WO1998039275A1

WO1998039275A1 - Gas generants comprising carbonato metal ammine complexes

Info

Publication number: WO1998039275A1
Application number: PCT/US1998/003885
Authority: WO
Inventors: Norman H. Lundstrom
Original assignee: Automotive Systems Laboratory, Inc.
Priority date: 1997-03-05
Filing date: 1998-02-27
Publication date: 1998-09-11

Abstract

High nitrogen gas generant compositions, useful in inflating passenger restraint gas inflator bags, comprise at least one carbonated metal coordination complex in combination with at least one oxygen rich oxidizer. The combination results in gas generants that are relatively more stable and less sensitive, and generate relatively more gas and less solids than known gas generant compositions. The use of an oxygen rich compound in conjunction with the carbonated complex ensures abundant gas generation, and yet inhibits the production of carbon monoxide.

Description

GAS GENERANTS COMPRISING CARBONATO METAL AMMINE COMPLEXES

BACKGROUND OF THE INVENTION

The present invention relates to nontoxic gas generating compositions which upon combustion, rapidly generate gases that are useful for inflating occupant safety restraints in motor vehicles and specifically, the invention relates to gas generants that produce combustion products having not only acceptable toxicity levels, but that also exhibit a relatively high gas volume to solid particulate ratio at acceptable flame temperatures.

The evolution from azide-based gas generants to nonazide gas generants is well-documented in the prior art. The advantages of nonazide gas generant compositions in comparison with azide gas generants have been extensively described in the patent literature, for example, U.S. Patents No. 4,370,181; 4,909,549; 4,948,439; 5,084,118; 5,139,588 and 5 , 035 , 757 , the discussions of which are hereby incorporated by reference.

In addition to a fuel constituent, pyrotechnic nonazide gas generants contain ingredients such as oxidizers to provide the required oxygen for rapid combustion and reduce the quantity of toxic gases generated, a catalyst to promote the conversion of toxic oxides of carbon and nitrogen to innocuous gases, and a slag forming constituent to cause the solid and liquid products formed during and immediately after combustion to agglomerate into filterable clinker-like particulates . Other optional additives, such as burning rate enhancers or ballistic modifiers and ignition aids, are used to control the ignitability and combustion properties of the gas generant.

One of the disadvantages of known nonazide gas generant compositions is the amount and physical nature of the solid residues formed during combustion. The solids produced as a result of combustion must be filtered and otherwise kept away from contact with the occupants of the vehicle. It is therefore highly desirable to develop compositions that produce a minimum of solid particulates while still providing adequate quantities of a nontoxic gas to inflate the safety device at a high rate.

While known nonazide gas generants provide operable amounts of gas with a minimum of solid combustion products, in many cases, the mass of gas generant required compared to the mass of gas produced is still cause for concern. The volume of the inflator necessarily reflects the gas generant required to produce the gas needed to deploy the airbag. A reduction in the volume of gas generant needed would result in a desirable reduction in inflator volume thereby enhancing design flexibility. Several compositions have been designed to reduce the volume of the gas generant charge and the inflator. For example, copending PCT Application No. PCT/US95/00029 discloses metal complexes used as gas generants. These complexes comprise a cationic metal template, an oxidizing anion to balance the charge of the complex, and a neutral ligand containing hydrogen and nitrogen. The complexes are desirable because they rapidly combust or decompose producing water and gases comprised only of hydrogen, oxygen, and/or nitrogen, and furthermore, occupy a relatively smaller volume when compared to known gas generant compositions. However, the neat metallic complexes are friction and impact sensitive, and therefore complicate safe handling, processing, and transportation requirements .

Description of the Related Art U.S. Patent No. 544,582 describes the use of metal ammine complexes and ammonium nitrate. Noncarbon-containing metal ammine complexes in combination with ammonium nitrate are used to increase the sensitivity and explosiveness of the ammonium nitrate when packed in high densities.

U.S. Patent No. 2,220,891 describes the use of metal ammine complexes in combination with ammonium nitrate. The noncarbonated metal ammine complexes increase the sensitiveness of the composition thereby providing high density compositions desirable in quarry blasting where it is important to secure the maximum blasting effect.

PCT Application No. US95/00029, WO 95/19944, describes the addition of noncarbon-containing metallic fuels and oxidizers to noncarbon-containing metal ammine complexes. Carbon containing species are not utilized because of the possibility of producing carbon monoxide. The application teaches away from the production of any gases containing anything other than nitrogen, oxygen, or hydrogen. The metal ammine complexes, utilized as gas generant compounds for occupant restraint airbags, are sensitive to friction and impact.

