ES2366329T3 - METAL COMPLEXES FOR USE AS GAS GENERATORS. - Google Patents

Abstract

A gas generating composition comprising: a nitrite amine complex or a nitrate amine complex of a cation of cobalt, magnesium, manganese, nickel, titanium, chromium, zinc, or tin, in which there is sufficient nitrite anion or nitrate anion to balance the charge of the cation, such that, when the nitrite amine complex or the nitrate amine complex goes into combustion, a mixture of gases containing nitrogen gas and water vapor is produced; and at least one compound containing cold combustion organic nitrogen.

Description

The present invention generally relates to gas generating compositions that are capable of combustion to generate gases. More particularly, the composition is oxidized to produce significant amounts of gases, particularly water vapor and nitrogen.

Gas-generating chemical compositions are useful in a number of different contexts. An important use for such compositions is in the operation of "air bags". Air bags are gaining acceptance to the point that many, if not all, new cars are equipped with such devices. Actually, many new cars are equipped with multiple air bags to protect the driver and passengers.

In the context of automobile air bags, sufficient gas must be generated to inflate the device within a fraction of a second. Between the time the car has impacted an accident, and the time that the driver would otherwise be driven against the steering wheel, the air bag must fully inflate. As a consequence, almost instantaneous gas generation is required.

There are a number of additional important design criteria that must be met. Car manufacturers and others have established the required criteria that they must meet 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 generating composition produce gas at a required rate. Likewise, the specifications establish strict limits on the generation of toxic or harmful gases or solids. Examples of restricted gases include carbon monoxide, carbon dioxide, NOx, SOx, and hydrogen sulfide.

The gas must be generated at a sufficiently and reasonably low temperature, so that a car occupant does not burn after impact with an inflated air bag. If the gas produced is too hot, there is a possibility that the occupant of the motor vehicle may burn after impact with a newly deployed air bag. Accordingly, it is necessary that the combination of the gas generator and the construction of the air bag insulates the occupants of the car from excessive heat. All this is required while the gas generator maintains an adequate combustion rate.

Another related, but important, design criterion is that the gas generating composition produces a limited amount of particulate materials. Particulate materials may interfere with the operation of the supplementary restraint system, present a risk of inhalation, irritate the skin and eyes, or constitute a hazardous solid residue that must be treated after the operation of the safety device. In the absence of an acceptable alternative, the production of irritating particles is one of the undesirable, but tolerated, aspects of the sodium azide materials currently used.

In addition to the production of limited quantities of particles, if they are produced, it is desirable that at least the set of any of said particles be easily filterable. For example, it is desirable for the composition to produce a filterable slag. If the reaction products form a filterable material, the products can be filtered and prevent them from escaping into the surrounding environment.

Both organic and inorganic materials and possible gas generators have been proposed. Such gas generating compositions include oxidants and fuels that react at rates high enough to produce large amounts of gas in a fraction of a second.

Currently, sodium azide is the most widely used and currently accepted gas generating material. Sodium azide nominally meets the specifications and guidelines of the industry. However, sodium azide presents a certain number of persistent problems. Sodium azide is highly toxic as a starting material, since its level of toxicity measured as LD50 in oral rat is within the range of 45 mg / kg. Workers who routinely manipulate sodium azide have experienced various health problems such as severe headaches, respiratory deficiencies, seizures, and other symptoms.

In addition, regardless of the auxiliary oxidant used, combustion products from a sodium azide gas generator include caustic reaction products such as sodium oxide, or sodium hydroxide. As oxidants for sodium azide, disulfide or molybdenum sulfide has been used. However, the use of such oxidants results in toxic products such as hydrogen sulphide gas and corrosive materials such as sodium oxide and sodium sulfide. The workers and occupants of rescued cars have complained about both the hydrogen sulphide gas and the corrosive dust produced by the operation of the gas generators based on sodium azide.

Similarly, increasing problems are anticipated in relation to waste from supplementary restraint systems inflated with unused gas, for example, car air bags, in scrapped cars. The sodium azide that remains in such supplementary restraint systems can leave the car discarded to become a water contaminant or a toxic waste. Actually, some have expressed concern that sodium azide could form heavy metal azides or explosive hydrazolic acid when they come into contact with battery acids, after being discarded.

Sodium azide-based gas generators are most commonly used for air bag inflation, but with the significant disadvantages of such compositions, many alternative gas generating compositions have been proposed to replace sodium azide. However, most of the proposed sodium azide substitutes fail to adequately meet all the criteria set forth above.

DE 4442170C discloses a gas generating composition comprising diamine copper (II) nitrate and nitroguanidine.

Therefore, it should be noted that there are a number of important criteria for the selection of gas generating compositions for use in supplementary restraint systems in automobiles. For example, it is important to select starting materials that are not toxic. At the same time, combustion products should not be toxic or harmful. In this regard, industry standards limit the allowable amounts of various gases and particles produced by the operation of supplementary restraint systems.

Therefore, it would be a significant advance to provide compositions capable of generating large amounts of gas that overcome the problems identified in the existing technique. It would be a further advance to provide a gas generating composition that was based on substantially non-toxic starting materials and that produced substantially non-toxic reaction products. It would be another further advance in the art to provide a gas-generating composition that produces very limited amounts of toxic or irritating particle debris and limited undesirable gaseous products. Likewise, it would be an advance to provide a gas generating composition that would form a solid slag easily filtered after the reaction.

Said compositions and methods for their use are disclosed and claimed in the present invention.

Accordingly, seen from a first aspect, the present invention provides a gas generating composition comprising: a nitrite amine complex or an amine nitrate complex of a cation of cobalt, magnesium, manganese, nickel, titanium, chromium, zinc, or tin, in which there is enough nitrite anion or nitrate anion to balance the cation charge, so that when the nitrite amine complex or the nitrate amine complex goes into combustion, a mixture of gases is produced that contain nitrogen gas and water vapor; and at least one compound containing cold burning organic nitrogen.

Seen from a further aspect, the present invention provides a gas generating device comprising a gas generating composition comprising: a nitrite amine complex or an amine nitrate complex of a cobalt, magnesium, manganese, nickel, titanium cation, chromium, zinc, or tin, so that when the nitrite amine complex or nitrate amine complex goes into combustion, a mixture of gases containing nitrogen gas and water vapor, enough nitrite anion or nitrate anion is produced to balance the charge of the cation and at least one compound containing cold burning organic nitrogen and an ignition element to initiate the combustion of the gas generating composition.

Seen from yet another aspect, the present invention provides an air bag inflation process comprising the combustion of a gas generating composition as defined in the present invention.

Seen from yet a still further aspect, the present invention provides a car air bag system comprising: a folded inflatable air bag; a gas generating device connected to the air bag for inflating the air bag, the gas generating device containing a gas generating composition as defined in the present invention; and an ignition element to ignite the gas generating composition.

In some cases, the oxidizing anion is part of the metal cation coordination complex. The complexes are formulated in such a way that, when the complex goes into combustion, a mixture of gases containing nitrogen gas and water vapor is produced. A binder can be provided to improve the compressive strength and other mechanical properties of the gas generating composition. Likewise, a coolant can be provided primarily to allow efficient combustion of the binder. Importantly, the production of undesirable gases or particles is substantially reduced or eliminated.

The complexes used within the scope of the present invention, burn or decompose rapidly to produce significant amounts of gas. The currently preferred metal incorporated into the complex is cobalt.

The metal cation acts as a mold or focal point for the complex. One or more of the oxidizing anions may also be coordinated with the metal cation. Examples of metal complexes included within the scope of the present invention include Co (NH3) 3 (NO2) 3 (trinitrotriaminecobalt (III)), and Co (NH3) 6 (NO3) 3 (hexaaminecobalt nitrate (III)).

It is within the scope of the present invention to include metal complexes containing a common ligand in addition to the neutral ligand. A few typical common ligands include: aqueous (H2O), hydroxo (OH), carbonate (CO3), oxalate (C2O4), cyano (CN), isocyanate (NC), chlorine (Cl), fluoro (F), and similar ligands . The metal complexes used within the scope of the present invention are also intended to include a common counterion, in addition to the oxidizing anion, to help balance the complex charge. A few typical common counterions include: hydroxide (OH -), chloride (Cl -), fluoride (F -), cyanide (CN -), carbonate (CO32-), phosphate (PO43-), oxalate (C2O42), borate ( BO45-) and ammonium (NH4 +).

It has been observed that the metal complexes containing the neutral ligands and the oxidizing anions described rapidly burn, producing significant amounts of gases. Combustion can be initiated by the application of heat or by the use of conventional ignition devices.

