MXPA99000916A - Metal complexes for use as gas generants - Google Patents

Abstract

Gas generating compositions and methods for their use are provided. Metal complexes are used as gas generating compositions. These complexes are comprised of a metal cation template, a neutral ligand containing hydrogen and nitrogen, sufficient oxidizing anion to balance the charge of the complex, and at least one cool burning organic nitrogen-containing compound. The complexes are formulated such that when the complex combusts, nitrogen gas and water vapor is produced. Specific examples of such complexes include metal nitrite amine, metal nitrate amine, and metal perchlorate amine complexes, as well as hydrazine complexes. A binder and co-oxidizer can be combined with the metal complexes to improve crush strength of the gas generating compositions and to permit efficient combustion of the binder. Such gas generating compositions are adaptable for use in gas generating devices such as automobile air bags.

Description

METAL COMPLEXES TO BE USED AS GENERATORS OF GAS FIELD OF THE INVENTION The present invention relates to complexes of transition metals or alkaline earth metals that are capable of combustion to generate gases. More particularly, the present invention relates to the provision of these complexes that rapidly oxidize to produce significant amounts of gases, particularly water vapor and nitrogen.

BACKGROUND OF THE INVENTION Chemical compositions that generate gases are useful in a number of different contexts. An important use for these compositions is in the operation of the "air bags". ' Airbags are gaining acceptance to the point that many, if not most, of the new cars are equipped with these devices. Recently, many new cars are equipped with multiple airbags to protect the driver and passengers. In the context of automobile airbags, enough gas must be generated to inflate the device within a fraction of a second. Between the time the car is hit in an accident, and the time when the driver will be pushed, on the other hand, against the driving wheel, the airbag must be inflated completely. As a result, almost instantaneous gas generation is required. There are a number of important, additional design criteria that must be met. Car manufacturers and others have set forth the required criteria that must be met in detailed specifications. The preparation of gas generating compositions that meet these important design criteria is an extremely difficult task. These specifications require that the gas generation composition produce gas at a required rate. The specifications also place strict limits on the generation of toxic or dangerous gases or solids. Examples of restricted gases include carbon monoxide, carbon dioxide, NOx, S0X, and hydrogen sulfide. The gas must be generated at a sufficiently low and reasonably low temperature so that a car occupant does not burn when impacted in an inflated bag of air. If the produced gas is overheated, there is a possibility that the occupant of the motor vehicle could be burned at the impact just by hitting a newly deployed airbag. Therefore, it is necessary that the combustion of the gas generator and the construction of the airbag isolate the occupants of the automobile from excessive heat. All this is required, as long as the gas generator maintains an adequate burn rate. Another design criterion, related, but important, is that the composition of the gas generator produces a limited amount of particulate materials. Particulate materials can interfere with the operation of the supplementary restraint system, present a danger of inhalation, irritate the skin and eyes, constitute a dangerous solid waste that must be treated after the operation of the safety device. In the absence of an acceptable alternative, the production of irritant particles is one of the undesirable but tolerated aspects of the commonly used sodium azide materials. In addition to producing limited amounts, if any, of materials in the form of particles, it is desired that at least the volume of these particulate materials be easily filtered. For example, it is desirable that the composition produces a filterable slag. If the reaction products form a filterable material, the products can be filtered and prevented from escaping into the surrounding environment. Both organic and inorganic materials have been processed as well as possible gas generators. These gas generating compositions include oxidants and fuels that react at sufficiently high rates to produce large quantities of gas in a fraction of a second. Nowadays, sodium azide is the gas generating material, most widely used and commonly accepted. Sodium azide nominally satisfies the specifications and industrial parameters. However, sodium azide has a number of persistent problems. Sodium azide is highly toxic as a starting material, since its toxicity level as measured by oral LD50 in rats is in the range of 45 mg / kg. Workers who regularly handle sodium azide have experienced several health problems such as severe headaches, shortness of breath, seizures, and other symptoms. In addition, no matter what auxiliary oxidant is used, the combustion products of a sodium azide gas generator include caustic reaction products such as sodium oxide, or sodium hydroxide. Molybdenum disulfide or sulfur have been used as oxidants for sodium azide. However, the use of these oxidants results in toxic products such as hydrogen sulfide gas of corrosive materials such as sodium oxide and sodium sulfide. Rescue workers and car occupants have complained about both hydrogen sulfide gas and the corrosive power produced by the operation of gas generators based on sodium azide.

There also anticipated increasing problems in relation to the elimination of the restriction systems, complementary, inflated with non-useful gases, for example, auto airbags, in the demolished cars. The sodium azide that remains in these complementary restriction systems can be extracted by leaching the demolished car to become a water pollutant or toxic waste. Recently, some have expressed interest that sodium azide could form heavy metal, explosive or hydrazoic acid azides when contacted with battery acids after disposal. Sodium azide-based gas generators most commonly used for the cooling of air pockets, but with the significant disadvantages of these compositions, many alternative gas generating compositions have been proposed to replace sodium azide. Most of the proposed replacements of sodium azide, however, fail to adequately address all of the criteria discussed above. Therefore, it will be appreciated, that, there a number of important criteria for selecting gas generating compositions for use in the supplementary, automobile, restriction systems. For example, it is important to select starting materials that not toxic. At the same time, combustion products should not be toxic or dangerous. In this regard, industrial standards limit the quantities available of the various gases and particles produced by the operation of the restraining, complementary systems. Therefore, it would be a significant advantage to provide compositions capable of generating large quantities of gas that will overcome the problems identified in the existing art. It would be an additional advantage to provide a gas generation that is based on substantially non-toxic starting materials and that produces substantially non-toxic reaction products. It would be another advantage in the art to provide a gas generating composition that produces very limited amounts of toxic or irritant wastes, in the form of particles and limited undesirable gaseous products. It would also be an advantage to provide a gas generating composition which forms a readily filterable solid slag in the reaction. These compositions and methods for their use described and claimed herein.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to the use of transition metal or alkaline earth metal complexes as gas generating compositions. These complexes comprised of a metal cation and a neutral ligand containing hydrogen and nitrogen. One or more oxidant anions provided to balance the charge of the complex. Examples of typical oxidizing anions that can be used include nitrates, nitrites, chlorates, perchlorates, peroxides and superoxides. In some cases, the oxidizing anion is part of the coordination complex of the metal cation. The complexes formulated such that when the complex is combusted, a gas mixture containing nitrogen gas and water vapor is produced. A binder can be provided to improve the grinding resistance and other metallic properties of the gas generating composition.

A co-oxidant may also be provided primarily to allow efficient combustion of the binder. Importantly, the production of undesirable gases or particulate material is substantially reduced or eliminated. Specific examples of the complexes used herein include metal nitrite amines, metal nitrate amines, metal perchlorate amines, metal nitrite hydrazines, metal nitrate hydrazines, metal perchlorate hydrazines, and mixtures thereof. The complexes within the scope of the present invention rapidly combust, or decompose to produce significant amounts of gas. The metals incorporated within the complexes transition metals, alkaline earth metals, metalloids, or lanthanide complexes. The currently preferred metal is cobalt. Other metals that also form complexes with the desired properties in the present invention include, for example, magnesium, manganese, nickel, titanium, copper, chromium, zinc, and tin. Examples of other metals include rhodium, iridium, ruthenium, palladium, and platinum. These metals are not as preferred as the metals mentioned above, mainly due to cost considerations. The transition metal cation or the alkaline earth metal cation acts as a template or coordination center for the transition metal complex. As mentioned above, the complex includes a neutral ligand containing hydrogen and nitrogen. this neutral ligand is preferably ammonia or a substituted ammonia ligand such as hydrazine or a substituted hydrazine ligand. If carbon is present in this neutral ligand, this neutral ligand is preferably aliphatic in nature rather than aromatic. Preferably, the neutral ligand is substantially or completely based on nitrogen and hydrogen atoms and contains little, if any, carbon atoms. neutral ligands containing hydrogen and nitrogen are described in F.A. Cotton and G. Wilkinson's Advanced Inorganic Chemistry, A Comprehensive Text, 4th Ed., Wiley-Interscience, 1980, pages 118-1132, which is incorporated herein by reference. The currently preferred neutral ligands are NH3 and N2H. One or more oxidizing anions can also be coordinated with the metal cation. Examples of metal complexes within the scope of the present invention include Cu (NH3). (N03) 2 (tetraamine copper (II) nitrate, Co (NH3) 3 (N02) 3 (trinitrotriamine cobalt (III)), Co (NH3) 6 (CIO.) 3 (hexahydrin-cobalt perchlorate (III), Co (NH3) 6 (N03) 3 (hexaamine-cobalt (III) nitrate), Zn (N2H4) 3 (N03) 2 (tris-hydrazine-zinc nitrate), Mg (N2H4) 222 (CIO.) 2 (bis-hydrazine-magnesium perchlorate), and Pt (N02) 2 (NH2NH2) 2 (bis-hydrazine-platinum nitrite (II). It is within the scope of the present invention to include metal complexes containing a common ligand in addition to neutral ligand. A few typical common ligands include: water (H20), hydroxo (OH), carbonate (C0), oxalate (C204), cyano (CN), isocyanate (NC), chlorine (Cl), fluoro (F), and similar ligands. Metal complexes within the scope of the present invention are also proposed to include a common counter ion, in addition to the oxidizing anion, to assist in balancing the charge of the complex. A few typical common counterions include: hydroxide (OH "), chloride (Cl"), fluoride (F ~), cyanide (CN "), carbonate (CO), carbonate (C03-2) phosphate (PO." 3), oxalate (C20.-2), borate (B04"5), ammonium (NH /), and the like, It was observed that the metal complexes containing the neutral ligands described and the oxidizing anions quickly combust to produce significant amounts of gases The combustion can be initiated by the application of heat or by the use of lighters, conventional.