SUMMARY OF THE INVENTION

The aforementioned problems are solved by a gas generant for a vehicle passenger restraint system employing at least one carbonato metal ammine complex and at least one oxidizer compound. The carbonated metal complex comprises at least one neutral ammonia ligand and at least one carbon-containing ligand coordinated to a transitional metal cation, and, at least one nitrate, nitrite, or perchlorate oxidizing anion to balance the complex charge. Incorporating the carbon ligand within the metal ammine complex decreases the impact and friction sensitivity of the complex, and also increases the gas generating properties of the composition.

Combining the carbonated metallic complex with an oxidizer results in a high density gas generant, and relatively speaking, produces abundant amounts of water vapor and gas such as carbon dioxide, nitrogen, and oxygen when compared to known gas generants. Carbon monoxide formation is inhibited by adding the oxygen rich compound. If desired, one or more azide or nonazide fuels may be added to the composition to enhance the gas generating properties.

The gas generants of this invention, preferably nonazide, are prepared by wet, aqueous or nonaqueous, and/or wet/dry blending and compaction of the comminuted ingredients. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the present invention, the preferred gas generant compositions comprise, in particular, at least one carbonated metal ammine coordination complex (hereinafter also referred to as a complex, carbonato complex, coordination complex, ammine complex, etc.) having at least one neutral ammonia ligand and at least one carbon containing ligand, each coordinated to a transition metal cationic template, and a nitrate, nitrite, or perchlorate based anion to balance the charge of the complex. The complex is combined with at least one organic and/or inorganic oxidizer, and if desired, one or more additional fuels. When choosing a balancing anion, nitrate based anions are preferred, however, other oxygenated ions may also be used as described above. The carbonated metal complex generally functions as a fuel and comprises 20-80%, but more preferably 35-65% by weight of the total gas generant composition. Although anhydrous complexes are discussed herein, one skilled in the art will readily appreciate that hydrated complexes may be incorporated in the same manner. In accordance with the present invention, exemplary examples of carbonated metal ammine complexes include, but are not limited to, carbonatopentamminecobalt (III) nitrate, Co(NH₃)₅C0₃N0₃, and carbonatotetramminecobalt (III) nitrate, Co(NH₃)₄C0₃N0₃. Other examples include cobalt (III), rhodium (III) , and iridium (III) carbonatopentammine complexes comprising perchlorate or halide based anions. The carbonated ligands contribute to low impact and friction sensitivity, in contrast to the elevated sensitivity of neat metal ammine complexes not containing carbon.

An oxidizer compound is selected from a group comprising alkali and alkaline earth metal nitrates, nitrites, and perchlorates; organic and inorganic nonmetal nitrates and nitrites; transitional metal oxides, nitrates, nitrites, complex polynitrites, and complex polynitrates; and combinations thereof. These include, for example, phase stabilized ammonium nitrate, ammonium nitrate, ammonium perchlorate, sodium nitrate, potassium nitrate, strontium nitrate, and copper oxide. Certain transitional metal complex polynitrites and polynitrates are commercially available from Aldrich Chemical, Alfa Aesar, Strem Chemical, and ACROS . Others may be prepared as taught in copending PCT Application No. US95/00029, the entire teachings of which are herein incorporated by reference. The oxidizer generally comprises 20-80%, but more preferably 35-65% by weight of the total gas generant composition.

A fuel rich system, combined with an oxidizer in the above percentages, ensures that the carbonated complexes produce minimal solids and advantageous gases such as carbon dioxide, nitrogen, water, and oxygen. The production of undesirable gases such as carbon monoxide is inhibited by the oxidizer rich mixture which readily reacts with carbon monoxide to form carbon dioxide. In addition, the oxidizer functions as a diluent and therefore also contributes to decreased sensitivity of the complex. Furthermore, as described below, addition of a diluent increases the density of the complex thereby accommodating a low volume gas generator.

If desired, nonazide fuels are preferably incorporated, however, high nitrogen azide or metal azido complex fuels, such as sodium azide, potassium azide, lithium azide, and azido pentammine cobalt (III) nitrate, may also be utilized. Nonazide fuels are selected from a group comprising azoles, tetrazoles, triazoles, and triazines; nonmetal and metal derivatives of tetrazoles, triazoles, and triazines; cyclic nitramines, linear nitramines, and caged nitramines; derivatives of guanidine, hydrazine, hydroxylamine, and ammonia; and mixtures thereof.