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 in the present invention, the term "common ligand" includes well-known ligands used by inorganic chemists to prepare coordination complexes with metal cations. Preferably, the common ligands are polyatomic molecules or ions, but some monoatomic ions, such as halogen ions, can also be used. Examples of common ligands included within the scope of the present invention include aqueous (H2O), hydroxo (OH), perhydrox (O2H), peroxo (O2), carbonate (CO3), oxalate (C2O4), carbonyl (CO), nitrosyl (NO), cyano (CN), isocyanate (NC), isothiocyanate (NCS), thiocyanate (SCN), chlorine (Cl), fluoro (F), amido (NH2), imido (NH), sulfate (SO4), phosphate (PO4), ethylenediaminetetraacetic acid (EDTA), and similar ligands. See, F. Albert Cotton and Geoffrey Wilkinson, Advanced Inorganic Chemistry, 2nd ed., John Wiley & Sons, p. 139-142, (1966) and James E. Huheey, Inorganic Chemistry, 3rd ed., Harper & Row, p. A-97-A-107, (1983).

In some cases, the complex may include a common counterion, in addition to the oxidizing anion, to help balance the charge of the complex. As used in the present invention, 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 (CO32-), sulfate (SO42-), phosphate (PO43-), oxalate (C2O42-), borate (BO45-) and ammonium (NH43 +). 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, p. A-97-A-103, (1983).

The gas generating ingredients are formulated in such a way that, when the composition goes into combustion, nitrogen gas and water vapor are produced. In some cases, small amounts of carbon dioxide or carbon monoxide are produced if a binder, co-oxidant or common ligand 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 speed sufficient to the quality of said materials for use as gas generating compositions in automobile air bags and other types of similar devices. Importantly, the production of other undesirable gases or particles is substantially reduced or eliminated.

The complexes that fall within the scope of the present invention are nitrate metal amines and nitrite metal amines. Metal amine complexes are defined as coordination complexes that include ammonia as the coordination ligand.

It has been suggested that, during the combustion of a complex containing nitrite and ammonia groups, the nitrite and ammonia groups carry out a diazotization reaction. This reaction is similar, for example, to the reaction of sodium nitrite and ammonium sulfate, which is established as follows:

2NaNO2 + (NH4) 2SO4 → Na2SO4 + 4H2O + 2N2

Compositions such as sodium nitrite and ammonium sulfate in combination, have little utility as gas generating substances. It has been observed that these materials carry out metathesis reactions, which result in unstable ammonium nitrite. In addition, most simple nitrite salts have limited stability.

On the contrary, the metal complexes used in the present invention are stable materials, which, in certain cases, are capable of carrying out the type of reaction set forth above. Likewise, the complexes of the present invention produce reaction products that include desirable amounts of non-toxic gases, such as water vapor and nitrogen. In addition, a soluble metal, or metal oxide slag, is formed. Accordingly, the compositions of the present invention avoid several of the limitations of the existing sodium azide gas generating compositions.

The currently preferred metal is cobalt. Cobalt forms stable complexes that are relatively cheap. In addition, the combustion reaction products of the cobalt complex are relatively non-toxic. Other preferred metals include magnesium, manganese, zinc, and tin. Examples of less preferred but usable metals include nickel, titanium or chromium.

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A few representative examples of amine complexes used within the scope of the present invention, and the associated gas-generating decomposition reactions, are as follows:

2Co (NH3) 3 (NO2) 3 - »2CoO + 9H2O + 6N2 + ½O2

2Cr (NH3) 3 (NO2) 3 - »Cr2O3 + 9H2O + 6N2

2B + 3Co (NH3) 6Co (NO2) 6 - »6CoO + B2O3 + 27H2O + 18N2

Mg + Co (NH3) 4 (NO2) 2Co (NH3) 2 (NO2) 4 - »2CoO + MgO + 9H2O + 6N2

10 [Co (NH3) 4 (NO2) 2] (NO2) + 2Sr (NO3) 2 - »10CoO + 2SrO + 37N2 + 60H2O

18 [Co (NH3) 6] (NO3) 3 + 4Cu2 (OH) 3NO3 - »18CoO + 8Cu + 83N2 + 168H2O

2 [Co (NH3) 6] (NO3) 3 + 2NH4NO3 - »2CoO + 11N2 + 22H2O

At the same time that the complexes of the present invention are relatively stable, it is also simple to initiate the combustion reaction. For example, if the complexes come into contact with a hot wire, rapid gas-producing combustion reactions have been observed. Similarly, it is possible to initiate the reaction by conventional ignition devices. One type of ignition device includes a number of granules.

or B / NO3 balls which is ignited, and which, in turn, is capable of igniting the compositions of the present invention. Another ignition device includes a quantity of granules of Mg / Sr (NO3) 2 / nylon.

It is also important to indicate that many of the complexes defined above produce a "stoichiometric" decomposition. That is, the compounds 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 a complete and effective reaction. Such fuels include, for example, boron, magnesium, aluminum, boron or aluminum hydrides, carbon, silica, titanium, zirconium, and other conventional combustible materials, such as conventional organic binders. Oxidizing species include nitrates, nitrites, chlorates, perchlorates, peroxides, and other similar oxidizing materials. Accordingly, while stoichiometric decomposition is attractive due to the simplicity of the composition and reaction, it is also possible to use complexes for which stoichiometric decomposition is not possible.

A few representative examples of nitrate complexes include: Co (NH3) 6 (NO3) 3, [Co (NH3) 5 (NO3] (NO3) 2, [Co (NH3) 5 (NO2)] (NO3) 2, and [Co (NH3) 5 (H2O)] (NO3) 2.

The preparation of metal nitrite or nitrate amine complexes used in the present invention are described in the literature. Specifically, reference is made to them by Hagel and others, in "The Triamines of Cobalt (III). I. Geometrical Isomers of Trinitroamminecobalt (III) ”, Inorganic Chemistry, p. 1496, (June 1970); G. Pass and H. Sutcliffe, Practical Inorganic Chemistry, 2nd Ed., Chapman & Hull, New York, (1974); Shibata et al., "Synthesis of Nitroammine-and Cyanoamminecobalt (III) Complexes With Potasium Tricarbonatocobaltate (III) as the Starting Material," Inorganic Chemistry, p. 1573, (Nov. 1964); Wieghardt et al., "Μ-carboxylatido-µ-hydroxo-bis [triammineco-bal (III)] Complexes", Inorganic Synthesis, p. 23, (1985); Laing, mer-and fac- [Co (NH3) 3NO2) 3]: Do They Exist? ”, J. Chem. Educ., P. 707, (1985); Siebert, "Isomere des Trinitroamminkobal (III)", Z. Anorg. There. Chem., P. 47, (1978). 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 described complexes can be processed into granules or balls usable for use in gas generating devices. Such devices include supplementary restraint systems for automobile air bags. Said gas generating compositions will comprise a quantity of the described complexes and, preferably, a binder and a co-oxidant. The compositions produce a mixture of gases, mainly nitrogen and water vapor, after decomposition or combustion. Likewise, the gas generating device will include means for initiating combustion of the composition, such as a hot wire or an ignition element. In the case of a car air bag system, the system will include the compositions described above; an inflatable, folded air bag; and means for igniting said gas generating composition within the air bag system. Automobile air bag 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, propylene carbonate, polyethylene glycol , naturally occurring gums, such as guar gum, gum arabic, cellulose and modified starches (a detailed exposition of such gums is that provided by CL Mantell, in The Water-Soluble Gums, Reinhold Publishing Corp., (1947) , which is incorporated herein by reference), polyacrylic acids, nitrocellulose, polyacrylamide, polyamides, including nylon, and other conventional polymer binders. Such binders improve mechanical properties or provide enhanced compression resistance. Although non-water miscible binders can be used in the present invention, it is currently preferred to use

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water soluble binders. Preferably, the concentration of binder is in the range of from 0.5 to 12% by weight, and more preferably from 2% to 8% by weight of the gas generating composition.

Applicants have found that the addition of carbon, such as carbon black or activated charcoal, to the gas generating compositions, significantly improves the action of the binder, possibly due to the binder reinforcement and, consequently, the formation of a micro -compound. Improvements in compressive strength from 50% to 150% have been observed with the addition of carbon black to compositions within the scope of the present invention. Ballistic reproducibility is enhanced as the compressive strength increases. Preferably, the carbon concentration is within the range of 0.1% to 6% by weight, and more preferably from 0.3 to 3% by weight of the gas generating composition.

The co-oxidant may be a conventional oxidant such as perchlorates, chlorates, peroxides, nitrites, and alkali, alkaline earth, lanthanide, or ammonium nitrates, including for example, Sr (NO3) 2, NH4ClO4, KNO3, and (NH4) 2Ce (NO 6.

Likewise, the co-oxidant may be an oxidizing agent containing a metal, such as metal oxides, metal hydroxides, metal peroxides, metal oxide hydrates, metal oxides hydroxides, hydrated metal oxides, and mixtures of those same, including those described in US Pat. No. 5,439,537 issued August 8, 1995, entitled "Thermite Compositions for Use as Gas Generants."