DETAILED DESCRIPTION OF THE INVENTION As discussed above, the present invention relates to gas generating compositions containing transition metal or alkaline earth metal complexes. These complexes are comprised of a metal cation template and a neutral ligand containing hydrogen and nitrogen. One or more oxidant anions are provided to balance the charge of the complex. In some cases, the oxidizing anion is part of the coordination complex with the metal cation. Examples of typical oxidizing anions that can be used include nitrates, nitrites, chlorates, perchlorates, peroxides and superoxides. The complexes can be combined with a binder or binder mixtures to improve the mill strength and other metallic properties of the gas generating composition. A co-oxidant may be provided primarily to allow efficient combustion of the binder. Metal complexes that include at least one common ligand in addition to the neutral ligand are also included within the scope of the present invention. As used herein, the term "common ligand" includes well-known ligands used by inorganic chemistries to prepare coordination complexes with metal cations. Common ligands are preferably polyatomic ions or molecules, but some monatomic ions, such as halogen ions, can also be used. Examples of common ligands within the scope of the present invention include aquo (H20), hydroxo (OH), perhydroxo (02H), peroxo (02), carbonate (C03), oxalate (C204), carbonyl (CO), nitrosyl (NO), cyano (CN), isocyanate (NC), isothiocyanate (NCS), thiocyanate (SCN), chlorine (Cl), fluoro (F), amido (NH2), imido (NH), sulfate (SO.), phosphate (PO.), tetraethylenediaminetetraacetic acid (EDTA), and similar ligands. See, F. Albert Cotton and Geoffrey Wilkinson, Advanced Inorganic Chemistry, 2nd ed., John Wiley & Sons, pp. 139-142, 1966 and James E. Huheey, Inorganic Chemistry, 3rd ed., Harper & Row, pp. A-97-A-107, 1983, which are incorporated herein by reference. Those skilled in the art will appreciate that suitable metal complexes within the scope of the present invention can be prepared containing a neutral ligand and another ligand not listed above. In some cases, the complexes may include a common counterion, in addition to the oxidizing anion, to help balance the charge of the complex. As used herein, the term "common counterion" includes well-known anions and cations used by inorganic chemicals as counterions. Examples of common counterions within the scope of the present invention include hydroxide (OH "), chloride (Cl"), fluoride (F "), cyanide (CN"), thiocyanate (SCN "), carbonate (C03" 2), sulfate (SO.-2), phosphate (PO. "3), oxalate (C20. ~ 2), borate (BO." 2), ammonium (NH /), and the like. See, Whitten, K.W., and Gailey, K.D., General Chemistry,. Saunders College Publishing, p. 167, 1981 and James E. Huheey, Inorganic Chemistry, 3rd ed., Harper & Row, pp. A-97-A-103, 1983, which are incorporated herein by reference. The gas generating ingredients are formulated such that when the composition is combusted, nitrogen gas and water vapor are produced. In some cases, small amounts of carbon dioxide and carbon monoxide are produced, if a binder, co-oxidant, common ligand or oxidizing anion contains carbon. The total carbon in the gas generating composition is carefully controlled to prevent excessive generation of CO gas. The combustion of the gas generator takes place at a rate sufficient to qualify these materials for use as gas generating compositions in automobile bags and other similar types of devices. Importantly, the production of other undesirable gases or particulate material is substantially reduced, or eliminated. Complexes falling within the scope of the present invention include metal nitrate amines, metal nitrite amines, metal perchlorate amines, metal nitrite hydrazines, metal nitrate hydrazines, metal perchlorate hydrazines, and mixtures thereof. Metal amine complexes are defined as coordination complexes that include ammonia as the coordination ligand. The amine complexes may also have one or more oxidizing anions, such as nitrite (N02"), nitrate (N03"), chlorate (C103"), perchlorate (CIO /), peroxide (022"), and superoxide (02"). ), or mixtures thereof, in the complex The present invention also relates to similar metal hydrazine complexes containing the corresponding oxidizing anions It is suggested that during the combustion of a complex containing nitrite and ammonia groups, and nitrite and Ammonia groups are subjected to a diazotization reaction.This reaction is similar, for example, to the reaction of sodium nitrite and ammonium sulfate, which is stated as follows: 2NaNo2 + (NH / 2SO4? Na2S04 + 4H20 + 2N_ Compositions such as sodium nitrite and ammonium sulfate in combination have little utility as gas generating substances. These materials are observed to undergo metathesis reactions that result in unstable ammonium nitrite. In addition, they have limited stability to the simpler nitrite salts. In contrast, the metal complexes used in the present invention are stable materials which, in certain cases, are capable of undergoing the type of reaction set forth above. The complexes of the present invention also produce reaction products that include desirable amounts of non-toxic gases such as water vapor and nitrogen. In addition, a stable metal, or metal oxide slag is formed. In this way, the compositions of the present invention avoid several of the limitations of the existing sodium azide gas generating compositions. Any transition metal, alkaline earth metal, metalloid, or lanthanide metal that is capable of forming the complexes described herein is a potential candidate for use in these gas generating compositions. Hor, considerations such as cost, activity, thermal stability, and toxicity may limit the most preferred group of metals. The currently preferred metal is cobalt. Cobalt forms stable complexes that are relatively cheap. In addition, the reaction products of the combustion of the cobalt complex are relatively non-toxic. Other preferred metals include magnesium, manganese, copper, zinc, and tin. Less preferred but useful examples of metals include nickel, titanium, chromium, rhodium, iridium, ruthenium, and platinum. A few representative examples of amine complexes within the scope of the present invention, and the associated gas generation decomposition reactions, are as follows: Cu (NH,) 2 (NO,) a-CuO + 3H20 + 2N, 2Co (NH3) 3 (N02) 3? 2CoO + 9H20 + 6N2 + M02 2Cr (NH3) 3 (N02) 3? Cr2Oa + 9H20 + 6N2 (Cu (NH3) (N03) 2 - Cu + 3N2 + 6H20 2B + 3C? (NH3) 6C? (N02) 4? 6C0O + B203 + 27H20 18N, Mg + Co (NHJ) (N02) 2Co (NH3) 3 (N02) <; - 2CoO + 10 [Co (NH3) «(N02) 2] (NO,) * 2Sr. { N03) 2? COOO + 2SrO + 37N2 + 60H2O 18IC? (NH,) ß] (N03) 3 * 4Cu2 (OH) 3N03 - I8C0O + 8Cu + 83N2 + 168H20 2 { C? (NK,) (N03) 3 + 2NH, N03 - * 2Co0 + 11N2 + 22H70 TiCl «(NH3) 2 + 3Ba02? TiOa + 2BaCl2 + BaO + 3H20 + N2 4 [Cr (NH3) sOH) (CIO /, + [SnCl «(NHj) 2]? 4CrCl3 + SnO + 35H20 + 11N2 10 [Ru (NH3) sN2] (NOj) 2 + 3Sr (N03) 3? 3SrO + lORu + 8N2 + 75H20 [Ni (H, 0) a (NH,) 4] (N03) 2 - Ni * 3N2 + 8H30 2 [Cr (02) 2 (NH3) j] + 4 NH, N03-7Na + 17H20 + C ^ O, 8 (Ni (CN) 2 (NH3)] - CíHí + 43KC10 <- 8NiO + 43KCl + 64C02 + 12N2 + 36H20 2 [Sm (02) 3 (NH3 )] + 4 [Gd.NH3) 5] (ClO «), - Sm2Oj + 4GdCl3 + 19N2 + 57H20 2Er (N03) 3 (NH3) 3 + 2 [Co (NH,) ß] (N03) 3 - Er203 + 12COO + 60N2 + 117H20 A few representative examples of hydrazine complexes within the scope of the present invention, and related gas generating reactions, are as follows: 52n (N2H,) (N03) 2 + Sr (N03) 2? 5ZnO + 21N2 + 30H2O + SrO Co (N2H4) 3 (NO,) 2? Co + 4N2 + 6H2O 3Mg (N2H4) 2 (ClO4) 2 + 2Si.N4? 6SiO2 + 3MgCl2 + 10N2 + 12H2O 2Mg (N2H4) 2 (NO3) 2 + 2 [Co (NHJ) «(N02) 2] NO2? 2MgO + 2CoO + 13N2 + 20H2O Pt (NO2) 2 (N2H4) 2? Pt 3N2 + 4H2O [Mn (N2H4) 3] (NO3) 2 + Cu (OH),? Cu + MnO + 4N, + 7H20 2 [a (N2H4) 4 (N03)] (NO,) a + H4NO3 - a2O, + 12N2 + 18H2O While the complexes of the present invention are relatively stable, it is also simple to initiate the combustion reaction. For example, if the examples are contacted with a hot wire, rapid gas-producing combustion reactions are observed. Similarly, it is possible to initiate the reaction by means of conventional igniter devices. One type of igniter device includes a number of granules or pellets of B / KN03 that are combusted, and which in turn is capable of combusting or igniting the compositions of the present invention. Another lighter device includes a quantity of granules of Mg / Sr (N03) 2 / nylon. It is also important to note that many of the complexes defined above suffer a "stoichiometric" decomposition. That is, the complexes decompose without reacting with any other material to produce large amounts of nitrogen and water, and a metal or metal oxide. However, for certain complexes, it may be desirable to add a fuel or oxidant to the complex in order to ensure complete and efficient reaction. These fuels include, for example, boron, magnesium, aluminum, boron or aluminum hydrides, carbon, silicon, titanium, zirconium, and other conventional, similar, combustible materials, such as conventional organic binders. Oxidant species include nitrates, nitrite, chlorates, perchlorates, peroxides, and other similar oxidizing materials.

In this way, while the stoichiometric decomposition is attractive due to the simplicity of the composition and reaction, it is also possible to use complexes for which the stoichiometric decomposition is not possible. As mentioned above, the nitrate and perchlorate complexes also fall within the scope of the invention. A few representative examples of these nitrate complexes include: Co (NH3) 6 (N03) 3, Cu (NH3). (N03) 2, [Co (NH3) 5] (N03)] (N03) 2, [Co (NH3) 5 (N02)] (N03) 2, [(Co (NH3) 5 (H20)] (N03) 5. A few representative examples of perchlorate complexes within the scope of the present invention include: [Co (NH3) 6. (C10 / 3, [C? (NH3 ) 5 (N02)] CIO., [Mg (N2H / 2] (C10.) 2. The preparation of the nitrite or metal nitrate amine complexes of the present invention are described in the literature, specifically Hagel et al. "The Traiamines of cobalt (III), I. Geometrical Iso ers of trini trotriamminecobalt (III)", 9 Inorganic Chemistry 1496 (June 1970), G. Pass and H. Sutcliffe, Practical Inorganic Chemistry, 2nd Ed., Chap an &Hull, New York, 1974, Shibata et al., "Synthesis of Nitroammine- and Cyanoammine-cobalt (III) Complexes With Potassium tricarbonatocobaltate (III) as the Starting Material, "3 Inorganic Chemistry 1573 (Nov. 1964); Wieghardt et al., "Μ-carboxylate-μ-hydroxo-bis [triamminecobalt (III)] Complexes, "23 Inorganic Synthesis 23 (1985); Laing, "mer- and fac- [Co (NH3) 3N02) 3]: Do They Exist?" 62 J.