Examples of guanidine derivative fuels, either separately or in combination, include, but are not limited to, guanidine nitrate, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate (wetted or unwetted) , guanidine perchlorate (wetted or unwetted) , triaminoguanidine perchlorate

(wetted or unwetted) , guanidine picrate, triaminoguanidine picrate, cyanoguanidine , nitroguanidine (wetted or unwetted) , and nitroaminoguanidine (wetted or unwetted) .

Other high nitrogen nonazides that may be employed as fuels in the gas generant compositions of this invention, either separately or in combination with the above described guanidine compounds, include 2, 4, 6-trihydrazino-s-triazine (cyanuric hydrazide) ; 2 , 4 , 6-triamino-s-triazine (melamine) ; other guanidine compounds such as the metal and nonmetal salts of nitroaminoguanidine, metal and nonmetal salts of nitroguanidine, metal and nonmetal derivatives or salts of cyanoguanidine ; nitroguanidine nitrate, and nitroguanidine perchlorate; azoles and tetrazoles such as urazole, aminourazole, lH-tetrazole, 5-aminotetrazole, 5-nitrotetrazole, 5-nitroaminotetrazole, 5, 5' -bitetrazole, diguanidinium-5, 5' - azotetrazolate, and diammonium 5, 5' -bitetrazole; triazoles such as nitrotriazole, nitroaminotriazole, 3-nitro-l, 2 , 4-triazole-5- one; triazines such as melamine nitrate; and metallic and nonmetallic salts of the foregoing azoles, tetrazoles, triazoles, and triazines including manganese 5 , 5 ' -bitetrazole . The high nitrogen fuel generally comprises 0-50% by weight of the total gas generant composition.

An auxiliary azide or nonazide fuel as described not only enhances the gas producing capabilities, but also functions as a diluent and in certain cases, increases the density of the gas generant compositions, as described below.

From a practical standpoint, the compositions of the present invention may also include some of the additives heretofore used with gas generant compositions such as slag formers, compounding aids, ignition aids, ballistic modifiers, coolants, and NOX and CO scavenging agents.

Ballistic modifiers influence the temperature and pressure sensitivity, and the rate at which the gas generant or propellant burns. The ballistic modifier (s) is selected from a group comprising alkali metal, alkaline earth metal, transitional metal, organometallic, and/or ammonium, guanidine, and triaminoguanidine salts of cyanoguanidine; alkali, alkaline earth, and transition metal oxides, sulfides, halides, chelates, metallocenes, ferrocenes, chromates, dichromates, trichromates, and chromites; and/or alkali metal, alkaline earth metal, guanidine, and triaminoguanidine borohydride derivatives; elemental sulfur; antimony trisulfide; and/or transition metal salts of acetylacetone; either separately or in combinations thereof. Ballistic modifiers are employed in concentrations from about 0 to 25% by weight of the total gas generant composition, and utilize metals selected from groups 1-14 (new IUPAC) of the periodic table.

The addition of a catalyst aids in reducing the formation of toxic carbon monoxide, nitrogen oxides, and other toxic species. A catalyst may be selected from a group comprising triazolates and/or tetrazolates; alkali, alkaline earth, and transition metal salts of tetrazoles, bitetrazoles, and triazoles; transition metal oxides; guanidine nitrate; nitroguanidine; amines; and mixtures thereof. A catalyst is employed in concentrations of 0 to 20% by weight of the total gas generant composition. Even though a very low concentration of solid combustion products are formed when the pyrotechnic gas generant compositions of the present invention are ignited, the formation of solid klinkers or slags is desirable in order to prevent unwanted solid decomposition products from passing through or plugging up the filter screens of the inflator. Suitable slag formers and coolants include lime, borosilicates, vycor glasses, bentonite clay, silica, alumina, silicates, aluminates, transition metal oxides, and mixtures thereof. A slag former is employed in concentrations of 0 to 10% by weight of the total gas generant composition.

An ignition aid controls the temperature of ignition, and is selected from the group comprising finely divided elemental sulfur, boron, carbon black, and/or magnesium, aluminum, titanium, zirconium, or hafnium metal powders, and/or transition metal hydrides, and/or transition metal sulfides, and the hydrazine salt of 3-nitro-l, 2 , 4-triazole-5-one, in combination or separately. An ignition aid is employed in concentrations of 0 to 20% by weight of the total gas generant composition.