Examples of metal oxides include, among others, the oxides of copper, cobalt, manganese, tungsten, bismuth, molybdenum, and iron, such as CuO, Co2O3, Co3O4, CoFe2O4, Fe2O3, MoO3, Bi2MoO6 and Bi2O3. 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 include, among others, Fe2O3 · xH2O, SnO2 · xH2O, and MoO3 · H2O. Examples of metal oxide hydroxides include, among others, CoO (OH2), FeO (OH) 2, MnO (OH) 2 and MnO (OH) 3.

Likewise, the co-oxidant can be a basic metal carbonate such as metal carbonate hydroxide, metal carbonate oxides, metal carbonate hydroxides oxides, and hydrates and mixtures thereof, including the oxidants described in the Patent from the USA No. 5,429,691, entitled "Thermite Compositions for Use as Gas Generants", which is incorporated herein by reference.

Table 1, below, lists examples of basic metal carbonates capable of functioning as co-oxidants in the compositions of the present invention:

Table 1

Basic metal carbonates

Cu (CO3) 1-xCu (OH) 2x, for example, CuCO3Cu (OH) 2 (malachite)

Co (CO3) 1-x (OH) 2x, for example, 2CoCO3 · 3Co (OH) 2 · H2O

CoxFey (CO) 2 (OH) 2, for example, Co0.69Fe0.34 (CO3) 0.2 (OH) 2

Na3 [Co (CO3) 3] · 3H2O

Zn (CO3) 1-x (OH) 2x, for example, Zn2 (CO3) (OH) 2

BiAMgB (CO3) C (OH) D, for example, Bi2Mg (CO3) 2 (OH) 4

Fe (CO3) 1-x (OH) 3x, for example, Fe (CO3) 0.12 (OH) 2.76

Cu2-xZnx (CO3) 1-y (OH) 2y, for example, Cu1,54Zn0,46 (CO3) (OH) 2

CoyCu2-y (CO3) 1-x (OH) 2x, for example, Co0.49Cu0.51 (CO3) 0.43 (OH) 1.1

TiABiB (CO3) x (OH) and, (O) 2 (H2O) C, for example, Ti3Bi4 (CO3) 2 (OH) 2O9 (H2O) 2

(BiO) 2CO3

Table 2, below, lists examples of basic metal nitrates capable of functioning as co-oxidants in the compositions of the present invention:

Table 2

Basic metal nitrates

Cu2 (OH) 3NO3 (gerhardite)

Co2 (OH) 3NO3

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CuxCo2-x (OH3) NO3, for example, CuCo (OH) 3NO3

Zn2 (OH) 3NO3

Mn (OH) 2NO3

Fe (NO3) n (OH) 3-n, for example, Fe4 (OH) 11NO3 · 2H2O

Mo (NO) 2O2

BiONO3H2O

Ce (OH) (NO3) 3 · 3H2O

In certain cases, it would be equally desirable to use mixtures of said oxidizing agents in order to enhance the ballistic properties or to maximize the filterability of the slag formed from the combustion of the composition.

Likewise, the present compositions may include additives conventionally used in gas generating compositions, propellants, and explosives, such as combustion rate modifiers, slag formers, non-stick agents, and additives that effectively remove NOx. Typical combustion rate modifiers include Fe2O3, K2B12H22, Bi2MoO6, and graphite carbon powders or fibers. A number of slag-forming agents are known and include, for example, clays, talcs, silicon oxides, oxides, hydroxides, alkaline earth oxalates, of which magnesium carbonate and magnesium hydroxide are examples. Likewise, a certain number of additives and / or agents are known to reduce or eliminate nitrogen oxides from the combustion products of a gas generating composition, including alkali metal salts and tetrazole complexes, aminotetrazoles, triazoles and heterocycles of related nitrogen, of which potassium aminotetrazole, sodium carbonate and potassium carbonate are examples. Likewise, the composition may include materials that facilitate the release of the composition from a mold such as graphite, molybdenum sulphide, calcium stearate, or boron nitride.

Typical ignition adjuvants / combustion rate modifiers that can be used in the present invention include oxides, nitrites and other metal compounds, such as, for example, Fe2O3, K2B12H22, BiO (NO3), Co2O3, CoFe2O4, CuMoO4, Bi2MoO6, MnO2, Mg (NO3) 2 · xH2O, Fe (NO3) 3 · xH2O, Co (NO3) 2 · xH2O, and NH4NO3. Coolers include magnesium hydroxide, cupric oxalate, boric acid, aluminum hydroxides, and silicotungstic acid. Chillers such as aluminum hydroxide and silicotungstic acid can also function as slag enhancers.

It should be noted that many of the above 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 may function as a co-oxidant, combustion rate modifier, cooler, and / or slag former.

Various important properties of hexaaminecobalt (III) nitrate gas generating compositions included within the scope of the present invention have been compared with commercial sodium azide gas generating compositions. These properties illustrate significant differences between conventional sodium azide gas generating compositions and gas generating compositions included within the scope of the present invention. These properties are summarized below:

Property

Typical invention range Typical sodium azide

Flame temperature

1577-1776 ° C 1127-1227 ° C

Generator gas fraction

0.65-0.85 0.4-0.45

Total carbon content in the generator

0-3.5% traces

Burning rate at 6,894 MPa

0.152-0.533 m / min 1,676-1.98 m / min

Surface area of the generator

2.0-3.5 cm2 / g 0.8-0.85 cm2 / g

Load weights in the generator

30-45 g 75-90 g

The term "generator gas fraction" means the fraction by weight of gas generated by weight of gas generator. Typical hexaamine cobalt (III) nitrate gas generating compositions have higher temperatures.

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preferred within the range of 1577 ° C to 1627 ° C, the fraction of generator gas 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 combustion rate of the generator at 6.89 MPa in the range of from 0.305 to 0.533 m / min, and the surface area of the generator in the range of 2.5 cm2 / g to 3.5 m2 / g.

The gas generating compositions of the present invention are easily adapted for use with conventional hybrid air bag inflator technology. The technology of the hybrid inflator is based on heating a stored inert gas (argon or helium) to a desired temperature by burning a small amount of propellant. Hybrid inflators do not require the cooling filters used with pyrotechnic inflators for cold combustion gases, since hybrid inflators are capable of providing a low temperature gas. The gas discharge temperature can be selectively changed by adjusting the weight ratio of inert gas to propellant weight. The higher the ratio of gas weight to propellant weight, the colder the gas discharge temperature will be.

A hybrid gas generating system comprises a pressure tank having a breakable opening, a predetermined amount of inert gas disposed within the pressure tank; a gas generating device for the production of hot combustion gases and having means of breaking the breakable opening; and means for ignition of 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 positioned relative to the pressure tank so that the hot combustion gases mix with the inert gas and heat it. Suitable inert gases include, among others, argon, helium and mixtures thereof. Mixed and heated gases leave the pressure tank through an opening and finally leave the hybrid inflator and deploy an inflatable bag or balloon, such as a car air bag.

Preferred embodiments of the invention provide combustion products with a temperature greater than about 1527 ° C, whose heat is transferred to the colder inert gas, resulting in a further improvement in the efficiency of the hybrid gas generating system.

Hybrid gas generating devices for supplementary safety restraint application are described by Frantom, in Hybrid Airbag Inflator Technology, Airbag Int'l Symposium on Sophisticated CarOccupant Safety Systems, (Weinbrenner-Saal, Germany, Nov. 2-3, ( 1992).

The at least one cold burning organic nitrogen compound may be, for example, guanidine nitrate. A cold burning organic nitrogen compound is a compound that has a relatively low heat of formation. In general, the heat of formation of the cold combustion compounds may be less than about -1,675x106 J / Kg (-400 cal / g), and preferably, less than about -2,512x106 J / Kg (-600 cal / g ). The heat of formation for guanidine nitrate, for example, is approximately -3,128x106 J / Kg (-747 cal / g).

In this preferred embodiment, the cold burning organic nitrogen compound is not the primary fuel of the formulation, but a secondary fuel. Fuels already disclosed above, such as, for example, hexaaminecobalt nitrate, can serve as the primary fuel.

In addition, a substance such as guanidine nitrate may also have some oxidizing capacity due to the presence, for example, of the nitrate group. However, the cold burning organic nitrogen compound is not the main oxidizing agent. However, it can act as a secondary oxidizing agent or as a co-oxidant, in conjunction with other oxidizing substances or co-oxidants indicated above, such as, for example, basic copper nitrate.

In addition to guanidine nitrate, additional cold-burning organic nitrogen compounds 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, glycine, glycine-ammonium nitrate complexes, and ethylene diamine dinitrate. However, guanidine nitrate is preferred. Mixtures of cold burning organic nitrogen compounds may be used.

In principle, the amount of cold burning organic nitrogen compound incorporated into the composition may generally be greater than 0% by weight and less than approximately 40% by weight, and preferably, between approximately 5% by weight and approximately 30% by weight. weight, and more preferably, between about 10% by weight and about 25% by weight. This embodiment of the present invention is not limited in theory, however, and in practice, the amount can be determined by a person skilled in the art, depending on what type of performance characteristics are the most important for the particular application of the air bag

The use of the cold burning organic nitrogen compound results in a high gas output with simultaneously improved filterability of the slag produced from combustion. In addition, the total cost of the composition can be reduced when a relatively less expensive cold burning organic nitrogen compound replaces a relatively more expensive ingredient such as, for example, hexaamine cobalt nitrate. In principle, the amount of NOx can also be reduced.