Chem Educ, 707 (1985); Siebert, "Isomere des Trinitrotri-amminkobalt (III), "441 Z. Anorg. Allg. Chem. 47 (1978), all of which are incorporated herein by this reference. Transition metal perchlorate amine complexes are synthesized by similar methods. As mentioned above, the amine complexes of the present invention are generally stable and safe for use in the preparation of gas generating formulations The preparation of metal perchlorate, nitrate and nitrite hydrazine complexes is also described in Literature Specific reference is made to Patil et al., "Synthesis and characterization of Metal Hydrazine Nitrate, Azide, and Perchlorate Complexes," 12 Synthesis and Reactivity in Inorganic and Metal Organic Chemistry, 383 (1982); Klyichnikov et al., "Preparation of some Hydrazine Compounds of Palladium," 13 Russian Journal of Inorganic Chemistry, 416 (1968); Klyichnikov et al., "Conversion of Mononuclear Hydrazine Complexes of Platinum and Palladium Into Binuclear Complexes," 36 Ukr. Khim. Z .., 687 (1970). The described complexes can be processed into pellets or pellets useful for use in gas generating devices. These devices include restriction systems, complementary, automobile airbag systems. These gas generating compositions will comprise an amount of the described complexes and preferably a binder and a co-oxidant. The compositions produce a mixture of gases, mainly nitrogen and water vapor, in the decomposition or burning. The gas generating device will also include a means for initiating combustion of the composition, such as a hot wire or lighter. In the case of a car airbag system, the system will include the compositions described above; a folded, inflatable air bag; means for igniting the gas generating composition within the air bag system. Automobile airbag systems are well known in the art. Typical binders used in the gas generating compositions of the present invention include binders conventionally used in propellant, pyrotechnic and explosive compositions including, but not limited to, lactose, boric acid, silicates including magnesium silicate, polypropylene carbonate, polyethylene glycol, naturally occurring gums such as guar gum, acacia gum, modified celluloses and starches (A detailed discussion of these gums is provided by CL Mantell, The Water-Soluble Gums, Reinhold Publishing Corp., 1947, which is incorporated herein by reference, polyacrylic nitrocellulose acids, polyacrylamide, polyamides, including nylon, and other polymeric binders. These binders improve the mechanical properties or provide improved grinding resistance Although water-immiscible binders can be used in the present invention, it is commonly preferred to use water-soluble binders The concentration of the binder is preferably in the range 0.5 to 12% by weight, more preferably from 2% to 8% by weight of the gas generating composition Applicants have found that adding carbon such as carbon black or activated carbon to the gas generating compositions improves the action binder perhaps significantly by reinforcing the binder of this ma nera, forming a microcomposite. Improvements in milling strength from 50% to 150% have been observed with the addition of carbon black to the compositions within the scope of the present invention. The ballistic reproducibility is improved as the resistance to grinding is increased. The carbon concentration is preferably in the range from 0.1% to 6% by weight, preferably from 0.3 to 3% by weight of the gas generating composition. The co-oxidant may be a conventional oxidant such as perchlorate, chlorate, peroxides, nitrites, and nitrates, alkaline, alkaline earth, lanthanide or ammonium, including, for example, Sr (N03) 2 / NH.ClO., KN03, and (NH / 2Ce (N03) 6.

The co-oxidant can also be a metal-containing oxidizing agent such as metal oxides, metal hydroxides, metal peroxides, hydrated metal oxides, metal oxide hydroxides, metal anhydride oxides, and mixtures thereof, including those described in the US Pat. United States No. 5,439,537 issued August 8, 1995, entitled "Thermite Compositions for Use as Gas Generants," which is incorporated herein by reference. Examples of metal oxides include, among others, the oxides of copper, cobalt, manganese, tungsten, bismuth, molybdenum, and iron, such as CuO, Co203, CO3O4, CoFe204, Fe203, M0O3, Bi2Mo06, and Bi203. Examples of metal hydroxides include, among others, Fe (OH) 3, Co (OH) 3, Co (OH) 2, Ni (OH) 2, Cu (OH) 2, and Zn (OH) 2. Examples of metal oxide hydrates and metal anhydrous oxides include, among others, Fe203'xH20, Sn02'xH20 and Mo03"H20, Examples of metal oxide hydroxides include, among others, CoO (OH) 2, FeO (OH) 2 , MnO (OH) and MnO (OH) 3. The co-oxidant can also be a basic metal carbonate such as metal carbonate hydroxides, metal carbonate oxides, metal carbonate hydroxide oxides, and hydrates and mixtures thereof, and a basic metal nitrate such as metal hydroxide nitrates, metal nitrate oxides, and hydrates and mixtures thereof, including those oxidants described in U.S. Patent No. 5,429,691, entitled "Thermite Compositions. for use as Gas Generants ", which is incorporated herein by reference Table 1, below, lists the examples of typical basic metal carbonates capable of functioning as co-oxidants in the compositions of the present invention. : Table 1 Metal Carbonates, Basic Cu (C03)? -x'Cu (OH) 2x, for example, CuC03'Cu (OH) 2 (malachite) Co (C03) i-x (OH) 2? , for example, 2Co (C03) '3Co (OH) 2-H20 CoxFe? (C03) 2 (OH) 2, for example, Coo.09Feo.34 (C03) 0.2 (OH) 2 Na2 [Co (C03) 3] -3H20 Zn (C03)? -? (OH) 2x, for example, Zn2 (C03) (OH) 2 BiAMgB (C03) c (OH) D, for example, Bi2Mg (C03) 2 (0H) 4 Fe (C03)? -x (0H) 3 ?, for example, Cu2-xZnx (C03)? -? (OH) 2 ?, for example, Cui.f.Zn0., 6 (C03) (OH) 2 CO? Cu2-? (CO3)? -x (OH) 2 ?, for example COO.HCUO.SI (C03) 0.43 (OH) 1.1 TiABiB (C03) x (OH)? (0) z (H20) C for example, Ti3Bi4 (C03) 2 (OH) 2O9 (H20) 2 (BiO) 2C03 Table 2, below, lists the examples of basic metal nitrates capable of functioning as co-oxidants in the compositions of the present invention.

Table 2 Metal Nitrates, Basic Cu2 (OH) 3N03 (gehardite) Co2 (OH) 3N03 CuxCo2.? (OH) 3NO3, for example, CuCo (OH) 3N05 Mn (OH) 2N03 Fe (N03) n (OH) 3-n, for example, Fe4 (OH) uNCV 2H20 MO (N03) 202 BiON03'H20 Ce (OH ) (N03) 3'3H20 In certain cases, it is also carried out by using mixtures of these oxidizing agents in order to improve the ballistic properties or to minimize the filterability of the slag formed from the combustion of the composition. The present compositions may also employ additives conventionally used in gas generating compositions, propellants, and explosives, such as combustion rate modifiers, slag formers, release agents, and additives that effectively remove N0X. Typical modifiers of the combustion rate include: Fe20, K2B? 2H_2, Bi2Mo06, and graphite powder or carbon fibers. A number of slag forming agents are known and include, for example, clays, talcs, silicon oxide, alkaline earth oxides, hydroxides, oxalates, of which magnesium carbonate and magnesium hydroxide are examples. A number of additives and / or agents are also known to reduce or eliminate the nitrogen oxides of the reaction products of a gas generating composition. Including the alkali metal salts and complexes of tetrazoles, aminotetrazoles, triazoles and related nitrogen heterocycles, of which are, for example, aminotetrazole of potassium, sodium carbonate, and potassium carbonate. The composition may also include materials that facilitate the release of the composition from a mold such as graphite, molidene sulphide, calcium stearate, or boron nitride. Typical ignition aids / burn rate modifiers that can be used herein include oxides of metals, nitrates and other compounds such as, for example, Fe203, K2B12H2'H20, BiO (N03), Co203 / CoFe204, CuMoO., Bi2Mo06, Mn02, Mg (N03) 2-? H20, Fe (N03) 3'xH20, Co (N03) 2 'xH20 and NH4N03. The coolants include magnesium hydroxide, cupric oxalate, boric acid, aluminum hydroxide, and silicotungstic acid. Coolants such as aluminum hydroxide and silicotungstic acid can also function as slag intensifiers. It will be appreciated that many prior additives can perform multiple functions in the gas generating formulation such as a co-oxidant or as a fuel, depending on the compound. Some compounds can function as a co-oxidant, modifier of the rate of combustion, refrigerant, and / or slag former. Several important properties of the typical hexaamine-cobalt (III) nitrate gas generating compositions within the scope of the present invention have been compared with those of the commercial gas-generating compositions of sodium azide. These properties illustrate the significant differences between conventional gas, sodium azide, and gas generating compositions within the scope of the present invention. These properties are summarized below: The term "gas generator fraction" means the weight fraction of the gas generator by weight of the gas generator. Typical gas generating compositions of hexaamine-cobalt (III) nitrate have more preferred flame temperatures in the range of 1850 ° K to 1900 ° K, the gas fraction of the generator in the range of 0.70 to 0.75, the total carbon content in the generator in the range of 1.5% to 3.0%, the speed and combustion of the generator at 70.31 kg / cm2 (1000 psi) in the range of 0.2 ips to 0.35 ips, and the surface area of the generator in the range of 2.5 cm2 / g to 3.5 cm2 / g. The gas generating compositions of the present invention are easily adapted for use with the conventional technology of hybrid airbag inflators. The technology of hybrid inflators is based on heating a stored inert gas (argon or helium) to a desired temperature by burning a small amount of the propellant. Hybrid inflators do not require cooling filters used with pyrotechnic inflators to cool the combustion gases, because the hybrid inflators are capable of providing a lower temperature gas. The gas discharge temperature can be changed selectively by adjusting the weight ratio of the inert gas to the weight of the propellant. The greater the ratio of gas weight to propellant weight, the colder the gas discharge temperature will be.

A hybrid gas generation system comprises a pressure tank comprising a breakable opening, a predetermined amount of inert gas placed within the pressure tank; a gas generating device for producing hot combustion gases and having a means for breaking the breakable aperture; and a means for igniting the gas generating composition. The tank has a breakable opening that can be broken by a piston when the gas generating device is turned on. The gas generating device is configured and placed in relation to the pressure tank so that the hot combustion gases are mixed with the inert gas, and heated thereto. Suitable inert gases include, among others, argon, helium and mixtures thereof. The mixed and heated gases leave the pressure tank through the opening and finally exit the hybrid cooler and deploy an inflatable bag or balloon, such as an automobile air bag. Preferred embodiments of the invention produce combustion products with a higher temperature of about 800 ° K, the heat of which is transferred to the colder inert gas causing a further improvement in the efficiency of the hybrid gas generation system. The gas generation devices, hybrids for complementary safety restriction applications, are described in Frantom, Hybrid Airbag Inflator Technology, Airbag Int '1 symposium on Sophisticated Car Occupant safety Systems, (Weinbrenner-Saal, Germany, Nov. 2 -3, 1992). A further, preferred embodiment of the present invention is the incorporation of at least one organic, cold-burn, nitrogen compound, such as, for example, guanidine nitrate in the gas generating composition. An organic, cold-burning nitrogen compound is a compound that has a relatively low heat of formation. In general, the heat of formation of the cold-burn compound may be less than about -400 cal / g, and preferably less than about -600 cal / g. The heat of formation for guanidine nitrate, for example, is about -747 cal / g. In this preferred embodiment, the cold-burning organic nitrogen compound is not the main fuel of the formation but is a secondary fuel. The fuels already described above, such as, for example, hexane-cobalt nitrate, can serve as the main fuel. In addition, a substance such as guanidine nitrate may also have some oxidizing capacity due to the presence of for example, the nitrate group. However, the organic, cold-burn nitrogen compound is not the primary oxidizing agent. However, it can act as a secondary oxidizing agent or as a co-oxidant together with the other oxidizing or co-oxidant substances mentioned above, such as, for example, basic copper nitrate. In addition to guanidine nitrate, the additional, organic, cold-burn nitrogen compounds for this preferred embodiment include guanidine salts such as, for example, the carbonate salt and guanidine derivatives such as, for example, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, nitroguanidine, urea, resin, glycine-nitrate ammonium complexes, and dinitrate of et i len-dimaine. However, guanidine nitrate is preferred.