Processing aids are utilized to facilitate the compounding of homogeneous mixtures. Suitable processing aids include alkali, alkaline earth, and transition metal stearates; aqueous and/or nonaqueous solvents; molybdenum disulfide; graphite; boron nitride; polyethylene glycols; polypropylene carbonates; polyacetals; polyvinyl acetate; fluoropolymer waxes commercially available under the trade name "Teflon" or "Viton", and silicone waxes. The processing aid is employed in concentrations of 0 to 15% by weight of the total gas generant composition.

The various components described hereinabove for use with the metal ammine complexes of the present invention have been used in other known nonazide gas generant compositions.

References involving nonazide gas generant compositions describing various additives useful in the present invention include U.S. Patents No. 5,035,757; 5,084,118; 5,139,588; 4,948,439; 4,909,549; and 4,370,181, the teachings of which are herein incorporated by reference . As taught in that art and as will be apparent to those skilled in the art, it is possible to combine the functions of two or more additives into a single composition. For example, an oxidizer containing an alkaline earth metal, such as strontium, may also function as a slag former, a ballistic modifier ignition aid, and a processing aid. Preparation of the carbonated coordination complexes of the present invention are described in the continuing series,

"Inorganic Synthesis", published by McGraw Hill. In Volume 4, page 171 (1953) , the synthesis of carbonatopentamminecobalt

(III) nitrate is described; in Volume 6, page 173 (1960) , the synthesis of carbonatotetramminecobalt (III) nitrate is described; and in Volume 17, page 152 (1977) , the synthesis of cobalt, rhodium, and iridium carbonato complexes as perchlorate or halide salts is taught. Each teaching in its entirety is herein incorporated by reference. Carbonatopentamminecobalt (III) nitrate is also commercially available and can be purchased from Aldrich, Inc.

The manner and order in which the components of the fuel composition of the present invention are combined and compounded is not critical so long as a uniform mixture is obtained and the compounding is carried out under conditions which do not create unduly hazardous conditions or cause decomposition of the components employed. For example, the materials may be wet blended, or dry blended and attrited in a ball mill or Red Devil type paint shaker and then pelletized by compression molding. The materials may also be ground separately or together in a fluid energy mill, sweco vibroenergy mill or bantam micropulverizer and then blended or further blended in a v-blender prior to compaction. Multimodal particle size distribution will provide an optimum fit to ensure that any interstitial voids are filled, thereby resulting in a high density gas generant composition. It should be noted that although the compositions of the present invention are less sensitive than compositions employing neat noncarbon-containing metal ammine complexes, carbonated complexes having a perchlorate anion may still be somewhat sensitive. As such, handling and compositional studies of perchlorate salts should be tailored to reflect the increased sensitivity.

Compositions having components more sensitive to friction, impact, and electrostatic discharge should be wet ground separately followed by drying. The resulting fine powder of each of the components may then be wet blended by tumbling with ceramic cylinders in a ball mill jar, for example, and then dried. Less sensitive components may be dry ground and dry blended at the same time.

When formulating a composition, the ratio of oxidizer to fuel, wherein the metal complex comprises the fuel, is adjusted such that the oxygen balance is between -10.0% and +10.0% 0₂ by weight of composition as described above. More preferably, the ratio of oxidizer to fuel is adjusted such that the composition oxygen balance is between -4.0% and 1.0% 0₂ by weight of composition. Most preferably, the ratio of oxidizer to fuel is adjusted such that the composition oxygen balance is between - 2.0% and 0.0% 0₂ by weight of composition. The oxygen balance is the weight percent of 0₂ in the composition which is needed or liberated to form the stoichiometrically balanced products. Therefore, a negative oxygen balance represents an oxygen deficient composition whereas a positive oxygen balance represents an oxygen rich composition. It can be appreciated that the relative amounts of oxidizer and fuel will depend on the nature of the selected complex.

The gas generant compositions of the present invention may incorporate fuels and oxidizers that further desensitize the carbonated metal ammine complexes due to a variety of physical and/or chemical parameters, such as chemical structure, hydration or water of crystallization, stoichiometry, particle size, packing, and coating.

