionally followed by a step of forming by pelletization.
  11. The compound as claimed in any one of claims 1 to 10, characterized in that it is in the form of granules, pellets or monolithic blocks.
  12. A pulverulent composition, which is a precursor of a compound as claimed in any one of claims 1 to 11, the composition of which corresponds to that of a compound as claimed in any one of claims 1 to 11.
  13. A gas generator, containing a gas-generating pyrotechnic solid charge, characterized in that said charge contains at least one compound as claimed in any one of claims 1 to 11.
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FR3007659B1 (en) 2013-06-28 2017-03-24 Herakles METHOD FOR DELIVERING A PRESSURIZED LIQUID FROM THE COMBUSTION GASES OF AT LEAST ONE PYROTECHNIC LOAD
FR3022906B1 (en) * 2014-06-30 2016-07-15 Herakles MONOLITHIC PYROTECHNIC BLOCKS GENERATORS OF GAS
GB2530295A (en) * 2014-09-18 2016-03-23 Ford Global Tech Llc Inflator propellant
FR3037812B1 (en) 2015-06-29 2017-08-04 Herakles FIRE EXTINGUISHER
JP6970190B2 (en) 2016-05-23 2021-11-24 ジョイソン セーフティー システムズ アクウィジション エルエルシー Gas generation compositions and their production and use methods
FR3061174B1 (en) 2016-12-22 2019-05-31 Airbus Safran Launchers Sas SOLID PYROTECHNIC OBJECTS GENERATORS OF GAS
JP7054126B2 (en) * 2017-03-23 2022-04-13 日本化薬株式会社 A gas generator composition, a molded product thereof, and a gas generator using the same.
CN107698414B (en) * 2017-10-24 2019-08-09 湖北航鹏化学动力科技有限责任公司 Gas generant composition, preparation method, application and gas generator
CN107698415A (en) * 2017-10-24 2018-02-16 湖北航鹏化学动力科技有限责任公司 A kind of gas generant composition, preparation method, application and gas generator
FR3077989B1 (en) 2018-02-20 2021-11-19 Arianegroup Sas FIRE EXTINGUISHER
CN111675589B (en) 2020-05-15 2021-08-06 湖北航鹏化学动力科技有限责任公司 Gas generating agent composition, preparation method and application thereof

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5139588A (en) * 1990-10-23 1992-08-18 Automotive Systems Laboratory, Inc. Composition for controlling oxides of nitrogen
EP0584899A3 (en) * 1992-08-05 1995-08-02 Morton Int Inc Additive approach to ballistic and slag melting point control of azide-based gas generant compositions.
DE19531130A1 (en) * 1995-08-24 1997-02-27 Bayern Chemie Gmbh Flugchemie Granulated or pelleted gas generating substance, suitable for use in airbags
US5608183A (en) * 1996-03-15 1997-03-04 Morton International, Inc. Gas generant compositions containing amine nitrates plus basic copper (II) nitrate and/or cobalt(III) triammine trinitrate
US6740180B1 (en) * 1997-07-15 2004-05-25 Anthony Joseph Cesaroni Thermoplastic polymer propellant compositions
DE29806504U1 (en) 1998-04-08 1998-08-06 Trw Airbag Sys Gmbh & Co Kg Azide-free, gas generating composition
DE29821541U1 (en) 1998-12-02 1999-02-18 Trw Airbag Sys Gmbh & Co Kg Azide-free, gas generating composition
US6143102A (en) * 1999-05-06 2000-11-07 Autoliv Asp, Inc. Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods
JP4641130B2 (en) * 2000-10-10 2011-03-02 日本化薬株式会社 Gas generating composition and gas generator using the same
FR2818636B1 (en) * 2000-12-22 2003-02-28 Poudres & Explosifs Ste Nale HYDROCARBON BINDER GAS GENERATING PYROTECHNIC COMPOSITIONS AND CONTINUOUS MANUFACTURING METHOD
CN1307129C (en) * 2002-11-22 2007-03-28 日本化药株式会社 Gas generating agent, process for production thereof, and gas generators for air bags
US20040173922A1 (en) * 2003-03-04 2004-09-09 Barnes Michael W. Method for preparing pyrotechnics oxidized by basic metal nitrate
US6958101B2 (en) * 2003-04-11 2005-10-25 Autoliv Asp, Inc. Substituted basic metal nitrates in gas generation
US20050016646A1 (en) * 2003-07-25 2005-01-27 Barnes Michael W. Chlorine-containing gas generant compositions including a copper-containing chlorine scavenger
JP4672974B2 (en) * 2003-10-22 2011-04-20 ダイセル化学工業株式会社 Gas generant composition
WO2005100905A1 (en) * 2004-04-16 2005-10-27 Nippon Kayaku Kabushiki Kaisha Igniter and gas generator having the same
FR2887247B1 (en) * 2005-06-15 2007-10-12 Snpe Materiaux Energetiques PROCESS FOR MANUFACTURING GAS GENERATOR PELLETS COMPRISING A DRY GRANULATION STEP
FR2892117B1 (en) * 2005-10-13 2008-05-02 Snpe Materiaux Energetiques Sa FAST GAS GENERATING PYROTECHNIC COMPOSITION AND PROCESS FOR OBTAINING THE SAME
JP5031255B2 (en) * 2006-03-02 2012-09-19 株式会社ダイセル Gas generant composition
FR2915746B1 (en) * 2007-05-02 2009-08-21 Snpe Materiaux Energetiques Sa PYROTECHNIC COMPOUND GAS GENERATOR; PROCESS FOR OBTAINING
JP2009137821A (en) * 2007-12-11 2009-06-25 Daicel Chem Ind Ltd Gas generating agent composition
JP5719763B2 (en) 2009-03-13 2015-05-20 日本化薬株式会社 GAS GENERATOR COMPOSITION, MOLDED BODY THEREOF, AND GAS GENERATOR USING THE SAME
FR2975097B1 (en) * 2011-05-09 2015-11-20 Sme PYROTECHNIC COMPOUNDS GENERATORS OF GAS

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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JP2014517803A (en) 2014-07-24
KR20140135089A (en) 2014-11-25
BR112013028948A8 (en) 2018-08-14
WO2012153062A3 (en) 2013-03-28
BR112013028948A2 (en) 2017-11-07
US20140116584A1 (en) 2014-05-01
CN103517887A (en) 2014-01-15
EP2707345A2 (en) 2014-03-19
UA112437C2 (en) 2016-09-12
CA2834973C (en) 2020-10-20
JP6092189B2 (en) 2017-03-08
CN105801326A (en) 2016-07-27
FR2975097B1 (en) 2015-11-20
MX338889B (en) 2016-05-04
WO2012153062A2 (en) 2012-11-15
MY184549A (en) 2021-04-01
CA2834973A1 (en) 2012-11-15
US9249063B2 (en) 2016-02-02
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CN103517887B (en) 2016-03-23
MX2013012914A (en) 2014-02-27

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