Preferred gas generating compositions comprise cold-burning organic nitrogen compounds and, in addition, comprise: 1) at least one primary fuel such as a metal complex such as, for example, haxaamine cobalt nitrate, Co (NH3) 6 (NO3 ), which is different from the cold-burning organic nitrogen compound, 2) a co-oxidant such as, for example, basic copper nitrate, Cu2 (OH) 3NO3, which is different from the cold-burning organic nitrogen compound , and 3) a binder that is preferably a water soluble binder such as, for example, guar gum.

In general, in this preferred embodiment, fuels, co-oxidants, and binders, which have been previously described in the present invention, can be used. However, preferred examples of fuels for this preferred embodiment include cobalt amine complexes, and hexaamine cobalt nitrate is particularly preferred. Preferred examples of co-oxidants include basic metal carbonates, basic metal nitrates, metal oxides, metal nitrates, and metal hydroxides. Basic copper nitrate is particularly preferred. Preferred examples of binders include water soluble or substantially water soluble polymers, including gums. Guar gum is particularly preferred.

The amounts of the ingredients such as fuel, co-oxidant, and binder in this preferred embodiment, can easily be determined by a person skilled in the art in view of the present disclosure. However, in particular, the amount of primary fuel, which is separate from the cold-burning organic nitrogen compound, can generally be between about 30% by weight and about 90% by weight, and preferably, between about 40% by weight and about 75% by weight. The sum of the amount of co-oxidant, taken in conjunction with the amount of cold burning organic nitrogen compound, may be between about 10% by weight and about 60% by weight, and preferably, between about 15% by weight and approximately 50% by weight. The amount of binder can 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 more preferably, between about 3% by weight and about 6% by weight. Although in theory, the compositions are generally used in a way that is stoichiometrically balanced, in practice, the compositions are often at least slightly rich in fuel, although compositions slightly rich in oxygen are in principle possible. Typically, the proportion of ingredients is adjusted to give the best performance balance with respect, for example, to the characteristics of effluent gases and slags.

Preferably, the composition also contains small amounts of carbon such as, for example, carbon black as a ballistic additive or combustion rate modifier, although it is optional. Typically, the amount of carbon black may be less than about 2% by weight, and preferably, less than about 1% by weight.

The cold burning organic nitrogen compound can be used to partially replace the combustible ingredient. In this case, the amount of co-oxidant can be increased to maintain the desired stoichiometry. This can result in cost savings since, for example, both basic copper nitrate and guanidine nitrate are significantly less expensive than hexaamine cobalt nitrate. Surprisingly, however, the overall performance of the generator is maintained despite the substitution. The maintenance of the overall performance is achieved from a volume perspective since the density of the mixture increases as the relative proportion of the basic copper nitrate increases.

In general, it is estimated that few, if any, occur chemical reactions when guanidine nitrate is mixed into the compositions, although the present invention does not share said chemical reaction theory. The formulations can be prepared by mixing the individual ingredients, or alternatively, preparing the formulations separately and mixing these formulations. Mixing of the individual ingredients is generally preferred. Mixing can be carried out 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 following non-limiting examples. Unless stated otherwise, the compositions are expressed in weight percent.

Example 1

With a quantity (132.4 g) of Co (NH3) 3 (NO2) 3, prepared according to the guidelines of Hagel et al., In “The Triamines of Cobalt (III). I. Geometrical Isomers of Trinitrotriaminecobalt (III), Inorganic Chemistry, p. 1496, (June 1970), a slurry was formed in 35 ml of methanol with 7 g of a 38 percent by weight solution of pyrotechnic grade vinyl acetate / vinyl alcohol polymer resin, commercially known as VAAR dissolved in acetate methyl. The solvent was allowed to partially evaporate. The paste-like mixture was forced to pass through a 20 mesh screen, allowed to dry to a firm consistency, and forced to pass through a sieve again. Then, the resulting granules were dried under vacuum at room temperature for 12 hours. By pressing the dried material granules of 1.27 cm in diameter were prepared. The granules were burned at several different pressures ranging from 4.14 to 22.75 MPa. The combustion rate of the generator was found to be 0.391 m / min at 6.89 MPa with a pressure exponent of 0.85 over the pressure range tested.

Example 2

The procedure of Example 1 was repeated, with 100 g of Co (NH3) 3 (NO2) 3 and 34 g of 12 weight percent solution of nylon in methanol. The granulation was carried out using 10 and 16 mesh sieves, followed by air drying. The combustion rate of this composition was found to be 0.442 m / min at 6.89 MPa with a pressure exponent of 0.74.

Example 3

In a manner similar to that described in Example 1, with 400 g of Co (NH3) 3 (NO2) 3, a slurry was formed with 219 g of a 12 percent by weight solution of nitrocellulose in acetone. Nitrocellulose contained 12.6 percent nitrogen. The solvent was allowed to partially evaporate. The resulting paste was forced through a 8 mesh screen followed by a 24 mesh screen. The resulting granules were air dried overnight and mixed with sufficient calcium stearate release agent to provide 0.3 percent by weight in the final product. A portion of the resulting material was pressed into 1.27 cm diameter granules and found to show a combustion rate of 0.419 m / min at 6.89 MPa with a pressure exponent of 0.79. The rest of the material was pressed into granules 0.318 cm in diameter by 0.178 cm thick on a rotary tablet press. The density of the granule was determined to be 1.88 g / cm3. The theoretical flame temperature of this composition was 2,085 ° C and was calculated to provide a mass fraction of gas of 0.72.

Example 4

This example discloses the preparation of a reusable stainless steel test device used for similar driver side gas generators. The test device, or simulator, was constituted by an ignition chamber and a combustion chamber. The ignition chamber was located in the center and had 24 0.254 cm ports that exited inside the combustion chamber. The ignition chamber was provided with an ignition hose. The wall of the ignition chamber was coated with 2.54x10-3 cm thick aluminum sheet before adding the granules of the mesh -24 / + 60 ignition element. The wall of the outer combustion chamber was constituted by a ring with nine exit ports. The diameter of the ports was varied by changing the rings. Starting from the inner diameter of the outer combustion chamber ring, the combustion chamber was provided with a 10.2x10-3 cm aluminum plate, a 30 mesh stainless steel sieve vent, four stainless steel sieve vents 14 mesh, a baffle ring, and the gas generator. The generator was kept intact inside the combustion chamber using a “donut” of 18 mesh stainless steel sieve. An additional baffle ring was placed around the outer diameter of the outer combustion chamber wall. The combustion chamber was provided with a pressure port. The simulator was attached at the same time to a 60-liter tank and an automotive air bag. The tank was provided with pressure, temperature, ventilation, and drainage ports. Automotive air bags have a maximum capacity of 55 liters and are built with two ventilation ports of 1.27 cm in diameter. Simulator tests involving an air bag were configured in such a way that the pressures of the bags were measured. The surface temperature of the outer layer of the bag was monitored during the inflation period by infrared radiometry, thermal imaging, and thermocouple.

Example 5

Thirty-seven and a half grams of the 0.318 cm diameter granules prepared as described in Example 3, were burned in a ventilated inflator test device inside a 60 liter collection tank as described in Example 4, with the further incorporation of a second sieved chamber containing 2 mesh sieve vents 30 and 2 mesh sieve vents 18. The combustion produced a combustion chamber pressure of 13.8 MPa and a pressure of 0.269 MPa in the 60 liter collection tank. The temperature of the gases in the collection tank reached a maximum of 407ºC at 20 milliseconds. Analysis of the gases collected in the 60-liter tank showed a concentration of nitrogen oxides (NOx) of 500 ppm and a concentration of carbon monoxide of 1,825 ppm. The total ejected particles, determined by washing the tank with methanol and evaporating the washing, were found to be 1,000 mg.

Example 6

The test of Example 4 was repeated, except that the 60-liter tank was replaced by a 55-liter ventilated bag, as is typically used in the driver's side automotive inflator clamping devices. A combustion chamber pressure of 13.1 MPa was obtained when a total inflation of the bag occurred. Approximately 60 milliseconds after the ignition, a peak pressure of the inner bag of 13.8x103 Pa was observed. The surface temperature of the bag was observed to remain below 83 ° C, which is an improvement over the inflators at Conventional azide base, while the inflation performance of the bag is almost typical of conventional systems.

Example 7 (for comparative purposes only)

The copper tetraamine salt was prepared by dissolving 116.3 g of copper (II) nitrate hemipentahydrate in 230 ml of concentrated ammonium hydroxide and 50 ml of water. After cooling the resulting hot mixture to 40 ° C, one liter of ethanol was added with stirring to precipitate the tetraamine nitrate product. The purple-blue solid

Dark was collected by filtration, washed with ethanol and air dried. The product was confirmed to be Cu (NH3) 4 (NO3) 2 by elemental analysis. The burning rate of this material, determined from pressed 1.27 cm diameter granules, was 0.274 m / min at 6.89 MPa.