For example, the use of a substantially insensitive fuel with a low sensitive carbonated metal ammine complex results in a high density, volumetrically efficient composition. The monomodal particle size of the carbonato complex contributes to the formation of interstitial voids that may be left vacant in a neat carbonated metal ammine complex. The vacancies contribute to sensitivity. By adding low sensitivity fuels, ground to the proper particle size, to the composition, the voids are filled with a negligible increase in volume. Filling the voids increases the density of the complex and results in more gas per gram of gas generant. As such, the gas generating properties are significantly enhanced without a substantial increase in gas generant volume, or in solids formation upon combustion. Furthermore, the less sensitive nature of the fuels decreases the sensitivity of the carbonato complexes once the interstitial voids are occupied. Optional coolants desensitize the carbonated complexes in the same manner.

In contrast, known metal ammine complex formulations as taught in WO 95/19944, utilize conventional inorganic metal fuels such as boron, magnesium, aluminum, silicon, titanium, and zirconium, and preclude the formation of gaseous carbon species upon combustion. Not only do certain of these fuels significantly increase the gas generant volume, they also result in more solids and less gas produced upon combustion. Practically speaking, greater volumetric efficiency facilitates increased design flexibility depending on the quantities of gas desired. Due to greater gas and minimal solids production, reduced filtration needs result in correspondingly smaller filters and inflators.

The compositions of the present invention are generally envisioned for use in conventional pyrotechnic gas inflators, for example, those referred to in U.S. Patent No, 4,369,079, incorporated herein by reference. Generally, the methods of the prior art involve the use of a hermetically sealed metallic cartridge containing fuel, oxidizer, slag former, initiator and other selected additives. However, the gas generants may also be tailored for use in hybrid inflators utilizing pressurized gases. Hybrid inflator technology is based on heating a stored inert gas such as argon or helium to a desired temperature by burning a small amount of propellant. Hybrid inflators that inherently operate at a lower temperature do not require cooling filters that must be used with pyrotechnic inflators to cool combustion gases.

The present invention is illustrated by the following theoretical examples wherein the components are quantified in weight percent of the total composition. Values of the products are obtained based on the given compositions and reactions .

Example 1: Carbonatopentamminecobalt (III) Nitrate and Ammonium Nitrate^* Co(NH₃)₅C0₃N0₃ + 5 NH₄N0₃ → CoO + 35/2 H₂0 + C0₂ + 8 N₂ +

1/4 0₂ A mixture of 39.94% Co (NH₃) ₅C0₃N0₃ and 60.06% NH₄N0₃ is prepared as follows. The components are separately ground to a fine powder by tumbling with ceramic cylinders in a ball mill jar. The powder is then separated from the grinding cylinders and granulated to improve the flow characteristics of the material. Next, the ground components are blended in a v- blender prior to compaction. If desired, the homogeneously blended granules may then be cautiously compression molded into pellets by methods known to those skilled in the art. The end products include 11.26% CoO (s) , 47.30% H₂0 (v) , 6.61% C0₂ (g) , 33.63% N₂ (g) , and 1.20% 0₂; the moles/100 gms of gas generant for each of these end products, respectively, is 0.150M, 2.628M, 0.150M, 1.201M, and 0.038M. The total weight percent of gaseous and vapor products is 88.74%. The total gaseous and vapor moles/lOOg of gas generant is 4.017M.

Any nitrate or nitrite, examples of which are phase stabilized ammonium nitrate, alkali metal nitrates, alkaline earth metal nitrates, transition metal nitrates, transitional metal complex polynitrites and polynitrates, inorganic nonmetallic nitrates, inorganic nonmetallic nitrites, organic nitrates, and combinations thereof, are applicable.

Example 2: Carbonatotetramminecobalt (III) Nitrate and

Ammonium Nitrate^*

Co(NH₃)₄C0₃N0₃ + 3 NH₄N0₃ → CoO + 12 H₂0 + C0₂ + 11/2 N₂

A mixture of 50.92% Co (NH₃) ₄C0₃N0₃ and 49.08% NH₄N0₃ is prepared as in Example 1. The end products include 15.34% CoO

(s) , 44.17% H₂0 (v) , 9.00% C0₂ (g) , and 31.49% N₂ (g) ; the moles/100 gms of gas generant for each of these end products, respectively, is 0.204M, 2.454M, 0.204M, andl.l25M. The total weight percent of gaseous and vapor products is 84.66%. The total gaseous and vapor moles/lOOg of gas generant is 3.783M.