Mixtures of nitrogen, organic, cold-burn compounds can be used. In principle, for this preferred embodiment, the amount of the nitrogen, organic, cold-burn compound incorporated in the composition, can be generally more than 0% by weight, and less than about 40% by weight, and preferably , between about 5% by weight and about 30% by weight, and more preferably between about 10% by weight and about 25% by weight. This embodiment of the present invention is not limited by theory, however, and in practice, the amount can be determined by a person skilled in the art depending on which performance characteristics are most important for the particular application of the airbag. In this preferred embodiment, the use of the nitrogen, organic, cold-burn compound results in high gas production with a substantially improved filterability of the slag produced from combustion. In addition, the total cost of the composition can be reduced with a relatively less expensive, cold-burning organic nitrogen compound, such as a guanidine nitrate replacing a relatively more expensive ingredient, such as, for example, hexaamine cobalt nitrate. In principle, the amount of N0X can also be reduced. In this preferred embodiment, the gas generating compositions comprise nitrogen, organic, cold-burn compounds, and in addition, they also comprise: 1) at least one main fuel such as a metal complex such as, for example, hexaamine cobalt nitrate, Co (NH3) e (N03) 3, which is different from the nitrogen, organic, cold-burn compound, 2) a co-oxidant such as, for example, basic copper nitrate, Cu2 (0H) 3N03, which is different than the compound of nitrogen, inorganic, cold-burn, and 3) a binder which is preferably a water-soluble binder such as, for example, guar gum. In general, in this preferred embodiment, fuels, co-oxidants, and binders can be used that have been previously described herein. However, preferred examples of fuels for this preferred embodiment include cobalt-amine complexes, and hexaamine-cobalt nitrate which is particularly preferred.

Preferred examples of co-oxidant include base metal carbonates, base metal nitrates, metal oxides, metal nitrates and metal hydroxides. The basic copper nitrate is particularly preferred. Preferred examples of binders include water-soluble or substantially water-soluble polymers, including gum. Guar gum is particularly preferred. The amounts of the ingredients such as fuel, co-oxidant and binder in this preferred embodiment can be readily determined by a person skilled in the art in view of the present disclosure. However, in particular, the amount of the main fuel, which with the exception of the nitrogen, organic, cold-burn compound, can be generally between about 30% and about 90% by weight, preferably between about 40% by weight. % by weight and approximately 75% by weight. The sum of the amount of the co-oxidant, taken together with the amount of the nitrogen, cold-burn organic compound, can be in general between about 10% by weight and about 60% by weight, and preferably, about 15% by weight and approximately 50% by weight. The amount of binder may generally be between about 0.5% by weight and about 12% by weight, and preferably between about 2% by weight and about 10% by weight, and most preferably, between about 3% by weight and about 6% by weight. Although in theory, the compositions are generally used such that they are put into stoichiometric equilibrium in practice, the compositions are often at least slightly fuel-rich, although in principle slightly oxygen-rich compositions are possible. Typically, the level of the ingredients is adjusted to give the best performance balance with respect to, for example, affluent gases and slag characteristics. Preferably, the compositions also contain small amounts of carbon such as, for example, carbon black as a ballistic additive or combustion rate modifier, although this is optional. The amount of carbon black, typically, may be less than about 2% by weight, and preferably less than 1% by weight.

The organic, cold-burn nitrogen compound can be used to partially replace the fuel ingredient. In this case, the amount of co-oxidants can be increased to maintain the desired stoichiometry. This can result in savings in the cost of living, for example, because both basic copper nitrate and guanidine nitrate are significantly less expensive than hexaamine cobalt nitrate. However, surprisingly, the full performance in the generator is maintained despite the replacement. The maintenance of full performance is achieved from a volume perspective because the density of the mixture increases as the relative proportion of basic copper nitrate increases. In general, it is believed that little chemical reaction occurs, if any, when the guanidine nitrate is mixed into the compositions, although the present invention is not bound by this theory of chemical reaction. Combinations may be prepared by mixing individual ingredients, or alternatively, by preparing separate formulations and mixing these formulations. The mixing of individual ingredients is generally preferred. Mixing can be general by conventional procedures with conventional equipment known in the art, followed by forming or granulating the composition.

EXAMPLES The present invention is further described in the non-limiting examples. Unless stated otherwise, the compositions are expressed in percent by weight.

Example 1 An amount (132.4 g) of Co (NH3) 3 (N02) 3, prepared according to the teachings of Hagel et al., "The Tria ines of Cobalt (III)." I. Geo etrical Isomers of trinitrot-romminecobalt (III), "9 Inorganic Chemistry 1496 (June 1970), was slurried in 35 ml of methanol with 7 g of a 38-fold solution. weight percent vinyl acetate / vinyl alcohol polymer resin, pyrotechnic grade, commonly known as VAAR dissolved in methyl acetate. The solvent is allowed to evaporate partially. The paste-like mixture is forced through a 20 mesh screen, allowed to dry to a stiff consistency, and forced again through a screen. The resulting granules were then dried in vacuo at room temperature for 12 hours. Half-inch diameter pellets of the desired material were prepared by pressing. The pellets were combusted at various erent pressures ranging from '42 .18 to 232.02 kg / cm2 (600 to 3300 psi). The combustion speed of the generator was found to be 0.601 cm (0.237 inches) per second at 70.31 kg / cm2 (1000 psig) with a pressure exponent of 0.85 over the tested pressure range.

Example 2 The procedure of Example 1 was repeated with 100 g of Co (NH3) 3 (N02) 3, and 34 g of a 12 weight percent solution of nylon in methanol. The granulation was achieved via sieves of 10 and 16 mesh followed by air drying. The combustion rate of this composition was found to be 0.736 cm (0.290 inches) per second at 70.31 kg / cm2 (1000 psig) with a pressure exponent of 0.74.

Example 3 In a manner similar to that described in Example 1, 400 g of Co (NH3) 3 (N02) 3 were re-slurried with 219 g of a 12 weight percent solution of nitrocellulose in acetone. The nitrocellulose contained 12.6 percent nitrogen. the solvent was allowed to partially evaporate. The resulting paste was forced through an 8 mesh screen followed by a 24 mesh screen. The resulting granules were dried in air overnight and mixed with sufficient calcium stearate mold release agent to provide 0.3 percent in weight in the final product. A portion of the resulting material was pressed into pellets of 1. 27 cm (one-half inch) in diameter and found to exhibit a burn speed of 0.689 cm (0.275 inches) per second at 70.31 kg / cm2 (1000 psig) with a pressure exponent of 0.79. The rest of the material was pressed into 0.317 cm pellets (1/8 inch) in diameter per thickness of 0.177 cm (0.07 inches) in a tablet press, rotary. The density of the pellets was determined, which is 1.88 g / cc. The theoretical flame temperature in this composition was 2.358 ° K and was calculated to provide a gas mass fraction of 0.72.

Example 4 This example describes the preparation of a reusable stainless steel test accessory used to simulate the gas generators, lateral, of the conductor. The test accessory, or simulator, consisted of an ignition chamber of a combustion chamber. The ignition chamber was placed in the center and had 24 holes 0.254 cm (0.10 inches) in diameter that go to the combustion chamber. The ignition chamber is equipped with a lighter detonator. The ignition chamber wall was lined with an 0.00254 cm (0.001 inch) thick aluminum sheet before the 24 / + 60 mesh lighter pellets were torn. The wall and exterior of the combustion chamber consisted of a ring with nine exit holes. The diameter of the holes was varied when changing the rings. Starting from the inside diameter of the outer ring of the combustion chamber, the combustion chamber was equipped with an aluminum plate of 0.0101 cm (0.0010.16 cm (4 inches)), one turn of 30 mesh stainless steel sieve, four turns of a 14 mesh stainless steel screen, a baffle ring, and a gas generator. The generator was left intact in the combustion chamber using an 18 mesh stainless steel sieve "donut." An additional deflector ring was placed around the outer diameter of the outer wall of the combustion chamber. The combustion chamber was equipped with a pressure orifice. The simulator joined either a 60 liter tank or a car airbag. The tank was equipped with pressure holes, temperature, vent, and drain. The car air bags have a maximum capacity of 55 liters and are constructed with two vent holes of 1.27 cm (1/2 inch) in diameter. The tests of the simulator comprising an air bag were configured such that the pressures of the bag were measured. The surface temperature of the outer shell of the bag was inspected during the event of cooling by infrared radiometry, thermal imaging, and thermocouple.

Example 5 Thirty-seven and one-half grams of the 0.125 cm (1/8 inch) diameter pellets prepared as described in Example 3 were combusted in a dewatering inflator test device in a 60-gallon collection tank. 1 as described in Example 4, with the additional incorporation of a second sieve chamber containing 2 rounds of 30 mesh screen and 2 turns of 18 mesh screen. The combustion produced a pressure in the combustion chamber of 908 kg / cm2 (2,000 psia) and a pressure of 17.71 kg / cm2 (39 psia) in the 60L collection tank. The temperature of the gases in the collection tank reached a maximum of 670 ° K at 20 milliseconds. The analysis of the gases collected in the 60 L tank showed a concentration of nitrogen oxides (NO ..) of 500 ppm and a concentration of carbon monoxide of 1,825 ppm. The particulate, ejected, total material as determined by rinsing the tank with methanol and evaporating the rinse was found to be 1,000 mg.

Example 6 The test of Example 4 was repeated except that the 60 L tank was replaced with a 55 L dewatered bag, as is typically employed in the inflator, automobile, driver-side restriction devices. A combustion chamber pressure of 862 kg / cm2 (1900 psia) was obtained with the occurrence of a complete cooling of the bag. An internal bag pressure of 0.908 kg / cm2 (2 psig) at most was observed approximately 60 milliseconds after ignition. The surface temperature of the bag was observed to be maintained below 83 ° C which is an improvement over conventional azide-based inflators, while the bag's cooling performance is completely typical of conventional systems.

Example 7 The nitrate salt of copper tetraamine was prepared by dissolving 116.3 g of copper (II) nitrate hemipentahydrate in 230 L of concentrated ammonium hydroxide and 50 mL of water.

Once the resulting hot mixture had been cooled to 40 ° C, one liter of ethanol was added with stirring to precipitate the tetraamine nitrate product. The dark purple-blue solid was collected by filtration, washed with ethanol, and dried with air. The product was confirmed to be Cu (NH3) 4 (N03) 2, by elemental analysis. The combustion rate of this material as determined from pellets of 1.27 CM (1/2 inch) in diameter, pressed, can be 0.457 CM (0.18 inches) per second at 70.31 kg / cm2 (1000 psig).