Example 8 (for comparative purposes only)

The copper tetraamine nitrate prepared in Example 7 was formulated with various supplemental oxidants and was

10 tested the combustion rate. In all cases, slurries of 10 g of material with approximately 10 ml of methanol were formed, dried, and pressed into granules of 1.27 cm in diameter. The combustion rates were measured at 6.89 MPa and the results are shown in the following table.

Copper Tetraamine Nitrate

Oxidizer Burning Rate (m / min)

88%

CoO (6%) Sr (NO3) 2 (6%) 0.198

92%

Sr (NO3) 2 (8%) 0.213

90%

NH4NO3 (10%) 0.381

78%

Bi2O3 (22%) 0.152

85%

SrO2 (15%) 0.274

Example 9

An amount of hexaamine cobalt (III) nitrate was prepared by replacing the ammonium chloride with ammonium nitrate in the process for the preparation of hexaamine cobalt (III) chloride as set forth by G. Pass and

H. Sutcliffe, in Practical Inorganic Chemistry, 2nd Ed., Chapman & Hull, New York, (1974). The prepared material was determined to be [Co (NH3) 6] (NO2) 3 by elemental analysis. A sample of the material was pressed into 1.27 cm diameter granules and a burning rate of 0.396 m / min at 13.8 MPa was measured.

Example 10

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

Formulation

Indicted Burning rate

12% (NH4) 2 [Ce (NO3) 6] 88% [Co (NH3) 6] (NO3) 3

Dry mixed 0.290 m / min at 11.7 MPa

12% (NH4) 2 [Ce (NO3) 6] 88% [Co (NH3) 6] (NO3) 3

Blended with 35% MeOH 0.305 m / min at 11.7 MPa

18% (NH4) 2 [Ce (NO3) 6] 81% [Co (NH3) 6] (NO3) 3 1% Carbon black

Blended with 10% H2O 0.305 m / min at 11.7 MPa

Example 11

The material prepared in Example 9 was used to prepare several mixtures of 10 g of generator composition using various supplementary oxidants. In all cases, the appropriate amount of hexaaminacobal-to (III) nitrate and co-oxidant (s) were mixed within approximately 10 ml of methanol, allowed to dry, and pressed into 1.27 cm granules. diameter. The granules were tested to determine the burning rate at 6.89 MPa and the results are shown in the following table.

Hexaamine Cobalt Nitrate (III)

Co-oxidizer Burning rate at 6.89 MPa

60%

CuO (40%) 0.229

70%

CuO (30%) 0.244

83%

CuO (10%) Sr (NO3) 2 (7%) 0.198

88%

Sr (NO3) 2 (12%) 0.213

70%

Bi2O3 (30%) 0.152

83%

NH4NO3 (17%) 0.229

Example 12

Binary compositions of hexaamine cobalt (III) nitrate ("HACN") and various supplemental oxidants were mixed in 20 gram batches. The compositions were dried for 72 hours at 93.3 ° C and pressed into 1.27 cm diameter granules. The combustion rates were determined by the combustion of the 1.27 cm granules at different pressures ranging from 6.89 to 27.6 MPa. The following table shows the results.

Composition

Burning rate m / min at x MPa Temp. ºC

Weight ratio

6.89 13.8 20.7 27.6

HACN 100/0

0.290 0.427 0.655 0.686 1583

HACN / CuO 90/10

0.396 0.533 0.594 0.671 1558

HACN / Ce (NH4) 2 (NO3) 6 88/12

0.244 0.335 0.457 0.579 -

HACN / Co2O3 90/10

0.152 0.320 0.396 0.518 1470

HACN / Co (NO3) 26H2O 90/10

0.198 0.335 0.533 0.625 1592

HACN / V2O5 85/15

0.183 0.244 0.320 0.457 1529

HACN / Fe2O3 75/25

0.183 0.183 0.259 0.350 1353

HACN / C3O4 81.5 / 18.5

0.198 0.305 0.381 0.457 1495

HACN / MnO2 80/20

0.168 0.259 0.335 0.457 -

HACN / Fe (NO3) 2 · 9H2O 90/10

0.213 0.335 0.472 0.732 -

HACN / Al (NO3) 26H2O 90/10

0.152 0.274 0.396 0.484 1572

HACN / Mg (NO3) 2 · 2H2O 90/10

0.244 0.366 0.488 0.594 1814

Example 13

A processing procedure was established for the preparation of small parallelepipeds (“pps”) of laboratory-scale gas generator. The equipment necessary for the formation and cutting of the pps included a cutting board, a roller and a cutting device. The cutting board consisted of a 22.9 x 45.7 cm sheet of metal with 1.27 cm wide paper spacers glued along the longitudinally along the edges. The spacers had a cumulative height of 0.109 cm. The roller consisted of a Teflon cylinder 30.5 cm long and 5.08 cm in diameter. The cutting device consisted of a shaft, cutting blades and spacers. The shaft had a 0.635 cm bolt on which a series of

15 seventeen stainless steel washers of 1,905 cm in diameter and 0.0127 cm thick, as cutting blades. Between each cutting blade, four brass spacer washers of 1.69 cm in diameter and 0.0508 cm thick were placed and the series of washers were secured by a nut. The repeated distance between the circular cutting blades was 0.216 cm.

A gas generating composition containing a water soluble binder was mixed dry and then

At the same time, batches of 50-70 g were mixed on a Spex mill / mixer for five minutes, with enough water so that the material once mixed had a pasty consistency.

A Velostat plastic sheet was glued to the cutting table with adhesive tape and the generator paste ball mixed with water was crushed by hand onto the plastic. A polyethylene plastic sheet was placed on the generating mixture. The roller was positioned parallel to the spacers located on the cutting board and the paste was crushed to a width of approximately 12.7 cm. Next, the roller was turned 90 degrees, placed on top of the spacers and the paste was crushed to the maximum amount allowed by the spacers on the cutting board. The polyethylene plastic was carefully removed from the generator and the cutting device was used to cut the paste both lengthwise and widthwise.

The Velostat plastic sheet on which the generator had been wound and cut, was released from the cutting table and placed longitudinally on a 10.2 cm diameter cylinder in a convection oven at 57.2 ° C. After about 10 minutes, the sheet was removed from the oven and placed on a 1.27 cm 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 in order to discover the cuts between the parallelepipeds ("pps"). The sheet was placed wide on the 10.2 cm diameter cylinder in the convention oven at 57.2 ° C and allowed to dry for another 5 minutes. The cuts were opened between the pps on the 1.27 cm diameter rod as before. At that time, it was very easy to peel the pps from the plastic. The pps were separated from each other also by gently rubbing them on a rough surface or on the fabric of a 12 mesh screen. This procedure breaks the pps into individual pieces with some remaining double pieces. The double pieces were separated into individual pieces using a razor blade. Next, the pps were introduced in a convection oven at 73.9-107 ° C to dry them completely. The compressive strengths (at the edges) of the pps thus formed were typically as high or higher than those of the 0.318 cm diameter granules with convex radii of curvature of 0.635 cm and a maximum height of 0.178 cm, formed on a rotary press This is remarkable since the latter are three times more massive.

Example 14

A gas generating composition was prepared using hexaamine cobalt (III) nitrate powder, [(NH3) 6Co] (NO3) (78.07%, 39.04 g), ammonium nitrate granules (19.93%, 9, 96 g) and ground polyacrylamide, 15 million p.mol. (2.00%, 1.00 g). The ingredients were dry mixed in a Spex mill / mixer for one minute. Deionized water (12% of the dry weight of the formulation, 6 g) was added to the mixture, which was mixed for an additional five minutes on the Spex mill / mixer. This resulted in a material with a pasty consistency, which was processed in the form of parallelepipeds (pps) as in Example 13. Three additional batches of generator were mixed and similarly processed. The pps from the four batches were mixed. The dimensions of the pps were 0.132 x 0.183 x 0.213 cm. The standard deviations on each of the dimensions were of the order of 0.0254 cm. The average weight of the pps was 6.62 mg. The apparent density, density determined by dimensional measurements, and the density, determined by solvent displacement, were determined to be 0.86 g / cm3, 1.28 g / cm3, and 1.59 g / cm3, respectively. Compressive strengths of 1.7 kg (over the narrowest edge) with a standard deviation of 0.7 kg were measured. Some of the pps were pressed into 1.27 cm diameter granules that weighed approximately three grams. From these granules, the burning rate was determined to be 0.198 m / min at 6.89 MP 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 (NO3) 2 / nylon ignition element granules were introduced into the ignition chamber. The diameter of the outlet ports of the outer combustion chamber wall was 0.476 cm. Thirty grams of the generator described in Example 14 were fixed inside the combustion chamber in the form of parallelepipeds. The simulator was attached to the 60-liter tank described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 15.9 MPa in 17 milliseconds, the 60-liter tank reached a maximum pressure of 0.234 MPa and the maximum tank temperature was 367 ° C. The proportions of NOx, CO and NH3 were 20, 380 and 170 ppm, respectively, and 1600 mg of particles were collected from the tank.