Example 3: Carbonatopentamminecobalt (III) Nitrate, Ammonium Nitrate^*, and Strontium Nitrate^*

Co(NH₃)₅C0₃N0₃ + 2 NH₄N0₃ + 1/2 Sr(N0₃)₂ → CoO + 1/2 SrO +

A mixture of 50.00% Co (NH₃) ₅C0₃N0₃, 30.08% NH₄N0₃, and 19.92% Sr(N0₃)₂ is prepared as in Example 1. The end products include 14.10% CoO (s) , 9.77% SrO (s) , 38.91% H₂0 (v) , 8.27% C0₂ (g) , and 28.95% N₂ (g) ; the moles/lOO gms of gas generant for each of these end products, respectively, is 0.188M, 0.094M, 2.162M, 0.188M, and 1.034M. The total weight percent of gaseous and vapor products is 85.90%. The total gaseous and vapor moles/lOOg of gas generant is 3.384M.

Example 4: Carbonatotetramminecobalt (III) Nitrate and Strontium Nitrate^*

Co (NH₃) ₄C0₃N0₃ + Sr (N0₃) ₂ → CoO + SrO + 6 H₂0 + C0₂ +

7/2 N₂ + 0₂

A mixture of 54.01% Co (NH₃) ₄C0₃N0₃ and 45.99% Sr(N0₃)₂ is prepared as in Example 1. The end products include 16.27% CoO (s) , 22.56% SrO (s) , 23.43% H₂0 (v) , 9.54% C0₂ (g) , 21.26% N₂ (g) , and 6.94% 0₂; the moles/lOO gms of gas generant for each of these end products, respectively, is 0.217M, 0.217M, 1.302M, 0.217M, 0.759M, and 0.217M. The total weight percent of gaseous and vapor products is 61.17%. The total gaseous and vapor moles/lOOg of gas generant is 2.495M.

While the foregoing examples illustrate the use of preferred fuels and oxidizers it is to be understood that the practice of the present invention is not limited to the particular fuels and oxidizers illustrated and similarly does not exclude the inclusion of other additives as described above and as defined by the following claims, or those readily apparent to one skilled in the art .

Claims

I CLAIM :

1. A gas generant composition useful for inflating an automotive air bag passive restraint system comprising: at least one carbon-containing metal coordination complex comprising a transition metal, a neutral ammonia ligand and a carbon-containing ligand each coordinated to said transition metal, and an anionic component to balance the charge of the complex; and at least one oxidizer selected from the group consisting of organic and inorganic oxidizers, and combinations thereof.

2. The gas generant composition of Claim 1 wherein said carbon-containing metal ammine complex is employed in a concentration of 20 to 80% by weight of the gas generant composition and said oxidizer is employed in a concentration of 20 to 80% by weight of the gas generant composition.

3. The gas generant composition of Claim 1 wherein said oxidizer is selected from the group consisting of alkali and alkaline earth metal nitrates, nitrites, and perchlorates; transition metal oxides, nitrates, nitrites, and complex polynitrates and polynitrites;, organic and inorganic nonmetallic nitrates and nitrites; and combinations thereof.

4. The gas generant of Claim 3 wherein said oxidizer compound is selected from the group consisting of phase stabilized ammonium nitrate, ammonium nitrate, ammonium perchlorate, sodium nitrate, potassium nitrate, strontium nitrate, and copper oxide.

5. The gas generant composition of Claim 1 further comprising a fuel selected from the group consisting of nonazide and azide fuels.

6. The gas generant composition of Claim 5 wherein said fuel is employed in a concentration of .1-50% by weight of the gas generant composition.

7. The gas generant composition of Claim 5 wherein said azide fuel(s) is selected from the group consisting of azide and metal azido complex fuels comprising sodium azide, potassium azide, lithium azide, and azido pentammine cobalt (III) nitrate.

8. The gas generant composition of Claim 5 wherein said nonazide fuels are selected from a group consisting of azoles, tetrazoles, triazoles, and triazines; derivatives of azoles, urazoles, tetrazoles, triazoles, and triazines; cyclic nitramines, linear nitramines, and caged nitramines; and derivatives of guanidine, hydrazine, hydroxylamine, and ammonia.