Example 8 The tetraamine copper nitrate prepared in Example 7 was formulated with various complementary oxidants and tested for the burning or burning rate. In all cases, 10 g of the material was prepared in slurry with approximately 10 mL of methanol, dried and pressed into pellets of 1.27 CM (1/2 inch) in diameter. The combustion speed was measured at 70.31 kg / cm2 (1000 psig), and the results are shown in the following table: Example 9 An amount of hexaamine-cobalt (III) nitrate was prepared by replacing ammonium chloride with ammonium nitrate in the process for preparing hexaamine-cobalt (III) chloride as taught by G. Pass and H. Sutcliffe, Practical Inorganic Chemistry, 2a Ed., Chapman & Hull, New York, 1974. The material prepared was determined to be [CO (NH3) 6] (N02), by elemental analysis. A sample was pressed into pellets of 1.27 cm (1/2 inch) in diameter, and the combustion rate of 0.66 cm (0.26 inches) per second was measured at 908 kg / cn / (2,000 psi).

Example 10 The material prepared in Example 9 was used to prepare three batches of the gas generator containing hexaamine-cobalt (III) nitrate as the fuel and ceric ammonium nitrate as the co-oxidant. The lots differ in the processing mode and the presence or absence of additives. The combustion rates were determined from pellets of combustion speed of 1.27 cm (1/2 inch) in diameter. The results are summarized below.

Example 11 The material prepared in Example 9 was used to prepare several mixtures of 10 g of generating compositions using various complementary oxidants. In all cases, the appropriate amount of the hexamine nitrate nitrate (III) and the co-oxidant (s) were mixed in approximately 10 L of methanol, allowed to dry, and pressed into 1.27 cm pellets (1/2 inch) in diameter. The pellets were tested for the combustion rate at 70.31 kg / cm2 (1000 psig), and the results are shown in the following table.

Example 12 The binary compositions of hexaaminecobalt (III) nitrate ("HACN") and various complementary oxidants were mixed in batches of 20 grams.

The compositions were dried for 72 hours at 93.3 ° C (200 ° F) and pressed into pellets of 1.27 cm (1/2 inch) in diameter. The burn rates were determined by burning pellets of 1.27 cubic feet (1/2 inch) at different pressures ranging from 70.31 to 281.2 kg / cm2 (1,000 to 4,000 psi). The results are shown in the following table .

Example 13 A processing method was contemplated to prepare small parallelepipeds ("pps") of gas generator at a laboratory scale. The equipment needed to form and cut the pps included a cutting board, a roller and a cutting device. The cutting board consisted of a sheet of 22.86 x 45.22 cm (9 inches x 18 inches) of metal with spacers of paper of 1.27 cm (0.5 inches) wide tapered along the longitudinal edges. The spacers had a cumulative height of 0.109 cm (0.043 inches). The roller consisted of 1 cylinder of 0.3040 meters (1 foot) in length, 5.08 cm (2 inches) in diameter of Teflon. The cutting device consisted of cutting blades, shaft and spacers. The tree was a 0.635 cm (1/4 inch) bolt in which a series of 17 stainless steel washers of 1,905 cm (3/4 inch) in diameter, 0.005 inches thick were placed as cutting blades. Between each carrier blade, four brass spacer washers of 1,693 cm (2/3 inch) in diameter and 0.508 cm (0.20 in) thick were placed, and the front sets were secured by means of a nut. The repetition distance between the circular cutting blades was 0.2159 cm (0.085 inches). A gas generating composition containing a water-soluble binder was mixed dry and then batches of 50-70 grams were mixed in a Spex mixer / mill for 5 minutes with sufficient water so that the material when mixed had a similar consistency to a pasta. A Velestal plastic sheet was tacked to the cutting board and the pasta ball of the generator mixed with water was flattened with the hand on the plastic. A sheet of polyethylene plastic was placed on the generating mix. The roller was placed parallel to the spacers on the cutting board and the pulp was flattened to a width of approximately 63.5 cm (25 inches). The roller was then turned to 90 degrees, placed on top of the spacers, and the pulp was flattened to the maximum amount allowed by the spacers of the cutting board. The polyethylene plastic was carefully peeled off the generator and the cutting device was used to cut the pulp both lengthwise and widthwise.

The Velostat plastic sheet in which the generator has been rolled up and cut has been detached from the cutting board and placed lengthwise on a 10.16 cm (4 inch) diameter cylinder in an oven. convection of 57.22 ° C (135 ° F). After about 10 minutes, the sheet was taken out of the oven and placed on a 1.27 cm (1/2 inch) diameter rod so that the two ends of the plastic sheet formed an acute angle with respect to the rod. The plastic moved back and forth on the rod to open the cuts between the parallelepipeds ("pps"). The sheet was placed widthwise on the 4-inch diameter cylinder in the 135 ° F convection oven and allowed to dry for another 5 minutes. The cuts were opened between the pps on the 1.27 cm rod (1/2 inch) in diameter as before. At this time, it was completely easy to separate the pps from the plastic. The pps separated from each other by rotating them gently in a pint cup or in the screens of a 12 mesh screen. This method breaks the pps into individual pieces with some remaining pairs. The pairs were divided into pieces Individuals by the use of a razor blade. The pps were then placed in a convection oven at 165-225 ° F to dry them completely. The resistance to grinding (at the edge) of the pps thus formed was typically as large or greater than that of the pellets of 1/8 diameter with a convex radius of 0.635 cm (1/4 inch) of curvature and a height maximum of 1,778 cm (0.70 inches) that was formed on a rotating plate. This is remarkable since the latter are three times more massive.

Example 14 A gas generating composition was prepared using hexaamine-cobalt (III) nitrate, [(NH3) 6 (Co] (N03) 3, powder (78.07%, 39.04 g), granules of ammonium nitrate (19.93 5, 9.96 g), and milled polyacrylamide, (molecular weight) MW 15 million, (2.00%, 1.00 g) The ingredients were mixed dry in a Spex mixer / mill for one minute, deionized water was added (12% of the dry weight of the formulation) (6 g), to the mixture that was mixed for an additional 5 minutes in the Spex mixer / mill This resulted in the material with a paste-like consistency that was processed in parallelepipeds (pps) as in Example 13. Mixed and they processed three additional lots of the generator in a similar way, the pps of the four lots were mixed in. The dimensions of the pps were 0.052 inches x 0.072 inches by 0.08 inches.The standard deviations of each of the dimensions were in the 0.0254 cm (0.010 inches) The average weight of pps fu e of 6.62 mg. Apparent bulk density, density as determined by dimensional measurements, and density as determined by solvent displacement, were determined to be 0.86 g / cc, 1.28 g / cc, 1.28 g / cc, and 1.59 g / cc, respectively. The 1.7 kg grinding strengths (at the narrowest edge) were measured with a standard deviation of 0.7 kg. Some of the pps were pressed into pellets of 1.27 c (1/2 inch) in diameter that weighed approximately 3 grams. These pellets fuel speed was determined to be from 0.13 ips to 70.31 kg / cm2 (1000 psi) with a pressure exponent of 0.78.

Example 15 A simulator was constructed according to Example 4. Two grams of a stoichiometric mixture of Mg / Sr (N03) 2 / nylon lighter pellets were placed in the igniter chamber. The diameter of the holes coming out of the outer wall of the combustion chamber was 3/16 of an inch. Thirty grams of the generator described in Example 14 in the form of parallelepipeds were secured in the combustion chamber. The simulator was attached to the 60 L tank described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 161.7 kg / cm2 (2300 psia) in 17 milliseconds, the 60 L tank reached a maximum pressure of 34 psia and the maximum tank temperature was 640 ° K. The NOx, CO and NH3 signals were 20, 380 and 170 ppm, respectively, and 1600 mg of the particulate material was collected from the tank.

Example 16 A simulator with the exact same igniter and the type of generator and the load weight were constructed as in Example 15. In addition, the diameters of the exit orifice of the combustion chamber, exterior were identical. The simulators were attached to a car safety bag of the type described in Example 4. After the ignition, the combustion chamber reached a maximum pressure of 140.67 kg / crt / (140.67 kg / cm2 (2000 psia)) at 15 ° C. milliseconds The maximum pressure of the inflated air bag was 0.06 kg / cm2 (0.9 psia). This pressure was reached in 18 milliseconds after the ignition. The maximum temperature of the surface of the bag was 67 ° C.

Example 17 A gas generating composition was prepared using hexaamine-cobalt (III) nitrate powder (76.29%, 76.29 g), ammonium nitrate granules (15.71%, 15.71 g, Dynamit Nobel, granule size <350 microns), powder of copper oxide formed pyrometallurgically (5.00%, 5.00 g) and guar gum (3.00%, 3.00 g). The ingredients were mixed dry in a Spex mixer / mill for one minute. Deionized water (18% dry weight of the formulation, 9 g) was added to 50 g of the mixture which was mixed for an additional five minutes in the Spex mixer / mill. This resulted in material with the paste consistency that was processed in parallelepipeds (pps) as in Example 13. The same process was repeated for the other 50 g of the dry blended generator and the two batches of pps were mixed together. The average decreases of the mixed pps were 1.77 cm (0.070 inches) by 0.205 cm (0.081 inches) x 0.223 cm (0.088 inches). The standard deviations in each of the divisions were in the order of 0.0254 cm (0.010 inches). The average weight of the pps was 9.60 mg. The apparent bulk density, density as determined by dimensional measurements, and density as determined by solvent displacement were determined to be 0.96 g / cc, 1.17 g / cc, and 1.73 g / cc, respectively. The 5.0 kg mill resistances (at the narrowest edge) were measured with a standard deviation of 2.5 kg. Some of the pps were pressed into pellets of 1.27 cm (1/2 inch) in diameter weighing approximately three grams. From these pellets the combustion speed was determined which is 0.20 ips in 100 psi with a pressure exponent at 0.67.

Example 18 A simulator was constructed according to Example 4. One gram of a stoichiometric mixture of Mg / Sr (N03) 2 / nylon and two grams of lightly oxidized B / KNO3 lighter granules were mixed and placed in the igniter chamber. The diameter of the holes that comes out of the outer wall of the combustion chamber was 0.166 inches. Thirty grams of the generator described in Example 17 in the form of parallelepipeds were secured in the combustion chamber. The simulator was attached to the 60 L tank described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 178.58 kg / cm2 (2540 psia) in 8 milliseconds, the 60 L tank reached a maximum pressure of 2.53 kg / cm2 (36 psia), and the maximum tank temperature was 600 ° K. The levels of NOx, CO, and NH3 were 50, 480, and 800 ppm, respectively, and 240 mg of the particulate material was collected from the tank.

Example 19 A simulator with the same igniter and generator type and exact load weight was constructed, as in Example 18. In addition, the outer diameters of the combustion chamber outlet orifices were identical. The simulator was attached to a car safety bag of the type described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 189.83 kg / cm2 (2700 psia) in 9 milliseconds. The maximum pressure of the inflated airbag was 0.1617 kg / cp / (2.3 psig). This pressure was reached 30 milliseconds after the ignition. The maximum temperature of the bag temperature was 73 ° C.