Example 16

A simulator was constructed with the same ignition element and exact type of generator and load weight as in Example 15. In addition, the diameters of the output ports of the external combustion chamber were identical. The simulator was attached to an automotive safety bag of the type described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 13.8 MPa in 15 milliseconds. The maximum pressure of the inflated air bag was 6.20x103 Pa. This pressure was reached 18 milliseconds after ignition. The surface temperature of the maximum 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 micrometers), pyrometallurgically formed cupric oxide powder (5.00%, 5.00 g) and guar gum (3.00%, 3.00 g). The ingredients were dry mixed in a Spex mill / mixer for one minute. Deionized water (18% of the dry weight of the formulation, 9 g) was added to 50 g of the mixture, which was mixed for an additional five minutes on the Spex mill / mixer. This resulted in a material with a pasty consistency, which was processed in the form of parallelepipeds (pps) as in Example 13. The same procedure was repeated for the other 50 g of dry mixed generator and the two lots of pps were mixed together. The average dimensions of the mixed pps were 0.178 x 0.206 x 0.224 cm. The standard deviations on each of the dimensions were of the order of 0.0254 cm. The average weight of the pps was 9.60 mg. The bulk density, density determined by dimensional measurements, and the density, determined by solvent displacement, were determined to be 0.96 g / cm3, 1.17 g / cm3, and 1.73 g / cm3, respectively. Compressive strengths of 5.0 kg (over the narrowest edge) were measured with a standard deviation of 2.5 kg. Some of the pps were pressed into 1.27 cm diameter granules that weighed approximately three grams. From these granules, the combustion rate was determined to be 0.305 m / min at 6.89 MP with a pressure exponent of 0.67.

Example 18

A simulator was constructed according to Example 4. One gram of a stoichiometric mixture of Mg / Sr (NO3) 2 / nylon and two grams of B / KNO3 ignition element granules slightly over-oxidized, mixed and introduced inside the ignition chamber. The diameter of the outlet ports of the outer combustion chamber wall was 0.431 cm. Thirty grams of the generator described in Example 17 were fixed inside the combustion chamber in the form of parallelepipeds. The simulator was attached to the 60-liter tank described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 17.5 MPa in 8 milliseconds, the 60-liter tank reached a maximum pressure of 0.248 MPa and the maximum tank temperature was 327 ° C. The proportions of NOx, CO and NH3 were 50, 480 and 800 ppm, respectively, and 240 mg of particles were collected from the tank.

Example 19

A simulator was constructed with the same ignition element and exact generator type and load weight as in Example 18. In addition, the diameters of the output ports of the external combustion chamber were identical. The simulator was attached to an automotive safety bag of the type described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 18.6 MPa in 9 milliseconds. The maximum pressure of the inflated air bag was 15.9x103 Pa. This pressure was reached 30 milliseconds after ignition. The surface temperature of the maximum bag was 73 ° C.

Example 20

A gas generating composition was prepared using hexaamine cobalt (III) nitrate powder (69.50%, 347.5 g), copper trihydroxy nitrate, [Cu2 (OH) 3NO3], powder (21.5%, 107 , 5 g), 10 micron RDX (5.00%, 25 g), 26 micron potassium nitrate (1.00%, 5 g) and guar gum (3.00%, 3.00 g). The ingredients were dry mixed with the aid of a 60 mesh sieve. Deionized water (23% of the dry weight of the formulation, 15 g) was added to 65 g of the mixture, which was mixed for an additional time of five minutes on the Spex mill / mixer. This resulted in a material with a pasty consistency, which was processed in the form of parallelepipeds (pps) as in Example 13. The same procedure was repeated for two additional 65 g batches of dry mixed generator and the three batches of pps were mixed together. The average dimensions of the pps were 0.145 x 0.198 x 0.213 cm. The standard deviations on each of the dimensions were of the order of 0.0254 cm. The average weight of the pps was 7.22 mg. The apparent density, density determined by dimensional measurements, and the density, determined by solvent displacement, were determined to be 0.96 g / cm3, 1.23 g / cm3, and 1.74 g / cm3, respectively. Compressive strengths of 3.6 kg (over the narrowest edge) were measured with a standard deviation of 0.9 kg. Some of the pps were pressed into 1.27 cm diameter granules that weighed approximately three grams. From these granules, the combustion rate was determined to be 0.411 m / min at 6.89 MP 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 (NO3) 2 / nylon and 1.5 grams of ignition element granules of slightly over-oxidized B / KNO3, were mixed and introduced into the ignition chamber. The diameter of the outlet ports of the outer combustion chamber wall was 0.450 cm. Thirty grams of the generator described in Example 20 were fixed inside the combustion chamber in the form of parallelepipeds. The simulator was attached to the 60 liter tank described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 21.0 MPa in 14 milliseconds. The proportions of NOx, CO and NH3 were 25, 800 and 90 ppm, respectively, and 89.0 mg of particles were 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) nitrate trihydroxy powder (19.00%, 111.5 g) and gum guar (3.00%, 17.61 g). The ingredients are mixed

5

10

fifteen

twenty

25

30

35

Dry rum and then mixed with water (32.5% of the dry weight of the formulation, 191 g) in a Baker-Perkins aggregate mixer for 30 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 on a Baker-Perkins mixer. The wet cake was introduced into a piston extruder with a drum diameter of 5.08 cm and a bore hole diameter of 0.23 cm. The extruded material was cut in lengths of approximately 30.5 cm, allowed to dry under ambient conditions overnight, was introduced into a closed container containing water in order to moisten it and, in this way, soften the material, cut at lengths of about 0.254 cm and dried at 73.9 ° C. The dimensions of the resulting extruded cylinders were of an average length of 0.287 cm and an average diameter of 0.231 cm. The apparent density, density determined by dimensional measurements, and the density, determined by solvent displacement, were 0.86 g / cm3, 1.30 g / cm3, and 1.61 g / cm3, respectively. Compressive strengths of 2.1 and 4.1 kg were measured on the circumference and axis, respectively. Some of the extruded cylinders were pressed into 1.27 cm diameter granules that weighed approximately three grams. From these granules, the combustion rate was determined to be 0.335 m / min at 6.89 MP with a pressure exponent of 0.29.

Example 23

Three simulators were constructed according to Example 4. 1.5 grams of a stoichiometric mixture of Mg / Sr (NO3) 2 / nylon and 1.5 grams of ignition element granules of slightly over-oxidized B / KNO3, were mixed and introduced into the ignition chambers. The diameter of the outlet ports of the outer combustion chamber wall were 0.450 cm, 0.406 cm and 0.386 cm, respectively. Within each of the combustion chambers thirty grams of generator described in Example 22 were fixed in the form of extruded cylinders. The simulators were successively subjected to the 60 liter tank described in Example 4. After ignition, the combustion chamber reached a maximum pressure of 10.9 MPa, 11.5 MPa and 13.1 MPa, respectively. Maximum tank pressures were 0.221 MPa, 0.234 MPa and 0.241 MPa, respectively. The NOx ratios were 85, 180, and 185 ppm, while the CO ratios were 540, 600, 600 ppm, respectively. The proportions of NH3 were below 2 ppm. The proportions of particles were 420, 350, and 360 mg, respectively.

Example 24

It has been found that the addition of small amounts of carbon to the gas generating formulations improves the compressive strength of parallelepipeds and extruded granules formed as in Example 13 or Example 22. The following table summarizes the strength enhancement compression with the addition of carbon to a typical gas generating composition included within the scope of the present invention. All percentages are expressed as percent by weight.

Table 3: Enhancement of compressive strength with carbon addition

HACN%

CTN% Guar% Carbon% Shape Resistance

65.00

30.00 5.00 0.00 EP 2.7 kg

64.75

30.00 4.50 0.75 EP 5.7 kg

78.00

19.00 3.00 0.00 pps 2.3 kg

72.90

23.50 3.00 0.60 pps 5.8 kg

78.00

19.00 3.00 0.00 EP 2.3 kg

73.00

23.50 3.00 0.50 EP 4.1 kg

HACN = Hexaaminacobalt (III) Nitrate, [(NH3) 6Co] (NO3) (Thiokol) CTN = Trihydroxy Copper Nitrate (II), [Cu2 (OH3) NO3] (Thiokol) Guar = Guar gum (Aldrich) Carbon = Carbon black “Monarch 1100” (Cabot) EP = Extruded granule (Example 22) pps = Parallelepiped (see Example 13) Resistance = compressive strength of pps or extruded granules in kilograms

5

10

fifteen

twenty

25

30

35

40

Example 25

Hexaamine cobalt (III) nitrate was pressed into four gram granules with a diameter of 1.27 cm. One half of the granules were weighed and placed in an oven at 95 ° C for 700 hours. After aging, they were weighed again. No weight loss was observed. The burning rate of the granules maintained at room temperature was 0.244 m / min and 6.89 MPa with a pressure exponent of 0.60. The burning rate of the granules maintained at 95 ° C for 700 hours was 0.229 m / min at 6.89 MPa with a pressure exponent of 0.68.