9. The gas generant composition of Claim 8 wherein said guanidine derivative is selected from the group consisting of guanidine nitrate, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate (wetted or unwetted) , guanidine perchlorate (wetted or unwetted) , triaminoguanidine perchlorate (wetted or unwetted) , guanidine picrate, triaminoguanidine picrate, cyanoguanidine, nitroguanidine (wetted or unwetted) , nitroaminoguanidine (wetted or unwetted) , metal and nonmetal salts of nitroaminoguanidine, metal and nonmetal derivatives and salts of cyanoguanidine; metal and nonmetal salts of nitroguanidine, nitroguanidine nitrate, nitroguanidine perchlorate, and mixtures thereof.

10. The gas generant composition of Claim 8 wherein said azoles and tetrazoles are selected from a group consisting of urazole, aminourazole, tetrazole, lH-tetrazole, 5- aminotetrazole, 5-nitrotetrazole, 5-nitroaminotetrazole, 5,5'- bitetrazole, diguanidinium-5 , 5' -azotetrazolate, diammonium 5, 5' -bitetrazole, manganese 5 , 5' -bitetrazole, metal and nonmetal salts of said azoles and tetrazoles, and mixtures thereof .

11. The gas generant composition of Claim 8 wherein said triazoles and triazines are selected from the group consisting of 2, 4, 6-trihydrazino-s-triazine, 2, 4, 6-triamino-s-triazine, melamine nitrate, triazole, nitrotriazole, nitroaminotriazole, 3-nitro-l, 2, 4-triazole-5-one, metallic and nonmetallic salts of said triazoles and triazines and mixtures thereof.

12. The gas generant of claim 1 further comprising a ballistic modifier selected from the group comprising organometallic compounds selected from the group consisting of metallocenes and chelates of metals, metal oxides, metal halides, metal sulfides, metal chromium salts or elemental sulfur, the metal being selected from Groups 1-14 of the Periodic Table of Elements; alkali metal, alkaline earth metal, guanidine and triaminoguanidine borohydrides; cyanoguanidine; an alkali metal, alkaline earth metal, or transition metal guanidine or triaminoguanidine salt of cyanoguanidine; nitroguanidine; and mixtures thereof, employed in a concentration of 0.1 to 25% by weight of the total gas generant .

13. The gas generant of claim 1 further comprising an inert slag former and coolant selected from the group consisting of lime, borosilicates, vycor glasses, bentonite clay, silica, alumina, silicates, aluminates, transition metal oxides, and mixtures thereof, employed in a concentration of 0.1 to 10% by weight of the total gas generant composition.

14. The gas generant of claim 1 further comprising a catalyst selected from the group consisting of triazolates and/or tetrazolates; alkali metal, alkaline earth metal and transition metal salts of tetrazoles, bitetrazoles, and triazoles; transition metal oxides; guanidine nitrate; nitroguanidine; and mixtures thereof, employed in a concentration of 0.1 to 20% by weight of the total gas generant

15. The gas generant composition of claim 1 further comprising an ignition aid selected from the class consisting of finely divided elemental sulfur, boron, carbon black, magnesium, aluminum, titanium, zirconium and hafnium, transition metal hydrides, transition metal sulfides and mixtures thereof, employed in a concentration of 0.1 to 20% by weight of the gas generant.

16. The gas generant composition of claim 1 further comprising a processing aid selected from the group consisting of molybdenum disulfide; graphite; boron nitride; alkali, alkaline earth, and transition metal stearates; polyethylene glycols; polypropylene carbonates; lactose; polyacetals; polyvinyl acetates; polycarbonates; polyvinyls; alcohols; fluoropolymers ; paraffins; silicone waxes; and mixtures thereof, employed in a concentration of 0.1 to 15% by weight of the gas generant .

17. The gas generant composition of claim 1 wherein said carbonated metal coordination complex is selected from the group consisting of carbonatopentamminecobalt (III) nitrate and carbonatotetramminecobalt (III) nitrate.

18. The gas generant composition of claim 1 wherein said anionic component is selected from the group consisting of nitrate and perchlorate based anions .

19. The gas generant composition of claim 1 comprising a mixture of carbonatopentamminecobalt (III) nitrate and ammonium nitrate .

20. The gas generant composition of claim 1 comprising a mixture of carbonatotetramminecobalt (III) and ammonium nitrate .

21. The gas generant composition of claim 1 comprising a mixture of carbonatopentamminecobalt (III) nitrate, ammonium nitrate, and strontium nitrate.

22. The gas generant composition of claim 1 comprising a mixture of carbonatotetramminecobalt (III) nitrate and strontium nitrate.