Example 20 A gas generating composition was prepared using hexaamine-cobalt (III) nitrate powder (69.50%, 347.5 g), copper (II) trihydroxy nitrate, [Cu2 (OH) 3N03], powder (21.5%, 107.5 g), RDX of 10 microns (5.00%, 25 g), potassium nitrate of 26 microns (1.00%, 5 g), and guar gum (3.00%, 3.00 g). The ingredients were mixed dry with the aid of a 60 mesh screen. Deionized water (23% dry weight of the formulation, 15 g) was added to 65 of the mixture which was mixed for an additional five minutes in the mixer / mill. Spex This resulted in material with a square-like consistency that was processed in parallelepipeds (pps) as in Example 13. The same process was repeated for two additional 65 g batches of the dry blended generator and the three batches of pps were mixed jointly. The average dimensions of the pps were 0.144 cm (0.057 inches) x 0.198 cm (0.078 inches) x 0.2133 cm (0.084 inches). The standard deviations in each of the measurements were in the order of 0.0254 cm (0.010 inches). The average weight of the pps was 7.22 mg. Apparent bulk density, density as determined by dimensional measurements and density as determined by solvent displacement were determined to be 0.96 g / cc, 1.2 g / cc, and 1.74 g / cc, crosslinked on the surface. The 3.6 kg ground resistance (at the narrowest edge) was measured with a standard deviation of 0.9 kg. Some of the pps were pressed into pellets of 1.27 cm (1/2 inch) in diameter weighing approximately three grams. From these pellets, the combustion rate was determined which is from 0.27 ips to 70.31 kg / cm2 (1000 psi) with a pressure exponent of 0.51.

Example 21 A simulator was constructed according to Example 4. 1.5 grams of a stoichiometric mixture of Mg / Sr (N0) 2 / nylon and 1.5 grams of B / KN03 lighter granules, slightly over oxidized, were mixed and placed in the chamber lighter The diameter of the holes that comes out of the outer wall of the combustion chamber was 0.449 cm (0.177 inches). 30 grams of the generator described in Example 20 were secured in the combustion chamber in the form of parallelepipeds. The simulator was attached to the 60 L tank described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 214.54 kg / cm2 (3050 psia) in 14 milliseconds. The levels of NOx, CO and NH3 were 25, 800 and 90 ppm, respectively, and 890 mg of particulate material was collected from the tank.

Example 22 A gas generating composition was prepared using hexaamine-cobalt (III) nitrate powder (78.00%, 457.9 g), copper (II) trihydroxy nitrate powder (19.00%, 111.5 g), and guar gum (3.00%, 17.61 g). The ingredients were mixed dry and then mixed with water (32.5% dry weight of the formulation, 191 g) in a Baker-Perkins pint mixer during minutes. To a portion of the resulting wet cake (220 g), an additional 9.2 grams of copper (II) trihydroxy nitrate and an additional 0.30 grams of guar gum were added, as well as 0.80 g of carbon black (Monarch 1100). This new formulation was mixed for 30 minutes in a Baker-Perkins mixer. The wet cake was placed in a hydraulic aricote extruder with a barrel diameter of 5.08 cm (2 inches) and a nozzle orifice diameter of 0.2381 cm (3/32 inch (0.09038 inches)). The extruded material was cut into sections of approximately one foot, allowed to dry under ambient conditions overnight, placed in a closed vessel containing water to thereby increase and soften the material, it was minced into sections of approximately 0.1 inches and dried at 73.88 ° C (165 ° F). The dimensions of the resulting extruded cylinders were an average length of 0.113 inches and an average diameter of 0.091 inches. The apparent volumetric velocity, the density as determined by dimensional measurements, and the density as determined by the displacement of the solvent were 0.86 g / cc, 1.30 g / cc, and 1.61 g / cc, respectively. The crushing strengths of 2.1 and 4.1 kg were measured in the circumference and the axis, respectively. Some of the extruded cylinders are pressed into pellets 1.27 cm (1/2 inch) in diameter weighing approximately 3 grams. From these pellets the combustion rate was determined which is from 0.2 ips to 70.31 kg / cm2 (1000 psi) with an exponent of 0.29.

Example 23 Three simulators were constructed according to Example 4. 1.5 grams of a stoichiometric mixture of Mg / Sr (N03) 2 / nylon and 1.5 grams of oxidizing granules of B / KN03, slightly oxidized were mixed and placed in the igniter chambers. The diameter of the holes coming out of the outer wall of the combustion chamber was 0.2971 cm (0.117 inches), 0.4216 cm (0.166 inches) and 0.3861 cm (0.152 inches), respectively. Thirty grams of the generator described in Example 22 was secured in the form of destroyed circuits in each of the combustion chamber. The simulants were joined, in their assignment to the 60 L tank described in Example 4. After the injection, the combustion chamber reached a maximum pressure of 1585 1665, and 1900 psia, respectively. The maximum tank pressures were 2.24, 2.39, 2.46 kg / cm2 (32, 34 and 35 psia), respectively. NOx levels were 85, 180 and 185 ppm, m whereas CO levels were 540, 600 and 600 ppm, respectively. The NH3 levels were below 2 ppm. The particle levels were 420, 350 and 360 mg, respectively.

Example 24 The addition of small amounts of carbon to the gas generating formulations has been found to improve the grinding resistance of the parallelepipeds and extruded pellets formed as in Example 13 or Example 22. The following table summarizes the improved resistance to ground with the addition of carbon to a typical gas generating composition within the scope of the present invention. The percentages are shown, percent by weight.

Table 3 Improved Ground Resistance with Carbon Addition HACN = hexaaminecobalt (III) nitrate, [(NH3) 6Co] (N03) 3 (Tiokol) CTN 0 copper trihydroxy nitrate (II) [Cu2 (0H3) N03] (Thiocol) Guar = guar gum (Aldrich) Carbon = carbon black (Monarch 1100"(Cabot) EP = Blocked pellet (see Example 22) pps. = parallelepipeds (see Example 13) strength = resistance to grinding of pps or pellets clogged in kilograms.

Example 25 Hexaamine-cobalt nitrate was pressed (III) in pellets of four grams with diameter of 1/2 inch Half of the pellets were weighed and placed in a 95 ° C oven for 700 hours. After aging, the pellets were weighed once more. No weight loss was observed. The combustion speed of the pellets maintained at room temperature was 0.16 ips and 70.31 kg / cm2 (1000 psia) with a pressure exponent of 0.60. The combustion speed of the pellets maintained at 95 ° C for 700 hours can be from 0.15 to 70.31 kg / cm2 (1000 psia) with a pressure exponent of 0.68.

Example 26 A gas generating composition was prepared using hexaamine-cobalt (III) powder (76.00%, 273.6 g), copper trihydroxine-treatment powder II) (16.00%, 57.6 G), potassium nitrate of 26 microns (5.00%, 18.00) g), and guar gum (3.00, 10.8 g). Deionized water (24.9% of the dry weight of the formulation, 16.2 g) was added to 65 g of the mixture that was mixed for an additional five minutes in the Spex mixer / mill. This resulted in material with a paste-like consistency that was processed in parallelepipeds (pps) as in Example 13. A process was repeated for the other batches of 50-65 g of the echo-blended generator and all batches of pps were They mixed together. The average dimensions of the pps were 0.1651 cm (0.065 inches) x 0.1778 cm (0.07 inches) x 0.2082 cm (0.082 inches). The standard deviations in each of the dimensions were in the order of 0.0127 cm (0.005 inches). The average weight of the pps was 7.42 mg. Apparent bulk density, density as determined by dimensional measurements, and density as determined by the displacement of solvents were determined to be 0.86 g / cc, 1.5 g / cc, and 1.68 g / cc, respectively. The 2.1 kg crushing strengths (at the narrowest edge were measured with the standard measurement of 0.3 kg.) Some of the pps were pressed into ten pellets of half an inch in diameter that grow approximately three grams, approximately 60 g of pps and five pellets of 1.27 cm (1/2 inch) in diameter were placed in an oven maintained at 107 ° C. After 450 hours at this temperature, weight losses of 0.25% and 0.41% were observed for the pps and the pellets, respectively The rest of the pps and the pellets were stored under ambient conditions, the data of the combustion velocity of both pellet assemblies were obtained and summarized in Table 4.

Table 4 Comparison of the Burning Speed Before and After Accelerated Aging Example 27 Two simulators were constructed according to Example 4. Each igniter chamber was placed in a stirred mixture of 1.5 g of a stoichiometric mixture of Mg / Sr (N03) 2 / nil, and 1.5 grams of lightener granules of B / KN03. about rusted. The diameter of the services that leaves the outer wall of the combustion chamber in each simulator was 0.4495 cm (0.177 inches). Thirty grams of the generator aged to the environment described in Example 26 in the form of parallelepipeds were secured in the combustion chamber of a simulator, while thirty grams of the pps of the generator aged at 107 ° C were placed in the other combustion chamber . The simulants were attached to the 60 L tank described in Example 4. The test fire is summarized in Table 5 below.

Table 5 Results of the Test Fire for the Aged Generator Example 28 A mixture of 2Co (NH3) 3 (N02) 3 and Co (NH3) 4 (N02) 2Co (NH3) z, was prepared and pressed into a pellet having a diameter of about 0.504 inches. The complexes were prepared within the scope of the teachings of Hagel, et al., Reference identified above. The pellets were identified in a test pump that was pressurized to 70.31 kg / cm2 (1000 psi) with nitrogen gas. The pellet was combusted with a hot wire and the combustion rate was measured and observed to be 0.38 inches per second. The theoretical calculations indicated a flame temperature of 1805 ° C. From the theoretical calculations, it is predicted that the main reaction products would be solid CoO and gaseous reaction products. The main gaseous reaction gas products are predicted to be as follows.

Product Volume H20 57.09 N2 38.6 02 3.1 Example 29 An amount of Co (NH3) 3 (N02) 3 / was prepared according to the teachings of Example 1 and tested using differential scanning calorimetry. It was observed that the complex produced a vigorous exotherm at 200 ° C.

Example 30 The theoretical calculations were undertaken for Co (NH3) 3 (N02) 3 • These calculations indicated a flame temperature of approximately 2,000 ° K and a gas yield of approximately 1.75 times that of a conventional, azide gas-generating composition of sodium, based on an equal volume of generating composition ("performance ratio"). The theoretical calculations were also undertaken by a series of gas generating compositions. The composition and data of the theoretical performance are shown below in Table 6.

Table 6 The performance ratio is a normalized relation to a unit volume of azide-based gas generator. The theoretical gas yield for a typical gas generator based on sodium azide (68% by weight of NaN3, 30% by weight of MoS2, 2% by weight of S) is about 0.85 g gas / cc of NaN3 generator .

Example 31 The theoretical calculations were carried out for the reduction of [Co (NH3) 6] (C10 / 3 and CaH2 as illustrated in Table 6 to evaluate its use as a hybrid gas generator.) If this formulation was left to combust in the presence of 6.80 times its weight in argon gas, the flame temperature decreased from 2577 ° C to 1085 ° C, assuming 100% efficient heat transfer.The exhaust gases consist of 86.8 5 by volume of argon, 1600 ppm by volume of hydrogen chloride, 10.2% by volume of water, and 2.9% by volume of nitrogen The total slag weight will be 6.1% in raisin.