Example 26

A gas generating composition was prepared using hexaamine cobalt (III) nitrate powder (76.00%, 273.6 g), copper (II) nitrate trihydroxy powder (16.00%, 57.6 g), nitrate 26 micron potassium (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, which was mixed for an additional five minutes on the Spex mill / mixer. This resulted in a material with a pasty consistency, which was processed in the form of parallelepipeds (pps) as in Example 13. The same procedure was repeated for the other batches of 50-65 g of dry mixed generator and all lots of pps were mixed together. The average dimensions of the pps were 0.165 cm x 0.188 cm x 0.208 cm cm. The standard deviations on each of the dimensions were of the order of 0.0254 cm. The average weight of the pps was 7.42 mg. The apparent density, density determined by dimensional measurements, and the density, determined by solvent displacement, were determined to be 0.86 g / cm3, 1.15 g / cm3, and 1.68 g / cm3, respectively. Compressive strengths of 2.1 kg (over the narrowest edge) were measured with a standard deviation of 0.3 kg. Some of the pps were pressed into ten granules of 1.27 cm in diameter that weighed approximately three grams. Approximately 60 g of pps and five 1.27 cm diameter granules 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 pps and granules, respectively. The rest of the pps and granules were stored under ambient conditions. Combustion rate data were obtained from both sets, which are summarized in Table 4.

Table 4

Comparison of combustion speed before and after accelerated aging

Storage conditions

Burning rate at 6.89 MPa Pressure exponent

24-48 hours at room temperature

0.229 m / min 0.72

450 hours at 107 ° C

0.229 m / min 0.70

Example 27

Two simulators were constructed according to Example 4. In each ignition chamber, a mixture of 1.5 grams of a stoichiometric mixture of Mg / Sr (NO3) 2 / nylon and 1.5 grams of element granules was introduced slightly over-oxidized B / KNO3 ignition. The diameter of the outlet ports of the outer combustion chamber wall in each simulator was 0.450 cm. Thirty grams of aged generator described in Example 26 were fixed in the combustion chamber of a simulator in the form of parallelepipeds, while thirty grams of generator pps aged at 107 ° C were set in the other combustion chamber. The simulators were attached to the 60 liter tank described in Example 4. Table 5, below, summarizes the results of the combustion test.

Table 5

Results of combustion test for aged generator

Temp. aging

MPa combustion pressure Mpa tank pressure Temp. tank (ºC) Proportion NH3 (ppm) Proportion CO (ppm) Proportion NOx (ppm) Proportion I participated (ppm)

Ambient

15.0 0.220 355 350 500 80 520

107 ° C

14.3 0.218 356 160 500 100 480

Example 28

A mixture of 2Co (NH3) 3 (NO2) and Co (NH3) 4 (NO2) 2Co (NH3) 2 (NO2) 4 was prepared and pressed into a granule having an approximate diameter of 1.28 cm. The complexes were prepared within the scope of the Hagel et al. Reference guidelines, identified above. The granule was introduced into a test pump, which was presumed

5 curled at 6.89 MPa with nitrogen gas.

The granule was ignited with a hot wire and the combustion rate was measured, observing that it was 0.579 m / min. Theoretical calculations indicated a flame temperature of 1805 ° C. From theoretical calculations, it was predicted that the main reaction products would be solid CoO and gaseous reaction products. The main reaction products were predicted to be the following:

10 Product Volume%

H2O 57.9

N2 38.6

O2 3.1

Example 29

An amount of Co (NH3) 3 (NO2) 3 was prepared according to the guidelines of Example 1 and tested using differential scanning calorimetry. It was observed that the complex produced a vigorous exotherm at 200 ° C.

Example 30

Theoretical calculations were performed for Co (NH3) 3 (NO2) 3. These calculations indicated a flame temperature of approximately 1727 ° C and a gas yield of approximately 1.5 times that of generating compositions

20 of conventional sodium azide gas based on the same volume of generating composition ("yield ratio"). Likewise, theoretical calculations were carried out for a series of gas generating compositions. Table 6, below, presents the compositional and theoretical performance data.

Table 6

Gas generator

Relationship Temperature (ºC) Performance ratio

Co (NH3) 3 (NO2) 3

- 1805 1.74

NH4 [Co (NH3) 2 (NO2) 4]

- 1381 1.81

NH4 [Co (NH3) 2 (NO2) 4] / B

99/1 1634 1.72

Co (NH3) 6 (NO3) 3

- 1585 2.19

[Co (NH3) 5 (NO3] (NO3) 2

- 1637 2.00

[Fe (N2H4) 3] (NO3) 2 / Sr (NO3) 2

87/13 2. 3. 4. 5 1.69

[Co (NH3) 6] (ClO4) 3 / CaH2

86/14 2577 1.29

[Co (NH3) 5 (NO2)] (NO3) 2

- 1659 2.06

25 The performance ratio is a normalized ratio to an azide-based gas generator volume unit. The theoretical gas yield for a typical azide-based gas generator (68% by weight of NaN3; 30% by weight of MoS2; 2% by weight of S) is approximately 0.85 g of gas / cm3 of generator of NaN3.

Example 31 (for comparative purposes only)

Theoretical calculations were carried out on the reaction of [Co (NH3) 6] (ClO4) 3 and CaH2 as listed in the Table

30 6, in order to evaluate its use in a hybrid gas generator. If this formulation is allowed to develop combustion in the presence of 6.80 times its weight in argon gas, the temperature of the flame decreases from 2577 ° C to 1085 ° C, assuming 100% thermal transfer efficiency. The gas output consisted of 86.6% 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 would be 6.1% by mass.

35

5

10

fifteen

twenty

25

30

35

Example 32

Nitrate complexes of pentaamine cobalt (III) were synthesized, which contained a common ligand in addition to NH3. Aqueopentaaminecobalt (III) nitrate and pentaaminecarbonatecobalt (III) nitrate were synthesized according to Inorg. Syn., Vol. 4, p. 171, (1973). Pentaaminehydroxocobalt (III) nitrate was synthesized according to H: J: S King, J. Chem. Soc., P. 2105, (1925) and O. Schmitz, Zeit. Anorg Chem., Vol. 300, p. 186, (1959). Three gas generating batches were prepared using the pentaamine cobalt (III) nitrate complexes described above. In all cases, guar gum was added as a binder. Trihydroxy copper (II) nitrate, [Cu2 (OH) 3NO3], was added as the co-oxidant, when necessary. The combustion rates were determined from granules of 1.27 cm in diameter. Table 7 summarizes the results.

Table 7

Formulation containing [Co (NH3) 5X] (NO3) and

Formulation

% H2O added Burning rate

97.0% [Co (NH3) 5 (H2O)] (NO3) 3 3% guar

27% 0.244 m / min at 6.89 MPa

68.8% [Co (NH3) 5 (OH)] (NO3) 3 28.2% [Cu2 (OH) 3NO3] 3.0% guar

55% 0.213 m / min at 6.89 MPa

48.5% [Co (NH3) 5 (CO3)] (NO3) 48.5% [Cu2 (OH) 3NO3] 3.0% guar

24% 0.213 m / min at 28.6 MPa

Example 33

A composition comprising the following starting ingredients was prepared: 1) 72.84% by weight of cobaltohexaamine 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 formulations were processed as described in Example 22, except that a single screw extruder was used and that a central perforation of 0.0899 cm was incorporated into the extruded cylinders. The formulations were tested by the same procedure described in Example 23 at various loads ranging from 32 to 38 grams. The results of the tests showed that the particle values were between 0.6 g and 1.0 g for all samples. Tank pressures ranged from 0.269 to 0.331 MPa, depending on the load.

Example 34

A mixture formulated 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 procedure described in Example 33.

An initial test assessment was carried out with a 35 g sample of extruded material as described in Example 23. The combustion pressure was 19.4 MPa, and the tank pressure was 0.275 MPa. The trace amounts of gaseous products were: ammonia (70 ppm), NOx (40 ppm) and CO (600 ppm). The values of the particles were only 0.281 g. The observed tank pressure of 0.275 MPa was comparable to that obtained with 33 g of formulation prepared according to Example 33, which typically provided 0.275 to 0.276 MPa under similar conditions.

Example 35

A mixture formulated to be extruded was prepared comprising: 1) 40.34% by weight of basic copper nitrate, 2) 37.86% by weight of hexaamine cobalt 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 procedure described in Examples 33 and 34. Expected, and thus obtained, results comparable to those of Example 34.

Gas generators are those described in US-A-5725699.