Example 32 The complexes of pentaamine-cobalt (III) nitrate containing a common ligand in addition to NH3 were synthesized. The aquopentaaminecobalt (III) nitrate and pentaaminecarbonatecobalt (III) nitrate were synthesized, according to Inorg. Syn., Vol. 4, p. 171 (1973). The pentane nitrate inohydroxicobalt to (III) was synthesized according to H.J.S.

King, J. Chem. Soc, p. 2105 (1925) and Zeit Anorg. Chem., Vol. 300 p. 186 (1959). Three batches of the gas generator were prepared using the pentaamine-cobalt (III) nitrate complexes described above. In all cases, guar gum was added as a binder. Copper (II) trihydroxyinitrate, [Cu2 (OH) 3N03], was added as the co-oxidant where necessary. The combustion rate was determined from pellets of combustion velocity of 1.27 cm (1/2 inch) in diameter. The results are summarized below in Table 7.

Table 7 Formulations Containing [Co (NH3) 5X] (N03) 2 Example 33 A formulation comprising the following starting ingredients was prepared: 1) 72.84% by weight of cobal tohexamine nitrate, 2) 21.5% by weight of basic copper nitrate, 3) 5.0% by weight of guar gum, and 4) 0.66% by weight of carbon. The formulation was processed as described in Example 22 except that an individual screw extruder was employed and the extruded cylinders were incorporated into a 0.035 inch center bore. The formulations were tested by the same processing described in Example 23 at various loads ranging from 32 to 38 grams. The results of the test showed that the values of the particulate material was from 0.6 g and 1.0 g for all samples. The pressures of the tanks varied from 2.74 to 3.37 kg / cm2 (39 to 48 psia) depending on the load.

Example 34 A formulation to be extruded was prepared, comprising: 1) 38.75% by weight of basic copper nitrate, 2) 36.38% by weight of hexaaminecobalt nitrate, 3) 19.5% by weight of guanidine nitrate, 4) 5.0 % by weight of guar gum, and 5) 0.37% by weight of carbon black. The mixture was prepared by mixing the ingredients according to the processing described in Example 33. An initial test duration was carried out with a sample of 35 g with the extruded material as described in Example 23. The combustion pressure it was 197.43 (2808 psi), and the tank pressure was 2.81 kg / cm2 (39.9 psia). The quantities of the trace gas products were: ammonia (70 ppm), N0X, (40 ppm), and CO (600 ppm). The values of the material in the form of particles were only 0.281 g. The pressure observed in the tank was 2.81 kg / cm2 (39.9 psia) compared to that obtained with 33 g of the formulation prepared according to Example 33, which typically provided 39 to 40 psia under similar conditions.

Example 35 A formulated mixture to be extruded was prepared, comprising: 1) 40.43% by weight of basic copper nitrate, 2) 37.86% by weight of hexaaminecobalt nitrate, 3) 15.8% by weight of guanidine nitrate, 4) 5.7% by weight of guar gum, and 5) 0.3% by weight of carbon black. The mixture was prepared by mixing the ingredients according to the processing described in Examples 33 and 34. Results comparable to those of Example 34 were expected and obtained. Gas generators are described in U.S. Patent Application No. of Series 08 / 507,552 filed July 26, 1995, which is a continuation in part of United States Patent Application Serial No. 08 / 184,456, filed on January 19, 1994, the full descriptions of which they are incorporated herein by reference.

Summary In summary, the present invention provides particulate materials that overcome some of the limitations of conventional azide-based gas generating compositions. The complexes of the present invention produce non-toxic gaseous products that include water vapor, oxygen and nitrogen, certain complexes are also capable of efficient decomposition to a metal or metal oxide, and nitrogen and water vapor. Finally, the reaction temperatures and combustion rate are within acceptable ranges. The invention can be incorporated into other specific forms without departing from its essential characteristics. The described modalities will also be considered in all aspects only as illustrative and not restrictive. The scope of the invention, therefore, is indicated by the appended claims in lieu of the foregoing description.

It is noted that in relation to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property:

Claims (88)

1. A gas generating composition, characterized in that it comprises: a metal cation complex, at least one neutral ligand containing hydrogen and nitrogen, and sufficient oxidizing anion to balance the charge of the metal cation such that when the complex is combusted, produces a gas mixture containing nitrogen gas and water vapor; and at least one organic, nitrogen-containing, cold-burn compound.

2. A gas generating composition according to claim 1, characterized in that the complex is selected from the group consisting of metal nitrite amines, metal nitrate amines, metal perchlorate amines, metal nitrite hydrazines, metal nitrate hydrazines, metal perchlorate hydrazines, and mixtures thereof.

3. A gas generating composition according to claim 1, characterized in that the complex is a metal nitrite amine.

4. A gas generating composition according to claim 1, characterized in that the complex is a metal nitrate amine.

5. A gas generating composition according to claim 1, characterized in that the complex is a metal perchlorate amine.

6. A gas generating composition according to claim 1, characterized in that the complex is a metal nitrite hydrazine.

7. A gas generating composition according to claim 1, characterized in that the complex is a metal nitrate hydrazine.

8. A gas generating composition according to claim 1, characterized in that the complex is a metal perchlorate hydrazine.

9. A gas generating composition according to claim 1, characterized in that the metal cation is a cation of transition metal, alkaline earth metal, metalloid, or lanthanide metal.

10. A gas generating composition according to claim 9, characterized in that the metal cation is selected from the group consisting of magnesium, manganese, nickel, titanium, copper, chromium, zinc, and tin.

11. A gas generating composition according to claim 1, characterized in that the metal cation is a transition metal cation.

12. A gas generating composition according to claim 11, characterized in that the transition metal cation is cobalt.

13. A gas generating composition according to claim 11, characterized in that the transition metal cation is selected from the group consisting of rhodium, iridium, ruthenium, palladium, and platinum.

14. A gas generating composition according to claim 1, characterized in that the oxidizing anion is coordinated with the metal cation.

15. A gas generating composition according to claim 1, characterized in that the oxidizing anion is selected from the group consisting of nitrate, nitrite, chlorate, perchlorate, peroxide, and superoxide.

16. A gas generating composition according to claim 1, characterized in that the oxidative, inorganic anion and the inorganic neutral ligand are free of carbon.

17. A gas generating composition according to claim 1, characterized in that the complex includes at least one other common ligand, in addition to the neutral ligand.

18. A gas generating composition according to claim 17, characterized in that the common ligand is selected from the group consisting of ligands of aquo (H20), hydroxo (OH), perhydroxime (02H), peroxo (02), carbonate (C03), carbonyl (CO), oxalate (20i), nitrosyl (NO), cyano (CN), isocyanate (NC), isothiocyanate (NCS), thiocyanate (SCN), amido (NH2), imido (NH), sulfate (SO /, chlorine (Cl), fluorine (F), phosphate (PO /, and ethylenediaminetetraacetic acid (EDTA).

19. A gas generating composition according to claim 1, characterized in that the complex includes a common counterion in addition to the oxidizing anion.

20. A gas generating composition according to claim 19, characterized in that the common counterion is selected from the group consisting of the counterions hydroxide (OH "), chloride (Cl"), fluoride (F "), cyanide (CN") ), thiocyanate (SCN "), carbonate (C03" 2), sulfate (SO / 2), phosphate (PO / 3), oxalate (C20 / 2), borate (BO / 5), and ammonium (NH4 +).

21. A gas generating composition according to claim 1, characterized in that the complex has a concentration in the gas generating composition from 30% to 90% by weight, wherein the gas generating composition additionally comprises a binder and a co-oxidant. , such that the binder has a concentration in the gas generating composition from 0.5% to 12% by weight, and wherein the sum of the amount of the co-oxidant and the cold-burn compound in the gas generating composition is from 10% up to 60% by weight.

22. A gas generating composition according to claim 1, characterized in that it also comprises a co-oxidant different from the cold-burn compound.

23. A gas generating composition in accordance with the rei indication 22, characterized in that the co-oxidant is selected from perchlorates, chlorates, peroxides, nitrites and nitrates alkali, alkaline earth, lanthanide, or ammonium.

24. A gas generating composition according to claim 22, characterized in that the co-oxidant is selected from metal oxides, metal hydroxides, metal peroxides, hydrated metal oxides, metal oxide hydroxides, hydrated metal oxides, basic metal carbonates, nitrates basic metals, and mixtures thereof.

25. A gas generating composition according to claim 22, characterized in that co-oxidant is selected from copper, cobalt, manganese, tungsten, bismuth, molybdenum and iron oxides.

26. A gas generating composition according to claim 22, characterized in that the co-oxidant is a metal oxide selected from CuO, Co203, Co304, CoFe204, Fe203, Mo03, Bi2Mo06, and Bi203.

27. A gas generating composition according to claim 22, characterized in that the co-oxidant is a metal hydroxide selected from Fe (OH) 3, Co (OH) 3, Co (0H) 2, Ni (OH) 2 , Cu (OH) 2, and Zn (OH) 2.

28. A gas generating composition according to claim 22, characterized in that the co-oxidant is a metal oxide hydrate or a hydrated metal oxide selected from Fe203-xH20, Sn02-xH20, and Mo03-H20.

29. A gas generating composition according to claim 22, characterized in that the co-oxidant is a metal oxide hydroxide selected from CoO (OH) 2, FeO (OH) 2, MnO (OH) 2, and MnO (OH) ) 3.

30. A gas generating composition according to claim 22, characterized in that the co-oxidant is a basic metal carbonate selected from metal oxide selected from CuC03 • Cu (OH) 2 (malachite), 2Co (C03) • 3Co (OH) 2-H20, C? 0.69Fe0.34 (C03) o.2 (OH) 2, Na3 [Co (C03) 3] -3H20, Zn2 (C? 3) (OH) 2, Bi2Mg ( C03) 2 (OH) 4, Fe (C03) 0.12 (OH) 2.76, CU1.54Zno.4e (C03) (0H) 2, CO0.49CU0.51 (C03) o.43 (OH)? 1 Ti3Bi4 (C03) 2 (OH) 209 (H20) 2, and (BiO) 2C03.

31. A gas generating composition according to claim 22, characterized in that the co-oxidant is a basic metal nitrate selected from Cu2 (OH) 3N03, Co2 (OH) 3N03, CuCo (OH) 3N03, Zn2 (OH) 3N03, Mn (OH) 2N03, Fe4 (OH) __N03 • 2H20, M (N03) 202, BiON03'H20, and Ce (OH) (N03) 3 • H20.

32. A gas generating composition according to claim 1, characterized in that it also comprises a binder.

33. A gas generating composition according to claim 32, characterized in that the binder is soluble in water.

34. A gas generating composition according to claim 33, characterized in that the binder is selected from naturally occurring gums, polyacrylic acids, and polyacrylamides.

35. A gas generating composition according to claim 32, characterized in that the binder is not soluble in water.

36. A gas generating composition according to claim 35, characterized in that the binder is selected from nitrocellulose, VAAR, and nylon.

37. A gas generating composition according to claim 1, characterized in that the complex is hexaamine cobalt nitrate (III), ([(NH3) 6Co] (N03) 3) and the co-oxidant is copper (II) trihydroxyinitrate (Cu2 (OH) 3N03).

38. A gas generating composition according to claim 1, characterized in that it also comprises carbon powder present from 0.1% to 6% by weight of the gas generating composition, wherein the composition exhibits improved grinding resistance compared to the composition without carbon powder.

39. A gas generating composition according to claim 1, characterized in that it also comprises carbon powder present from 0.3% to 3% by weight of the gas generating composition.

40. A method for inflating an air bag, characterized in that it comprises combusting a gas generating composition containing a complex of a transition metal cation or an alkaline earth metal cation, at least one neutral ligand containing hydrogen and nitrogen, and sufficient oxidizing anion to balance the charge of the metal cation, such that when the gas generating composition is combusted, a mixture of gases containing nitrogen gas and water vapor is produced, wherein the composition additionally contains less a nitrogen-containing, organic, cold-burning compound.

41. A method for inflating an air bag according to claim 40, characterized in that the combustion of the metal complex is initiated by heat.

42. A method for inflating an air bag according to claim 40, characterized in that the complex is selected from the group consisting of metal nitrite amines, metal nitrate amines, metal perchlorate amines, metal nitrite hydrazines, hydrazines of metal nitrate, metal perchlorate hydrazines, and mixtures thereof.

43. A method for inflating an air bag according to claim 40, characterized in that the complex is a metal nitrite amine.

44. A method for inflating an air bag according to claim 40, characterized in that the complex is a metal nitrate amine.

45. A method for inflating an air bag according to claim 40, characterized in that the complex is a metal perchlorate amine.

46. A method for inflating an air bag according to claim 40, characterized in that the complex is a metal nitrite hydrazine.

47. A method for inflating an air bag according to claim 40, characterized in that the complex is a metal nitrate hydrazine.

48. A method for inflating an air bag according to claim 40, characterized in that the complex is a metal perchlorate hydrazine.

49. A method for inflating an air bag according to claim 40, characterized in that the transition metal cation is cobalt.

50. A method for inflating an air bag according to claim 40, characterized in that the transition metal cation or the alkaline earth metal cation is selected from the group consisting of magnesium, manganese, nickel, titanium, copper, chromium and zinc.

51. A method for inflating an air bag according to claim 40, characterized in that the transition metal cation is selected from the group consisting of rhodium, iridium, ruthenium, palladium, and platinum.

52. A method for inflating an air bag according to claim 40, characterized in that the oxidizing anion is coordinated with the metal cation.

53. A method for inflating an air bag according to claim 40, characterized in that the oxidizing anion is selected from the group consisting of nitrate, nitrite, chlorate, perchlorate, peroxide, and superoxide and mixtures thereof.

54. A method for inflating an air bag according to claim 40, characterized in that the oxidative anion, inorganic and the inorganic neutral ligand are free of carbon.

55. A method for inflating an air bag according to claim 40, characterized in that the complex includes at least one other common ligand, in addition to the neutral ligand.

56. A method for inflating an air bag according to claim 40, characterized in that the common ligand is selected from the group consisting of ligands of aquo (H20), hydroxo (OH), perhydroxo (02H), peroxo (02) carbonate (C03), carbonyl (CO), oxalate (C20 / nitrosyl (NO), cyano (CN), isocyanate (NC) isothiocyanate (NCS), thiocyanate (SCN), amido (NH2) imido (NH), sulfate (S04) ), chlorine (Cl), fluorine (F) phosphate (P04), and ethylenediaminetetraacetic acid (EDTA).

57. A method for inflating an air bag according to claim 40, characterized in that the complex includes a common counterion in addition to the oxidizing anion.

58. A method for inflating an air bag according to claim 57, characterized in that the common counterion is selected from the group consisting of the counterions hydroxide (0H ~), chloride (Cl "), fluoride (F"), cyanide (CN "), thiocyanate (SCN"), carbonate (C03 ~ 2), sulfate (S0-2), phosphate (P04"3), oxalate (C204" 2), borate (B04"5), and ammonium (NH4 +).

59. A method for inflating an air bag according to claim 40, characterized in that the complex and the oxidizing anion combined have a concentration in the gas generating composition from 50% to 80% by weight, eh where the gas generating composition comprises additionally a binder and a co-oxidant, such that the binder has a concentration in the gas generating composition from 0.5% to 10% by weight, and the co-oxidant has a concentration in the gas generating composition from 5% to 50 % in weigh.

60. A method for inflating an air bag according to claim 40, characterized in that the gas generating composition that is put into combustion further comprises a cooxidant.

61. A method for inflating an air bag according to claim 60, characterized in that the co-oxidant is selected from perchlorates, chlorates, peroxides, and alkali, alkaline-earth, lanthanide, or ammonium nitrates.

62. A method for inflating an air bag according to claim 60, characterized in that the co-oxidant is selected from metal oxides, metal hydroxides, metal peroxides, hydrated metal oxides, metal oxide hydroxides, hydrated metal oxides, metal carbonates basic, basic metallic nitrates, and mixtures thereof.

63. A method for inflating an air bag according to claim 60, characterized in that co-oxidant is selected from copper, cobalt, manganese, tungsten, bismuth, molybdenum and iron oxides.

64. A method for inflating an air bag according to claim 60, characterized in that the co-oxidant is a metal oxide selected from CuO, Co203, Co304, C? Fe204, Fe20, M0O3, Bi2Mo06, and Bi203.

65. A method for inflating an air bag according to claim 60, characterized in that the co-oxidant is a metal hydroxide selected from Fe (OH) 3, Co (OH) 3, Co (OH) 2, Ni ( OH) 2, Cu (OH) 2, and Zn (OH) 2.

66. A method for inflating an air bag according to claim 60, characterized in that the co-oxidant is a metal oxide hydrate or a hydrated metal oxide selected from Fe203'xH20, Sn02-xH20, and Mo03-H20.

67. A method for inflating an air bag according to claim 60, characterized in that the co-oxidant is a metal oxide hydroxide selected from CoO (OH) 2, FeO (OH) 2, MnO (OH) 2, and Mn0 (0H) 3.

68. A method for inflating an air bag according to claim 60, characterized in that the co-oxidant is a basic metal carbonate selected from metal oxide selected from CuC03-Cu (OH) 2 (malachite), 2Co (C03) • 3Co (OH) 2-H20, Coo.69Feo.34 (CO3) 0.2 (OH) 2, Na3 [Co (C03) 3] • 3H20, Zn2 (C? 3) (OH) 2, Bi2Mg ( C03) 2 (OH) 4, Fe (C03) 0.12 (OH) 2.76, Cu1.54Zno.4e (C03) (OH) 2, CO0.49CU0.51 (C03) 0.43 (OH) 1.1, TÍ3BÍ4 (C03) 2 (OH) 209 (H20) 2, and (BiO) 2C03.

69. A method for inflating an air bag according to claim 60, characterized in that the co-oxidant is a basic metal nitrate selected from Cu2 (0H) 3N03, Co2 (0H) 3N03, CuCo (OH) 3N03, Zn2 (OH) 3N03, Mn (0H) 2N03, Fe4 (OH)? _N03-2H20, Mo (N03) 202, BiON03-H20, and Ce (OH) (N03) 3-3H20.

70. A method for inflating an air bag according to claim 40, characterized in that the gas generating composition that is put into combustion further comprises a binder.

71. A method for inflating an air bag according to claim 70, characterized in that the binder is soluble in water.

72. A method for inflating an air bag according to claim 71, characterized in that the binder is selected from naturally occurring gums, polyacrylic acids, and polyacrylamides.

73. A method for inflating an air bag according to claim 70, characterized in that the binder is not soluble in water.

74. A method for inflating an air bag according to claim 73, characterized in that the binder is selected from nitrocellulose, VAAR, and nylon.

75. A method for inflating an air bag according to claim 40, characterized in that the complex is hexaaminecobalt (III) nitrate, ([(NH3) eCo] (N03) 3) and the co-oxidant is copper (II) trihydroxyinitrate ( Cu2 (OH) 3N03).

76. A method for inflating an air bag according to claim 40, characterized in that it further comprises carbon powder present from 0.1% to 6% by weight of the gas generating composition, wherein the composition exhibits improved resistance to grinding in comparison to the composition without carbon dust.

77. A method for inflating an air bag according to claim 40, characterized in that it also comprises carbon powder present from 0.3% to 3% by weight of the gas generating composition.

78. A gas generating device characterized in that it comprises: a gas generating composition, comprising: a complex of a transition metal cation or an alkaline earth metal cation and a neutral ligand containing hydrogen and nitrogen, such that when put into combustion the complex, a mixture of gases containing nitrogen gas and water vapor is produced; sufficient oxidant anion to balance the charge of the metal cation; and at least one nitrogen-containing, organic, cold-burned compound; and a lighter to start combustion of the composition.

79. A gas generating device according to claim 78, characterized in that the lighter for initiating combustion includes a lighter composition comprising a mixture of different lighter compositions.

80. A gas generating device according to claim 78, characterized in that the igniter for initiating the combustion includes a igniter composition comprising a mixture of Mg / Sr (N03) 2 / nylon and B / KN03.

81. An automobile air bag system, characterized in that it comprises: an air bag, inflatable, folded; a gas generating device connected to the air bag for inflating the air bag, the gas generating device containing a gas generating composition comprising: a complex of a transition metal cation or an alkaline earth metal cation and a neutral ligand containing hydrogen and nitrogen, such that when the complex is combusted, a gas mixture containing nitrogen gas and water vapor is produced; sufficient oxidant anion to balance the charge of the metal cation; and at least one nitrogen-containing, organic, cold-burned compound; and a lighter to ignite the gas generating composition.

82. A vehicle comprising a complementary restriction system, characterized in that it has an air bag system comprising: an air bag, inflatable, folded; a gas generating device connected to the air bag for inflating the air bag, the gas generating device containing a gas generating composition comprising: a complex of a transition metal cation or an alkaline earth metal cation and a neutral ligand containing hydrogen and nitrogen, such that when the complex is combusted, a gas mixture containing nitrogen gas and water vapor is produced; sufficient oxidant anion to balance the charge of the metal cation; and at least one nitrogen-containing, organic, cold-burned compound; and a lighter to ignite the gas generating composition.

83. A gas generating composition according to claim 1, characterized in that the cold-burn compound has a heat of formation of less than about -400 cal / g.

84. A gas generating composition according to claim 1, characterized in that the cold-burn compound has a heat of formation of less than about -600 cal / g.

85. A gas generating composition according to claim 1, characterized in that the cold-burn compound is a guanidine salt or a guanidine derivative.

86. A gas generating composition according to claim 1, characterized in that the cold-burn compound is guanidine nitrate.

87. A gas generating composition according to claim 1, characterized in that the amount of the cold-burn compound is greater than about 0% by weight and up to about 40% by weight.

88. A gas generating composition, characterized in that it comprises: a complex of a metal cation and an aliphatic, neutral ligand containing hydrogen and nitrogen, such that when the complex is combusted, a gas mixture containing nitrogen gas is produced and water vapor; and an amount of oxidizing anion that is sufficient to at least partially balance the charge of the metal cation.