Summary

In summary, the present invention provides gas generating compositions that overcome some of the limitations of conventional azide based gas generating compositions. The complexes used in the present invention produce non-toxic gaseous products that include water vapor, oxygen, and nitrogen. Some of the complexes are also capable of effective decomposition to a metal or metal oxide, and nitrogen and water vapor. Finally, reaction temperatures and combustion rates are within acceptable ranges.

Claims (40)

1. A gas generating composition comprising: a nitrite amine complex or a nitrate amine complex of a cation of cobalt, magnesium, manganese, nickel, titanium, chromium, zinc, or tin, in which there is sufficient nitrite anion or nitrate anion to balance the cation charge, of such that when the nitrite amine complex or the nitrate amine complex goes into combustion, a mixture of gases containing nitrogen gas and water vapor is produced; Y at least one compound containing cold burning organic nitrogen.

2.

A gas generating composition as defined in claim 1, wherein the cation is cobalt.

3.

A gas generating composition as defined in claim 1, wherein the nitrite anion or nitrate anion is coordinated with the cation.

Four.

A gas generating composition as defined in claim 1, wherein the nitrite amine complex or the nitrate amine complex is carbon free.

5.

A gas generating composition as defined in claim 1, wherein the nitrite amine complex or the nitrate amine complex includes at least one other common ligand, in addition to the amine ligand.

6.

A gas generating composition as defined in claim 5, wherein at least one other common ligand is selected from the group consisting of aqueous (H2O), hydroxo (OH), and carbonate (CO3) ligands.

7.

A gas generating composition as defined in claim 1, wherein the nitrite amine complex or the nitrate amine complex has a concentration in the gas generating composition of from 30% by weight to 90% by weight, in that the gas generating composition further comprises a co-oxidant, and in which the sum of the amount of the co-oxidant and the at least one compound containing cold burning organic nitrogen in the gas generating composition is from 10% by weight up to 60% by weight.

8.

A gas generating composition as defined in claim 1, further comprising a co-oxidizer other than the at least one compound containing cold burning organic nitrogen.

9.

A gas generating composition as defined in claim 8, wherein the co-oxidant is selected from perchlorates, chlorates, peroxides, nitrites, and alkali, alkaline earth, lanthanide, or ammonium nitrates.

10.

A gas generating composition as defined in claim 8, wherein the co-oxidant is selected from metal oxides, metal hydroxides, metal peroxides, metal oxide hydrates, metal oxide hydroxides, hydrated oxides of metal, basic metal carbonates, basic metal nitrates, and mixtures thereof.

eleven.

A gas generating composition as defined in claim 8, wherein the co-oxidant is selected from oxides of copper, cobalt, manganese, tungsten, bismuth, molybdenum, and iron.

12.

A gas generating composition as defined in claim 8, wherein the co-oxidant is a metal oxide selected from CuO, Co2O3, Co3O4, CoFe2O4, Fe2O3, MoO3, Bi2MoO6, and Bi2O3.

13.

A gas generating composition as defined in claim 8, wherein 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.

14.

A gas generating composition as defined in claim 8, wherein the co-oxidant is a metal oxide hydrate or hydrated metal oxide selected from Fe2O3 · xH2O, SnO2 · xH2O, and MoO3 · H2O.

fifteen.

A gas generating composition as defined in claim 8, wherein the co-oxidant is a metal oxide hydroxide selected from CoO (OH) 2, FeO (OH) 2, MnO (OH) 2, and MnO (OH) 3.

16.

A gas generating composition as defined in claim 8, wherein the co-oxidant is a basic metal carbonate selected from CuCO3 · Cu (OH) 2 (malachite), 2CoCO3 · 3Co (OH) 2 · H2O, Co0.69 Fe0.34 (CO3) 0.2 (OH) 2, Na3 [Co (CO3) 3] · 3H2O, Zn2 (CO3) (OH) 2, Bi2Mg (CO3) 2 (OH) 4, Fe (CO3) 0.12 (OH) 2.76, Cu1.54Zn0.46 (CO3) (OH) 2, Co0.49Cu0.51 (CO3) 0.43 (OH) 1.1, Ti3Bi4 (CO3) 2 (OH) 2O9 (H2O) 2, and (BiO) 2CO3.

17.

A gas generating composition as defined in claim 8, wherein the co-oxidant is a basic metal nitrate selected from Cu2 (OH) 3NO3, Co2 (OH) 3NO3, CuCo (OH) 3NO3, Zn2 (OH ) 3NO3, Mn (OH) 2NO3, Fe4 (OH) 11NO3 · 2H2O, Mo (NO3) 2O2, BiONO3 · H2O, and Ce (OH) (NO3) 3 · 3H2O.

18.

A gas generating composition as defined in claim 1, further comprising a binder.

19.

A gas generating composition as defined in claim 18, wherein the binder is water soluble.

twenty.

A gas generating composition as defined in claim 19, wherein the binder is selected from naturally occurring gums, polyacrylic acids, and polyacrylamides.

twenty-one.

A gas generating composition as defined in claim 18, wherein the binder is not soluble in water.

22

A gas generating composition as defined in claim 21, wherein the binder is selected from nitrocellulose, vinyl acetate / vinyl alcohol polymeric resin (VAAR) and nylon.

2. 3.

A gas generating composition as defined in claim 1, wherein the nitrite amine complex or the nitrate amine complex is hexaamine cobalt (III) nitrate ([(NH3) 6Co] (NO3) 3) and the co -oxidant is copper (II) nitrate trihydroxy (Cu2 (OH) 3NO3).

24.

A gas generating composition as defined in claim 1, further comprising carbon powder present from 0.1% by weight to 6% by weight of the gas generating composition, wherein the composition shows compressive strength. improved compared to the carbon-free composition.

25.

A gas generating composition as defined in claim 1, further comprising carbon powder present from 0.3% by weight to 3% by weight of the gas generating composition.

26.

A gas generating composition as defined in claim 1, wherein at least one compound containing cold burning organic nitrogen has a heat of formation of less than about -400 cal / g.

27.

A gas generating composition as defined in claim 1, wherein at least one compound containing cold burning organic nitrogen has a heat of formation of less than about -600 cal / g.

28.

A gas generating composition as defined in claim 1, wherein at least one compound containing cold burning organic nitrogen is a guanidine salt or a guanidine derivative.

29.

A gas generating composition as defined in claim 1, wherein at least one compound containing cold burning organic nitrogen is a guanidine nitrate.

30

A gas generating composition as defined in claim 1, wherein the amount of at least one compound containing cold burning organic nitrogen in the gas generating composition is greater than about 0% by weight and up to about 40% in weigh.

31.

A gas generating composition as defined in claim 1, wherein the nitrite amine complex or the nitrate amine complex is the primary fuel and the at least one compound containing cold burning organic nitrogen is the secondary fuel.

32

A gas generating composition as defined in claim 22, wherein the co-oxidant is the primary oxidant and the at least one compound containing cold burning organic nitrogen is secondary oxidant.

33.

A gas generating composition as defined in claim 1, wherein the at least one compound containing cold burning organic nitrogen is a guanidine carbonate salt, aminoguanidine nitrate, diaminoguanidine nitrate, urea, glycine, a complex of glycine-ammonium nitrate, or ethylene diamine dinitrate.

3. 4.

A gas generating composition as defined in claim 1, wherein the amount of at least one compound containing cold burning organic nitrogen is between about 5% by weight and about 30% by weight.

35

A gas generating composition as defined in claim 1, wherein the amount of at least one compound containing cold burning organic nitrogen is between about 10% by weight and about 25% by weight.

36.

A gas generating composition as defined in claim 1, wherein the nitrite amine complex or the nitrate amine complex has a concentration in the gas generating composition of from 40% by weight to 75% by weight, in that the gas generating composition further comprises a co-oxidant, and in which the sum of the amount of the co-oxidant and at least one compound containing cold burning organic nitrogen in the gas generating composition is between 15% by weight and 50% by weight.

37.

A gas generating device comprising:

a gas generating composition comprising: a nitrite amine complex or a nitrate amine complex of a cation of cobalt, magnesium, manganese, nickel, titanium, chromium, zinc, or tin, such that, when the nitrite amine complex or the nitrate amine complex goes into combustion, a mixture of gases is produced that with 5 has nitrogen gas and water vapor; enough nitrite anion or nitrate anion to balance the charge of the cation; Y at least one organic compound containing cold burning organic nitrogen; Y an ignition element to initiate the combustion of the gas generating composition. 38. A gas generating device as defined in claim 37, wherein the ignition element 10 for starting combustion includes an ignition composition comprising a mixture of different ignition compositions. 39. A gas generating device as defined in claim 37, wherein the ignition element for initiating combustion includes an ignition composition comprising a mixture of Mg / Sr (NO3) 2 / nylon and B / KNO3 . A method of inflating an air bag comprising the combustion of a gas generating composition as defined in claim 1. 41. A car air bag system comprising: a folded inflatable air bag; a gas generating device connected to the air bag to inflate the air bag, containing the gene device A gas generator a gas generating composition as defined in claim 1; and an ignition element to ignite the gas generating composition.